Metal Organic Framework MOF

Coordination Chemistry Reviews 446 (2021) 214115
Contents lists available at ScienceDirect
Coordination Chemistry Reviews

journal homepage: www.elsevier.com/locate/ccr
Review
Metal organic frameworks as hybrid porous materials for energy storage

and conversion devices: A review
Sakshi Chuhadiya, Himanshu, D. Suthar, S.L. Patel, M.S. Dhaka ⇑
Department of Physics, Mohanlal Sukhadia University, Udaipur 313001, India
a r t i c l e i n f o a b s t r a c t
Article history: Recent technological advances and increasing energy demands have triggered the development and syn-
Received 13 February 2021 thesis of novel materials for efficient energy storage and conversion devices in order to cater the energy
Accepted 26 June 2021 need of the society. The metal organic frameworks (MOFs), are porous crystalline hybrid materials fash-
Available online 15 July 2021
ioned by linkage of the metal centers (clusters) and organic linkers (organic ligands), have been recog-
nized as very active research domain due to their broad range of applications as energy storage and
Keywords: conversion materials, regioselective chemical refinements, and petrochemicals for more than the past
Metal organic frameworks
decade or so. In the current research domain, the emerging MOFs have attracted research community
Synthesis routes
Solar cells
due to their unique properties including tunable porosities, high surface area, modifiable morphologies,
Fuel cells layer by layer design and high-quality crystalline product. The present review deals with the state-of-the-
White light emitting diodes art MOFs design, compositions and recent developments and breakthroughs with special reference to the
Lithium-ion batteries energy conversion and storage device applications such as solar cells, fuel cells, white light emitting
Sodium-ion batteries diodes, Lithium-ion batteries, Sodium-ion batteries, Zinc-air batteries, Aluminum-air batteries and super-
Zinc-air batteries capacitors. The review also highlights various synthesis routes, progress in synthesis of the ultra-high
Aluminum-air batteries porous MOFs along with the current challenges and future applications of the promising MOF materials.
Supercapacitors
Ó 2021 Elsevier B.V. All rights reserved.
Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2. Synthesis routes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.1. Solvothermal synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.2. Microwave-assisted synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.3. Electrochemical synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.4. Mechanochemical synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.5. Ultrasonic assisted synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
2.6. Crystal transformation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
3. Metal organic framework (MOF) thin films . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
3.1. Substrates for the fabrication of MOF thin films . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
3.2. Fabrication of MOF thin films. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
3.2.1. Surface-supported metal–organic frameworks (SURMOFs) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
3.2.2. Polycrystalline thin films . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
4. Applications of metal-organic framework nanomaterials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
4.1. MOFs applications in electrochemical energy conversion devices . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
4.1.1. Solar cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
4.1.2. Fuel cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
4.1.3. White light emitting diodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
4.2. MOFs applications in electrochemical energy storage devices. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
4.2.1. Lithium-ion batteries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
⇑ Corresponding author.
E-mail addresses: [email protected], [email protected] (M.S. Dhaka).
https://doi.org/10.1016/j.ccr.2021.214115
0010-8545/Ó 2021 Elsevier B.V. All rights reserved.
S. Chuhadiya, Himanshu, D. Suthar et al. Coordination Chemistry Reviews 446 (2021) 214115
4.2.2. Sodium-ion batteries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19

4.2.3. Zinc-air batteries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
4.2.4. Aluminum-air batteries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
4.2.5. Supercapacitors. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
5. Challenges and opportunities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
Declaration of Competing Interest . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
Acknowledgement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
1. Introduction followed by exposing the pores. It is also used to purify the air
before breathing. Both the zeolite and activated carbon have
The increasing standardization of mankind warns towards numerous applications in adsorption, catalysis, gas/vapor separa-
growing energy crisis since the energy demand would be double tion and gas storage, but most of the important applications of
of current supply by 2050. The existing fossil fuels like oil, coal, the zeolite and activated carbon comprise ion-exchange properties
petroleum products are at highly depleting state whereas their [3].
stocks are limited and these are environmental unfriendly. The Owing to the huge current requirement of the high-
modern era of cutting-edge technology needs alternative energy performance energy conversion and storage devices, the research
resources with environmental aspects where efficient energy con- and development of advanced and functional materials are extre-
version and storage devices play important role. The fictionaliza- mely required which come into existence with extraordinary prop-
tion of surfaces or interfaces of the materials is technologically erties of nanomaterials [9]. The MOFs fulfill all the conditions
significant and prominent task where the key issues comprise which are required for the development of high performance
modifying, escalating, upgrading, tailoring or augmenting the energy storage and conversion devices. Also, the MOFs act as a
material’s surface properties including physical properties such potential component in the nanodevices [10–12]. Recent research
as structural, optical, surface morphological, topographical, electri- progress in MOF-nanomaterials involves the synthesis of unique
cal analysis and chemical properties like reactivity, porosity etc. structure and scarifying templates by the coordination of metal
The performance or efficiency of the energy storage and conversion ions with the organic ligand (organic linker). The MOFs exhibit
devices depends on structural parameters, surface morphology, reticular design and to demonstrate influential capability of the
reactivity towards ions/molecules, ionic and electronic conductiv- MOFs as precursor materials with unique structure, two powerful
ity of the materials and therefore, it becomes very important to designs approach viz. supermolecular building block (SBB) and
modify the chemical and physical properties of materials in a very supermolecular building layer (SBL) are recently implemented for
flexible way [1–3]. The porous materials such as Zeolite, activated the preparation of various novel porous materials. Also, the
carbon, and metal organic frameworks (MOFs) are having the eye- researchers reported Hierarchically porous MOFs (HPMOFs) which
catching potentials because these materials have an extreme possess high thermal stability [13–17]. The development of MOFs
degree of flexibility due to the shelf grafted surface which builds has created a new belief in veterans and scientists owing to their
the possibility to load pores with functional molecules and desired flexibility and extended chemical functionalization vis-à-vis to
functionality [4]. The high interactive ability of ions, atoms and the zeolites.
molecules with uniform or non-uniform pores to the porous mate- The metal organic frameworks (MOFs), are the porous crys-
rials not only makes these materials scientifically and technologi- talline hybrid materials fashioned by the linkage of metal centers
cally important but interesting too. The porous materials are (cluster) and organic ligands (organic linkers), that’s why these
defined on the basis of their adsorption properties which are clas- MOFs are also known as porous coordination polymers [18–19].
sified in accordance to their pore size. The materials which are hav- Generally the MOFs are developed via the coordination bonds
ing pore size within the range of 2 nm and lesser are micro pores, which establish the connection between metal enclosed inorganic
within the range of 2–50 nm are meso pores and above the size of compound and organic ligand (moieties) and thus create the three
50 nm are recognized as macro pores. The pore size, shape and vol- dimensional interconnected network. The high dispersed and
ume to the porous materials could be tailored employing coordina- exposed metal sites of MOFs provide a new era of possibilities in
tion solid materials which lead to admirable properties and the design of both the chemical and geometrical shape of internal
premium applications [5–7]. The porous materials enticed che- surface of the nanoporous materials. The chemical constitution to
mists, physicists and material scientists due to peculiar properties the MOFs allows superficial module of the nanostructure. The
and commercial interest which allow mass transmit from the exte- design and engineering of developed MOF’s coordination network
rior solid particles to the interior of materials or vice versa. The depend upon the nature of metal center and properties of ligand
chemical reaction proceeds within a material’s cavity, possesses concerned viz. bond angle, length, bulkiness, chirality etc. as well
unique kinetics and properties in term of porosity and polarity [8]. as ligand/metal ratio, nature of solvent and temperature. The syn-
The most common inorganic and ubiquitous substance which thesized MOF materials have been demonstrated as potential can-
exhibits uniform porosity is zeolite. Zeolite exhibits broad range didates for development in innovative energy technologies such as
of crystalline structures with certain amount of diversity. This class white light emitting devices and near infrared light emitting
of materials mostly contains Aluminum, Silicon and chalcogens. devices. On the basic level, MOFs enhanced beauty of not only
Similarly, another important common organic porous substance the chemical but physical sciences too by epitomizing the chemical
is activated carbon which has characteristic features as non- structure and power of combining the organic and inorganic
uniform pores shape and size where the pore diameter varies Chemistry. The MOFs catch the attention of the researchers due
within a particular range. The activated carbon is technologically to their unique properties such as highly regularized pores, modu-
influential material with the surface area upto 2000 m2g1 and it lar structures (rigid and flexible), smaller density, large surface
possesses high adsorption rate of gases (molecules). The gas mask area, high degree of crystallinity, tunable textures, thermal stabil-
is an important application of the activated carbon, which has the ity, and tunable optoelectronic and magnetic properties [20–27].
capability to take into account the active particles on the surface A typical structure of formation of MOFs is shown in Fig. 1 whereas
2
Fig. 1. Typical structure representing formation of Metal Organic Frameworks (MOFs).
an overview of properties, synthesis routes and applications of structure [31]. Also, stepwise synthesis of MOFs with rational
MOFs is demonstrated in Fig. 2. design for wide variety of potential applications in the field of
The term MOF was popularized in 1995 after a work reported luminescence and heterogeneous catalysis were reported [32].
on Cu-based metal organic frameworks (MOFs) employing The stability of the MOF composites in humid atmosphere and
hydrothermal synthesis route and the advanced properties of that the synthesis of MOF composites at room temperature lead to
Cu-MOFs were comprised 3D structure obtained by the interlock- the progress of the next generation electric power source and
ing of 2D sheets [28–29]. The first MOF with stable framework energy storage devices [33]. High theoretical energy density and
and high porosity was recognized as MOF-5 which was synthesized specific capacity have made the Lithium-based batteries as promis-
by combining Zn2+ ions and 1,4 dicarboxybenzene (H2BDC) [30]. ing energy storage device [34].
Unfortunately, this discovered porous MOF-5 which boosted MOF The MOF based thin films are applied to the photovoltaic
domain was moisture sensitive, and a new challenge took place devices where the films are developed employing the chemical
to prepare MOF which possessed stability in humid atmosphere, route-based liquid-phase epitaxy method [35] and applied as con-
and therefore, work on stability of MOFs was endeavored in water stituent layers to hike the device performance. As far as consider-
and humid atmosphere where water adsorption and desorption ing the present scenario, there is a necessity to focus work on long
mechanism of more than 50 MOF composites were reported which term stable and cost-effective energy conversion and storage
maintained structural regularity with complexity of the MOF devices which could be carried out by incorporating the potential
Fig. 2. An overview of MOFs synthesis, properties, and applications.
3
and outstanding properties of bulk MOFs and MOF thin films. The fuel cells and white light emitting diodes (WLEDs) while the
MOF thin films enable well-structured growth of pores on different Lithium-ion batteries (LIBs), Sodium-ion batteries (NIBs), Zinc-air
substrates which yield uniform morphology, flexible flow of batteries (ZABs), Aluminum-air batteries (AABs) and Supercapaci-
charges or absorbed molecules and well-oriented frameworks tors are potential energy storage devices which have been covered
vis-à-vis to the bulk MOF frameworks. In order to eliminate the in the present review. As described above, herein, applications of
complexity of preparation of the MOFs and derivatives concerned MOFs in energy storage and energy conversion devices are exten-
at high temperature, four well known MOFs: MOF-5, MOF-74, sively discussed with special reference to the conversion or solar
MOF-177 and MOF-199 were prepared at room temperature [36]. cell devices where MOF based thin film layers could be employed
Nowadays, the world is driven by the nanotechnology and accord- as constituent layers like optical window, absorber, buffer, pho-
ingly as per need of the technology, MOF based nanorods, nan- toanode, additives and transport layers to the solar cell technology
otubes and nanowires were synthesized and implicated in concerned.
technology concerned [37]. The nanostructure MOF composites
have increased the photocatalytic activities in energy conversion 2. Synthesis routes
devices [38]. The first integrated Nitrogen-doped Carbon (NC) as
the core and graphite Carbon (GC) core shell structured ZIF- In order to implicate the MOFs in technology, synthesis of the
8@ZIF-67 possessed the specific capacitance of 270 F g1 and cur- functionalized nanoscale MOF-derived materials is highly desired.
rent density 2 A g1 [39]. The synthesis of these porous materials has drawn huge attention
As far available literature and in view of the specific properties, during the last two decades due to large variety of aesthetically
the MOF based materials are implemented extensively so far in the interesting structures and applications as discussed in the intro-
energy storage devices, catalysis [40], biomedical imaging and drug duction part. The synthesis involves building porous materials
delivery [41], magnetic resonance imaging [42], Hydrogen storage without breaking interior bonding of organic linkers which
[43], Chemical sensors [44] and separations of hydrocarbons [45]. depends on various parameters viz. pH, solvent, reaction time,
The limited stocks and fast depletion to the fossil fuels, increase pressure and temperature [46]. The synthesis also seeks organic–
in global warming and environmental pollution warrant the soci- inorganic materials which significantly make improvement in sta-
ety for clean and abundant energy sources and therefore, alterna- bility and porosity and the resultant structure of MOFs depends on
tive energy resources are required where solar energy is the best the geometry of ligands [47]. It has been observed that an isomor-
among the others which is clean energy resource too. The solar cell phous ligand increases the conduction of charge carriers in MOF
device is comprised of several layers and implication of the MOF derivatives [48]. As discussed earlier, a variety of synthesis routes
thin films could enhance the performance of the MOF based solar to the MOFs have been employed so far and an overview of differ-
cell devices. The suitable properties of the MOF thin films may help ent MOFs synthesis routes along with reaction temperature and
to develop the cost effective and efficient device which could be final MOF products is depicted in Fig. 3.
champion in view of the Shockley Queisser limit based upon the
principle of detailed balance which limits the power conversion 2.1. Solvothermal synthesis
efficiency of solar cell devices.
In this review, initially various synthesis routes of MOFs nano- Solvothermal synthesis takes place in sealed container at auto-
materials are described followed by incorporation of MOFs thin genous pressure and temperature above the boiling point of the
film section where substrates and fabrication techniques of SUR- solvent concerned [49]. In this synthesis route, organic ligands
MOF and polycrystalline thin films are discussed. Later part of this and metal salt precursors are dissolved in a solvent followed by
review is extensively devoted to the energy conversion and storage loading the mixed solution into a stainless steel-lined Teflon auto-
devices where the energy conversion devices comprise solar cells, clave and then heating the autoclave in an oven above the boiling
Fig. 3. An overview of MOFs synthesis methods, reaction temperatures, and final MOFs products.
4
point of the solvent typically having a temperature range of 100- MIL-100 structure were synthesized with engineered surfaces,
200° C. The autoclave is heated for duration of 48–96 h or more cores and imaging properties, where the results opened new per-
according to nature of precursor materials where heterogenous spectives to cure diseases with antiviral and anticancer drugs
reaction is occurred. A relatively high pressure is generated inside [58]. Similarly, Iron Carboxylate MOF composites were developed
the autoclave to increase the reaction rate which promotes the by microwave-assisted synthesis route which possessed MIL-101
nucleation and formation of the MOF crystals. The final crystalline structure and showed potential candidature in the field of anti-
product is obtained during a period of few to several days using cancer drug delivery [59].
centrifuge machine in different spells and the corresponding reac-
tion specific is called hydrothermal reaction. The solvothermal syn- 2.3. Electrochemical synthesis
thesis route of MOFs is attractive because it mitigates the solubility
issue of heavy organic ligands and initiates the rapid nucleation The high investment cost and requirement of high temperature
process for development of singular complexes. The most com- are the major drawbacks of solvothermal and microwave-assisted
monly used organic solvents are NN-diethylformamide, NN- synthesis routes. In order to overcome and mitigate these prob-
dimethylformamide, glycol, acetone, ethanol, methanol, acetoni- lems, synthesis of MOF nanomaterials at room temperature by
trile and water [30]. The advantage of the solvothermal method varying solvent is highly desired. The electrochemical synthesis
includes easy operation, simple equipment and high-quality crys- is one such method that does not need metal ions and gives ever-
talline product [50]. Employing the solvothermal method, Cobalt lasting production of MOF nano crystals using electrical energy
and Cadmium based MOFs were synthesized at 85 °C by taking within a period of 10–30 min. This method is fast, clean and envi-
5-aminoisophthalic acid as an organic ligand. These synthesized ronmentally friendly because water is only the byproduct which
Co-MOF and Cd-MOF are applied as an anode material in both obtained at the end of the reaction. The principle of electrochemi-
the LIBs and SIBs and the obtained results showed good improve- cal synthesis route depends on anodic dissolution which contains
ment in electrochemical properties [51]. organic ligands and electrolytes [49]. During the synthesis, the
metal ions instead of metal salt are inserted in anode, organic link-
2.2. Microwave-assisted synthesis ers are put at the cathode whereas conducting salt is introduced in
electrochemical cell. Through the electrochemical synthesis
As described above, the MOFs are typically synthesized using method, Cu-based MOF composites were synthesized, where a
the solvothermal synthesis route, but this route takes long reaction copper plate of thickness 5 mm is arranged as an anode in an elec-
time from several days to weeks with heavy thermal energy con- trolytic cell along with an organic linker,1,3,5-benzenetricarboxy
sumption and costly and bulky apparatus. Therefore, in order to late (BTC) and on applying a bias voltage of 12–19 V, an electric
overcome this problem, a capable route, microwave-assisted syn- field was induced across the electrodes. Under the effect of this
thesis was evolved. If look at the origin of the microwaves, these induced electric field, Cu released electrons to form Cu2+ cations,
were discovered by P.L. Spencer in 1946 which are electromagnetic and then these Cu2+ cations linked with the BTC in the solvent to
waves whose wavelength ranges between 1 m and 1 mm and cor- form greenish blue MOFs. This prospective could be undertaken
responding frequency ranges from 300 MHz to 300 GHz. The to apply MOF in gas processing for future industrial purpose [13].
domestic microwave ovens are typically manufactured at fre-
quency of 2.45 GHz [52]. The microwave-assisted synthesis is an 2.4. Mechanochemical synthesis
effective synthesis route which uses microwave radiation and
has been applied to synthesize the zeolite, microporous and meso- The solvothermal, microwave assisted and electrochemical syn-
porous materials [53]. Applying the microwave energy, organic thesis routes of MOFs are temperature and pressure dependent
reactions could be carried out using supramolecular Chemistry methods. In order to synthesize the MOFs at room temperature
within the period of 4 min to 4 h [54]. Due to the suitable monitor- without pressure dependency, a new synthesis route is developed
ing of temperature and pressure conditions, the synthesis of the which is known as Mechanochemical synthesis method. It is easy,
MOFs in the microwave oven is easy and favorable. In economical and environmentally friendly which is based upon the
microwave-assisted synthesis, an oscillating electric field acceler- performance of the chemical reaction by applying mechanical
ates the movement of dipole molecules present in the mixture forces like tensile, compressive and shear forces which cultivate
and the heated liquid phase improves the nucleation rate of the the initiation of mechanochemical synthesis. The mechanochemi-
MOF materials. The advantages of the microwave-assisted synthe- cal synthesis route has been efficiently employed for the fast syn-
sis method involve facile morphological control and good quality of thesis of the MOF materials. There are several reasons which
the product within a short period of time [30]. This method mainly attract the synthesis of MOFs via mechanochemistry methods
focuses on high crystallization, control on phase, formation of which includes (a) synthesis process at room temperature without
nanomaterials, and enhancement in product quality through the volatile organic solvent and (b) short reaction time i.e. total time
improvement in morphology and purity of the product [55]. The taken in synthesis is 30 min-2 h instead of long time with qualita-
microwave assisted synthesis route was employed to synthesize tive higher yield. The grinding mechanism categorizes the
Cr-MIL-100 organic–inorganic hybrid materials within a period of mechanochemical method as Neat grinding (NG), Liquid-assisted
few hours and the obtained physicochemical properties of Cr- grinding (LAG), and ion-and-liquid assisted grinding (ILAG) meth-
MIL-100 demonstrated that the material was found very similar ods where the neat grinding method avoids the use of solvent
to that of the MOFs synthesized by the conventional solvothermal [60]. The solvent-free MOFs synthesis method was employed by
method. These findings increased the application horizons of the using a ball mill where the monohydrate copper acetate and ison-
microwave-assisted synthesis route in the production of the por- icotinic acid were ground together. This method emersed with
ous crystalline hybrid nanomaterials [56]. The porous ZnO nanos- higher efficiency to synthesize MOF materials vis-à-vis to the other
tructures were synthesized using the microwave-assisted conventional methods [61]. In this order, azine-functionalized Zn
synthesis route and then converted these into porous ZnO–ZnSe (II) MOFs were synthesized to enhance the catalytic performance
nanocomposites employing the microwave-assisted dissolution in the Knoevenagel condensation reaction. The Zinc based azine-
recrystallization method [57]. The potential applications to the functionalized pores materials were developed employing
MOF derivatives also involve drug delivery using non-toxic porous mechanochemical synthesis method followed by undertaking the
nanocarriers and in order to demonstrate it, Fe-based MOFs having catalytic behavior of the synthesized MOFs in the Knoevenagel
5
condensation reaction. It was noticed that the basicity of azine Table 2

functionalized organic ligand improved the rate of reaction [62]. The main advantages and disadvantages of different MOFs synthesis routes.
The selective CO2 capture in MOFs with Azine-functionalized pores Method (s) Advantage (s) Disadvantage (s) Ref.
was generated by mechanochemical synthesis route [63]. Solvothermal Simple and easy to This method [64–
Synthesis operate includes long 65]
2.5. Ultrasonic assisted synthesis High crystalline reaction time
product is from several
obtained by vary- days to weeks.
The morphology and crystallite size are also important param- ing reaction Bulky apparatus
eters in the technological implications of the MOFs, and to acquire parameters such and high cost of
uniform morphology and crystallite size, the ultrasonic assisted as temperature, hydrothermal
synthesis method has been employed to prepare the MOF materi- solvent and reac- autoclave and
tion time. hot air oven.
als within a short time of 30–180 min with rapid nucleation. In this
During reaction
method, the ultrasonic radiation (20 kHz–10 MHz) causes a cavita- process, large
tion phenomenon in the mixture and consequently, tiny bubbles amount of sol-
are formed in the solution. These bubbles grow up to a certain vent waste
extent and then rupture to form transient hotspots in the presence occurs.
Microwave- Fast crystallization High investment [52,66]
of ultrahigh local pressure and temperature. This method leads to Assisted yields and high- cost.
extremely rapid cooling or heating during the reaction and under Synthesis quality product High technical
such extreme conditions, the formation of MOF materials takes within a short complexity.
place which has homogeneous crystalline structure [30]. This syn- duration. Reduces
Precise control on mechanical sta-
thesis route is considered as top-down approach for the develop-
the phase selectiv- bility of the
ment of metal organic coordination compounds. ity, particle size product.
distribution and
2.6. Crystal transformation morphology.
Electrochemical Fast and cleaner Quality of the [67–
Synthesis synthesis method. obtained pro- 68]
The crystal transformation is an innovative method to synthe- Instead of metal duct is inferior.
size MOF materials which involves either the substitution of metal salt, metal ions
or the exchange of ligands. By changing specific conditions like are used.
temperature, pressure etc., the metal nodes or ligands are replaced Environmentally
friendly because
with an old framework to form a new framework. The advantage of
water is obtained
this synthesis route embraces lower reaction potential barriers as a byproduct.
which promote the formation of high quality MOF materials [30]. Mechanochemical Solvent free syn- It is difficult to [60,69]
An overview of energy source, reaction time and temperature Synthesis thesis route. isolate single
for different synthesis routes is depicted in Table 1. The synthesis Temperature and crystals for
pressure indepen- characterization.
methodologies of the MOFs have some set of unique advantages dent method
and disadvantages which are outlined in Table 2. where only the
The scientific community always tries to develop cost effective, mechanochemical
stable and higher efficient technology in synchronization with force is desired.
Short reaction
environment ever since invention of photovoltaic effect in 1839,
time typically lies
transistor in 1948 and first Silicon based solar cell during 1954. within 30 min-2 h.
The optoelectronic devices comprise different constituent layers Ultrasonic Environmentally Ultrasonic [70–
viz. absorber, active, window, transport etc. which need optimiza- Assisted friendly and low waves break the 71]
tion of physical and chemical properties in order to develop highly Synthesis cost. crystallites
Homogeneous which make it
efficient devices. The introduction of MOF materials opened new particle size with difficult to study
horizons for the device development including solar cells, sensors, uniform the crystallinity
optoelectronic devices etc. So far available literature, the metal morphology. of materials.
organic frameworks have also been developed as thin films and Reduces reaction
time.
applied as constituent layers to develop optoelectronic and solar
Crystal Reduces reaction It is complicated [30]
cell devices. The next section comprises detailed deliberations on Transformation potential barriers. to substitute or
the MOF thin films and their applications in the technology con- exchange metal
cerned. To develop high performance solar cell devices, the scien- ion or an organic
tists always try to optimize the constituent layers in light of the ligand with new
frame.
available solar irradiance on the earth surface and accordingly,
Table 1 optical energy band gap for the absorber or active layer is kept in
Different MOFs synthesis routes with reaction time and operating temperature. the vicinity of the optimal one i.e. 1.4 eV with high absorbance
Synthesis route Energy source (s) Reaction time Temperature while for the optical window, buffer and transport layers it should
(s) duration be more than 2.0 eV with low absorbance and high transmittance.
Solvothermal Thermal energy 48–96 h 353–453 K
Microwave Microwave 4 min-4 h 303–373 K 3. Metal organic framework (MOF) thin films
assisted radiation
Ultrasonic Ultrasonic 30 min-3 h 273 – 313 K
assisted radiation The demand for advanced nanomaterials for the energy storage
Mechanochemical Mechanical 30 min-2 h 298 K and conversion devices is increasing day by day and to develop
energy efficient and stable devices, the MOF thin films have been paid
Electrochemical Electrical energy 10–30 min 273–303 K
attention potentially with maximum structural quality and mini-
6
mum defect density where MOF films are usually obtained by with a far-red emitted squaraine dye could be used as an antennae
depositing the bulk MOF powder on the different solid substrates for light harvesting, while the porphyrin-based MOF films for effi-
[72]. Nowadays, the emerging new technologies enable mankind cient energy transport and light-harvesting in solar energy storage
to control the thickness and dimension of the MOF thin films with and conversion devices [76]. The HKUST-1 membrane was pre-
good homogeneity and morphology. The development of thin films pared on an a alumina (porous metal) substrate using coordination
of MOFs has paramount importance for certain purposes e.g. Chemistry of H3BTC and Cu2+ followed by investigating the H2
growth of porous multilayer assemblies and composite mem- selectivity with respect to N2, CH4 and CO2 gases concerned. This
branes. MOFs based thin films have been studied so far to gain sus- work established a new way to synthesize MOF based membranes
tainability and clean energy in various applications such as energy [83]. The LBL method was used for the successful growth of
storage and conversion devices, water splitting, CO2 reduction, HKUST-1 and ZIF-8 MOF thin films on Silica foam, where two dif-
thermoelectric devices, field-effect transistors, chemical sensors, ferent homogenous MOF thin films on mesoporous Silicon foam
smart membranes, catalytic coatings and liquid separation. Similar substrate were taken into account by demonstrating that the LBL
to that of the typical thin films, the MOF thin film thickness also method has recognized as a unique potential route to prepare hier-
ranges from micrometer to several nanometers [73]. The thin films archical hybrid porous system for various applications [85]. An
exhibit different properties as compared to their bulk counterparts innovative strategy has been proposed to improve the performance
due to high surface to volume ratio. The properties of thin films of chemiresistor gas sensors by merging highly sensitive metal
vary with development techniques, parameters, substrate nature oxide with high catalytic activities of the MOF thin films. In this
and temperature, vacuum, concentration of the precursors etc. work, a metal oxide nanowire was used as core matter for the
Therefore, it is necessary to focus on the used substrates and tech- gas sensing chemical reaction that was based on oxidation which
niques to demonstrate the viability of the MOF thin films in the took place between adsorbed Oxygen species and its surface. The
technology specific. ejected electrons due to the oxidation move toward conduction
band of metal oxide which led to change in conductivity of metal
3.1. Substrates for the fabrication of MOF thin films oxide [86]. For better enantiomer separation, MOF functionalized
thin films were grown using the LBL liquid phase epitaxy methods
The underlying substrate plays an important role in the device [87]. Thus, nature of substrates considerably modifies the proper-
development for epitaxial growth of the constituent layers. The ties of MOF thin films and the selection of suitable substrate is cru-
thin film growth mechanism comprises nucleation, coalescence, cial in order to achieve higher performance of devices concerned.
channels, holes, and continuous deposition on the used substrate.
As far available literature, several methods have been employed 3.2. Fabrication of MOF thin films
to develop highly oriented MOF thin films with maximum struc-
tural quality and minimum defect density and device develop- The supramolecular Chemistry holds one of its prospects for the
ment. These methods include liquid-phase epitaxy (LPE), spin- fabrication of novel functional MOF thin films incorporating two
coating technique (SCT), atomic layer deposition (ALD), bottom- types of MOF thin films termed as surface supported MOF (SUR-
up molecular assembly (BMA), electrochemical fabrication (ECF) MOF) thin films and polycrystalline MOF thin films. The
and chemical vapor deposition (CVD) method [72]. The surface approaches to fabricate SURMOF thin films and polycrystalline
chemistry between the substrates and MOF nanoparticles plays a MOF thin films are entirely different and categorized as solution-
vital role to achieve good quality thin films with epitaxial growth based chemical routes and vacuum-based physical routes. The
and therefore, selectivity of the substrate is very important in order solution-based MOF thin films are prepared by immersing the sub-
to tailor the properties of the MOF thin films. Different substrates strate into a solution containing metal cluster and organic linkage.
have been employed so far to fabricate MOF thin films and devices The solution-based MOF thin film fabrication methods include
concerned including Gold [74], Lead [75], Silicon [76], Indium- Liquid-phase epitaxy (LPE), Liquid-liquid interface (LLI), Bottom-
doped tin oxide (ITO) or Fluorine-doped tin oxide (FTO) coated up modular assembly (BMA), Air-liquid interface (ALI), Substrate-
conducting glass substrates [77–78], polymer [79], stainless steel seeded heteroepitaxy (SSH), Electrochemical deposition (ECD)
[80], Chromium [81], alumina [82], porous metal [83], Iron [84], and Spin-coating method. The vacuum-based MOF thin films are
Silicon foam [85], metal oxide nanowire [86], capillary column deposited under high vacuum conditions where chemical vapor
[87], a-Al2O3 [88], silk [89], polystyrene fiber [90], Titanium diox- deposition (CVD) and Atomic layer deposition (ALD) are two sorts
ide [91], Silicon oxide [92] and polyethersulfone [93]. The sub- of vacuum-based techniques [72]. The growth techniques for the
strates for the deposition of MOF films are chosen based upon deposition of the MOF thin films are schematically shown in Fig. 4.
the intend application concerned. The deposition of MOF thin films The MOF thin films play vital role in energy storage and conver-
on different substrates is discussed in this section whereas poten- sion devices as these films possess diversity in topological struc-
tial applications are discussed in later section. tures along with flexible properties, providing abundant
For the growth and nucleation of the MOF thin films, a self- catalytically active sites and fast charge transfer for efficient elec-
assembled monolayer on Gold substrate using COOH/CF3- trocatalytic performance in energy storage devices. Therefore,
terminated pattern was done to synthesize thin films of MOF- these films and synthesis routes concerned are discussed in detail.
5@SAM which contained diethylformamide inside the pores of
the MOF-5. The XRD pattern of these fabricated thin films was 3.2.1. Surface-supported metal–organic frameworks (SURMOFs)
compared with bulk polycrystalline MOF-5 which showed evi- The surface-supported metal–organic frameworks (SURMOFs)
dence for the retained cubic structure of the MOF-5 crystallites thin films are ultrathin layers having an order of nanometer with
composing the thin films [74]. The Gold substrates were also low roughness and extraordinary smoothness. These thin films
employed to prepare self-assembled layers using COOH- are quasi-epitaxial grown on the solid substrate where the thick-
terminated pattern to synthesize MOF thin films [94]. The L2- ness of the thin films and crystallite size are controlled precisely.
MOF and DA-MOF thin films were developed using layer-by-layer The self-assembled monolayers (SAMs) are found eye-catching
(LBL) method where 3-aminopropyl-trimethoxysilane (3-APTMS) interfaces for the growth of SURMOFs. The ideal SURMOF thin films
was used to functionalize the surface of Silicon substrate. By infil- have large in-plane single crystal domains. The SURMOF thin films
trating the pores of DA-MOF with DMF and ethanol, highly porous are mainly useful for the development of multilayered architec-
MOF thin films were achieved. These porphyrinic MOF thin films tures owing to the higher crystallinity, smoothness, orientation
7
Fig. 4. Classification of MOF thin films on the basis of deposition methods.
and flexible growth process. These thin films are fabricated dipping, sliding boat and rotating crucible methods is depicted in
employing two methods viz. Liquid-Phase Epitaxy and Langmuir- Fig. 5 (a), (b), (c) and (d) respectively.
Blodgett method.
3.2.1.2. Langmuir Blodgett method. The Langmuir-Blodgett (LB)
technique is used to build up monolayer MOF thin films and highly
3.2.1.1. Liquid-Phase epitaxy (LPE). The Liquid-Phase epitaxial (LPE) organized multilayers of an amphiphile. This method enables pre-
deposition is undertaken from concentrated and diluted solutions cise control over the monolayer thickness, homogeneous deposi-
at high and low temperatures, respectively, and typically by using tion of the monolayer over large areas and to make multilayer
dilute solutions. The LPE method is a stepwise process wherein the structures with varying layer composition. The LB method is
layer-by-layer adsorption is taken place from liquid solution to the accomplished by successively dipping a solid substrate up and
surface concerned. The LPE method allows, firstly the deposition down through the monolayer while simultaneously keeping the
through lower growth rates for better thickness control, secondly surface pressure constant with a computer-controlled feedback
through lower growth temperature for better structural stoichiom- system. Consequently, large number of monolayers are deposited
etry and thirdly to reduce the possibility of unnecessary sponta- onto the solid substrate. In the LB method, the layers are generally
neously nucleated crystallites. Further the LPE growth route is stacked via weak interactions e.g. p stacking. In this way, multi-
sub-categorized as (a) Nelson method which is the most primary layer structures could be produced and these multilayer structures
LPE method, (b) dipping method which is used to prepare simple are commonly called Langmuir-Blodgett films [96].
structured MOF thin films, (c) Sliding-boat method which includes
several solution wells and graphite slider to deposit multiple epi- 3.2.2. Polycrystalline thin films
taxial layers as well as widely used for growth of the heterostruc- The polycrystalline thin film is an assembly of randomly ori-
tures, and (d) rotating-crucible method which uses a centrifuge to ented MOF particles on the substrate where the probability of ori-
grow multiple thin-layers on large diameter substrate with an entations of MOF nanoparticles in a particular direction is high
acceptable homogeneity [95]. The experimental setup of Nelson, with respect to the substrate [97]. In the polycrystalline MOF films,
Fig. 5. LPE growth techniques (a) Nelson method, (b) Dipping method, (c) sliding-boat method, and (d) rotating-crucible method.
8
the crystals could be well inter grown or scattered and thickness of give information about the phase and structure, surface topogra-
such films is influenced by the size of MOF particles. The polycrys- phy and morphology, respectively in order to evaluate structural
talline MOF thin films could be deposited employing a variety of parameters, grain growth, film thickness and roughness of the
methods including direct synthesis and seeded growth which are films. The study on the homogeneity and roughness of SURMOFS
described herein. thin films is conveniently undertaken by AFM or scanning force
microscopy (SFM) because sometimes prepared materials are insu-
3.2.2.1. Direct synthesis. In the direct synthesis method, a substrate lators and possess low densities those are not sensitive to electron
is used either directly or modified by functionalized group through beams and therefore, it is not easily done by SEM whereas, in poly-
self-assembled monolayers (SAM) with appropriate growth solu- crystalline MOF thin films, SEM easily provides morphology and
tion. During the growth, the crystals connected to the substrate film thickness. The potential applications of the MOFs depend on
concerned are formed in continuous and intergrown style. On the how easily a guest molecule accessible to pores, and therefore
basis of yield crystallization, ambient temperature, rate of diffusion porosity measurement is an important characterization tool for
and used solution, this technique is further classified into four cat- MOF materials. The porosity measurement could be done at low
egories as (a) in-situ crystallization method [98], (b) growth at temperature because at high-temperature, MOF thin films may
room temperature [36], (c) dip coating in mother solution method be cracked due to thermal expansion of either the substrate or
[99] and (d) slow diffusion of reactants methods [100]. The in-situ the developed thin films which affect the morphology of the
crystallization method was employed to fabricate Sr1-xEuxIm2 MOF MOF thin films concerned. The porosity is typically assessed by
thin films where Europium (Eu) and Strontium (Sr) are used as gas adsorption measurements. The X-ray photoelectron spec-
metal ions and anionic imidozolate as an organic linker and MOF troscopy (XPS) and Infrared spectroscopy (IRS) are used to get
thin films are deposited on the anodic aluminium oxide (AAO). This information on the oxidation and coordination state of the metal
study added a novel coating advance approach for the formation of ions in MOF materials or thin films concerned [97].
luminescent MOF thin films where the EuSr-MOF growth inside
AAO channels was verified by the SEM and EDX spectroscopies
[101]. In order to mitigate the difficulty of maintaining high tem-
4. Applications of metal-organic framework nanomaterials
perature and pressure, a new method was developed for the
growth of MOF thin film at the room temperature [36]. To possess
The modern era of cutting-edge technology consumes more
good CO2 sorption capability, the dip coating in mother solution
power and to cater this along with environmental aspects, recent
method was used to fabricate Cr-MOF thin films on alumina sub-
research has been focused on the development of MOFs for clean
strate in the presence of polyethylenimine which enhanced the
energy applications including Lithium-based (Lithium-ion/
selectivity of the MOF films for CO2 with respect to N2. The XRD,
Lithium-sulfur /Lithium-oxide) batteries, fuel cells, supercapaci-
SEM and IR spectroscopy confirmed the fabrication of thin films
tors, solar cells and Hydrogen production and storages. Pioneering
which were observed to be free from cracks and then the fabricated
the Chemistry of electrochemical energy storage devices and syn-
thin films run through CO2 sorption measurement which provided
thesis of new materials with advanced properties as well as
good sorption capability [82].
enhanced efficiency and performance are immense challenge.
The maximum output efficiency and performance of the energy
3.2.2.2. Seeded growth. The seeded growth method is a two-step
storage devices depend on higher charge/discharge rate, higher
method where seeds are prepared in first step followed by deposi-
theoretical capacity, greater electronic stability, properties of
tion of the prepared seeds as thin films on the substrate in the sec-
anode/cathode materials and therefore, researchers have devoted
ond step. In this method, MOF nano crystals [102], non-MOF
large amount of time with dedicated hard work on the develop-
particles [103] and co-ordination polymers are used as seeds
ment of the next-generation electrochemical energy storage
[104] whereas the MOF thin films are chosen as seed layers
devices along with breakthrough advances in the power conver-
[105]. This method becomes attractive for growth of MOF films
sion efficiency of the solar cell devices [107–110]. MOFs are con-
due to lower nucleation density of various MOF materials on por-
sidered as appreciable materials for pervasive technical
ous substrates.
applications due to synergistic effect between the metal clusters
As so far available literature, the fabrication of MOF thin films is
and multifunctional organic ligands which could lead to induce
mostly undertaken employing the direct growth method and step-
diverse properties of MOFs as required for various devices. Besides
wise LBL growth routes. The direct growth method involves the
the energy storage and conversion applications, the MOFs are also
fabrication of MOF thin films of more or less densely packed struc-
having potential candidature in drug delivery, proton conduction
ture from solvothermal mother solution, whereas the stepwise LBL
and sensing applications. This section summarizes diverse applica-
growth method involves growth of MOF nanoparticles onto a sub-
tions of the MOF materials in the technological development to
strate. The obtained MOF thin films from these methods are homo-
cater current energy needs of the modern world. The potential
geneous and well ordered, while these methods take long time to
applications of MOFs are graphically represented in Fig. 6.
prepare MOF thin films. To undertake gas separation, Cu-based
microporous MOF membranes were prepared on alumina sub-
strates by using the seeded growth method and findings revealed
to the ideal moderate selectivity for Hydrogen and Nitrogen gases 4.1. MOFs applications in electrochemical energy conversion devices
[106].
The SURMOF thin films have a low order of thickness, and The electrochemical processes are regarded as clean approach
therefore many issues are arisen when undertaking the character- since these have lower influence on the environment. In sustain-
izations of these thin films like surface morphology, porosity mea- able energy conversion processes, the electrochemical conversion
surements and crystalline structure. The characterization of has huge contribution in current scenario of modern technology.
polycrystalline thin films is relatively easy due to greater film The MOF materials and derivatives concerned have been showed
thickness vis-à-vis to the SURMOF thin films. The microstructural potential applications in various electrochemical energy conver-
properties are undertaken by employing XRD (X-ray diffraction), sion devices owing to their outstanding properties where the pre-
atomic force microscopy (AFM) and scanning electron microscopy sent review focuses on the solar cells, fuel cells and white light
(SEM) along with transmission electron microscopy (TEM) which emitting diodes.
9
Fig. 6. A graphical view of potential applications of MOF materials and their derivatives.
4.1.1. Solar cells and theoretical approaches. As per need for the solar cells, the
Solar energy is one of the ultimate potential energy resources to semiconducting nature and properties of MOFs materials and
replace conventional non-renewable energy resources like fossil derivatives could be tuned by controlling the size of inorganic
fuels and coals. A solar cell is typically a p-n junction, based upon metal clusters, substituting the organic linkers and adjusting the
the photovoltaic effect where both the electrons and holes are the coordination modes in order to achieve the high efficiency and sta-
charge carriers and contribute to the photocurrent [111]. The first bility of solar cell devices concerned. The greater light harvesting
crystalline Silicon based solar cell device was demonstrated in the property and huge surface area of MOFs make them attractive
year 1954 and now the Si-based technology achieved the power recipes for absorber layer or photoanode applications for the tech-
conversion efficiency of more than 26% and the technology has nology concerned. The solar cells are usually suffered from defects
dominated the market ever since its invention in view of panel effi- and imperfections which lead to reduce the performance of
ciency and stability. Later, after the first generation, the second and devices. The MOFs could be used as surface modifier or additive
third generations to the solar cells are focused on the materials for efficient passivation of such defects in perovskite solar cells
reduction along with the cost effectiveness including organic and and thereby enhancing the performance of devices. The MOF thin
perovskite solar cells. In this order, the dye-sensitized solar cells films could be used as electron transport layer (ETL), hole transport
(DSSCs) are developed, which consist of a dye molecule loaded layer (HTL), photoanode and as a counter electrode (CE) in solar
photoanode, an electrolyte-containing redox couple, and a cat- cell devices [112–114]. The utilization of MOF thin films in device
alytic material-loaded counter electrode (CE). The MOF materials architectures of perovskite and dye sensitized solar cells is demon-
enhance the performance and stability of different photovoltaic strated in Fig. 7 where these layers could be applied for light
devices including organic–inorganic hybrid perovskite solar cells absorption or photo anode purposes according to the technology
(PSCs) and organic solar cells (OSCs). The performance parameters concerned.
of a solar cell device embrace the open-circuit voltage (VOC), short In the year 2007, it was demonstrated experimentally that the
circuit current density (JSC), fill factor (ff) and power conversion semiconducting nature of MOF-5 offered the novel opportunities
efficiency (PCE) those could be improved using MOF materials in solar cell device development [115]. The optical energy band
where the Physics and Chemistry of solar cells concerned are avail- gap of MOF-5 was measured using diffuse reflectance optical spec-
able extensively in the literature. A typical solar cell device is hav- tra which was found to be 3.4 eV and revealed that MOF-5 is a wide
ing an absorber layer with an optical window which develops an band gap semiconducting material [116]. The MOF thin films were
asymmetric junction to drive the photo generated charge carriers applied in dye-sensitized solar cells (DSSCs) as an interfacial mod-
towards the electrodes concerned and further on introduction of ifier and it was observed that the highly porous nature of MOFs
advance techniques and synthesis routes, the device architectures enhanced the dye storing capacity owing to its electrical insulating
have been modified by employing the buffer and transport layers. property where the interfacial MOF layer suppressed the interfacial
As stated previously, each constituent layer needs optimization for charge recombination. Herein, a thin layer of thickness 2 nm of ZIF-
the physical and chemical properties in order to develop highly 8 was grown on the TiO2 and the obtained open circuit voltage
efficient, stable and cost-effective solar cell device. The MOFs are (Voc) was observed to be increased which ascribed to the inhibited
found promising solar cell materials owing to their appropriate interfacial charge recombination due to ZIF-8 shell material. An
semiconducting nature which is verified by various experimental increment in Voc was measured under dark condition by employing
10
Fig. 7. The role of MOF thin films in perovskite and dye-sensitized solar cells.
the electrochemical impedance spectroscopy and I-V characteris-

tics [113]. To apply MOF thin films as light absorber or sensitizer
in TiO2 based solar cells, Cu-MOF thin layers of copper (II)
benzene-1,3,5-tricarboxylate were developed using the LBL tech-
nique on FTO coated glass substrate with a very thin layer of
TiO2. The TiO2 based solar cell devices were developed with and
without iodine-doped Cu-MOFs as an active layer. In this work,
the bulk MOF powder was prepared by using a solvothermal
method where the XRD and FTIR analysis strongly pointed out that
the powder and the LBL thin films are essentially comprised of the
same elements and EDX analysis confirmed the existence of Cop-
per, Oxygen, and Carbon elements in both the bulk MOFs and thin
films concerned. The UV–Visible absorption measurements
showed that an increase in the number of LBL cycles has increased
the intensity of absorption peak not only before but after Iodine
doping too. The electrical conductivity of Cu-MOFs was switched
from insulator to electrical conducting regime by Iodine doping Fig. 8. The energy band diagram for the TiO2/Cu-MOF system showing suitable
where a rise in electrical conductivity was observed due to interac- energy cascade for the unidirectional flow of the charge carriers, herein FTO is used
as transparent conducting oxide substrate. Reprinted with permission from Ref.
tion between the host MOFs and Iodine molecules. The HOMO and
[117]. Copyright (2014) American Chemical Society.
LUMO energy levels were estimated to be 5.37 eV and 3.82 eV,
respectively. The Iodine doped Cu-MOF was used as the sensitizer
and a good energy cascade was formed between the TiO2 and MOF
heterojunction. On illumination, the MOF absorbed light caused gradually increased with an increase in LBL cycles from 0 to 15
excitation of electrons from HOMO to LUMO energy levels revealed which improved the performance of the solar cells while the best
to the transition of electrons to the conduction band of TiO2. The performance of device was observed after 13 LBL cycles. The SEM
electrons were finally moved towards and collected by the FTO image of the 13 LBL cycle was shown in Fig. 9 along with the cur-
electrode, whereas the vacancies of electrons in HOMO level were rent–voltage (J-V) characteristics of device concerned [117].
filled by the electrons from the redox mediator present in the elec- Afterwards a hierarchical ZnO-based photovoltaic device was
trolyte. It was demonstrated that before Iodine doping, the cell designed with the configuration FTO/ZnO/ZnO scattering layer/
exhibited a power conversion efficiency of 0.008% only while the ZIF-8 where hierarchical ZnO was used as the light scattering layer
Iodine doping under similar conditions enhanced it to 0.26% which and the achieved performance parameters for the device con-
exhibited a great hike. The electrochemical impedance spec- cerned comprised Jsc = 8.13 mAcm2, Voc = 663 mV, 0.68 FF and
troscopy suggested that the Iodine doping significantly reduced 3.67% PCE. The XRD and SEM analysis showed that ZnO aggregated
the charge-transfer resistance which introduced Cu-MOFs as a sen- and hierarchical ZnO parallelepipeds were formed due to decom-
sitizer. Fig. 8 represents energy band diagram of the TiO2/Cu-MOF- position of MOF-5, respectively [118]. In order to investigate the
based device which presented suitable energy cascade for the uni- feasibility of Ru-based MOFs as a sensitizer in a TiO2 based liquid
directional flow of the charge carriers. The flow of charge carriers junction for thin-film solar cells, the Ru-MOF thin films were
11
Fig. 9. (a) Top SEM view of the 13 LBL Cu-MOF films, inset embraces the cross-sectional view, and (b) Current-voltage (J-V) characteristics of the developed solar cell devices
at various LBL cycles: A: 0, B: 4, C: 6, D: 8, E: 10, F: 11, G: 12, H: 13, I: 14, J: 15 LBL cycles where Fig. 8 gives self explanatory device architecture. Reprinted with permission
from Ref.[117]. Copyright (2014) American Chemical Society.
developed using the LBL technique followed by the Iodine doping the conduction band of TiO2, which was advantageous to apply
and then device development. The findings suggested that the these MOFs as sensitizer [119].
Iodine doping significantly reduced the charge-transfer resistance In order to enhance light harvesting properties and to maximize
and facilitated the charge transfer process from MOFs to TiO2. electrolyte compatibility of the MOF based DSSCs, the porphyrin
The XRD patterns of MOF powder and thin films are demonstrated dye was tailored with Cobalt. The molecular engineering in por-
in Fig. 10 where the findings assured that both the bulk MOF pow- phyrin dye resulted into 0.91 V open circuit voltage, 18.1 mA cm2
der and thin films concerned embraced constituent elements. The short circuit current density, 0.78 fill factor and 13% PCE [120]. To
SEM analysis showed that the films were consisting of densely develop the MOFs based Platinum-free counter electrode (CE) for
agglomerated MOF nanoparticles. The UV–Visible absorption spec- efficient DSSCs, the Cobalt sulfide (CoS) nanoparticles-based CE
tra showed absorption peak at 535 nm owing to the d-d transition were synthesized via surfactant-assisted preparation of the MOFs
in Ruthenium metal ion of the framework. The TiO2 films loaded by and ZIF67 followed by subsequent oxidation and sulfide conver-
MOFs exhibited broad humps at around 530 nm to 540 nm and sion. It is shown that CoS materials have great potential to replace
these absorption humps could be due to d-d transition of Ruthe- the Platinum (Pt) CE in DSSCs, and the CoS-based DSSCs were
nium ions in the framework. On the basis of HOMO-LUMO energy achieved power conversion efficiency close to that of the Pt-
gap, the LUMO level of the MOFs was predicted higher than that of based DSSCs. The SEM images, elemental mapping, electrochemical
and XRD findings demonstrated the higher external surface and
roughness for synthesized CoS nanoparticles vis-à-vis to the con-
ventional Pt counter electrode. The obtained results indicated an
increment in open circuit voltage (Voc) and decrement in the short
circuit photocurrent density (Jsc). Herein, cetyl trimethylammo-
nium bromide (CTAB) was used in an effective way to control the
particle size of ZIF67 and as the particle size decreased, the power
conversion efficiency was increased. The larger value of fill factor
and improvement in power conversion efficiency of 8.1% vis-à-vis
to the efficiency of 8.0% of Pt based DSSCs directly showed that
CoS nanoparticles have potential to replace the expensive Pt CE
material [121]. The metal–organic gel (MOG) electrolyte was pre-
pared by assembling Aluminum ion and 1,3,5-
benzenetricarboxylate (H3BTC) followed by applying MOG elec-
trolyte in quasi-solid state DSSCs along with the optimization of
the MOG electrolyte where the DSSCs concerned achieved PCE of
8.60% [122]. To perform Iodine doping, the Co-based MOF thin
films were developed by cobalt (II) 2,6- naphthalene dicarboxylic
acid (Co3(NDC)3) onto a non-conducting amine-functionalized
glass substrate employing the LBL and doctor-blade (DB) tech-
niques. It was demonstrated that the electrical conductivity of
Fig. 10. The X-ray diffraction patterns of (a) bulk Ru-MOFs powder for reference, the films was significantly improved by Iodine doping. The
(b) doctor blade TiO2 films on FTO coated glass substrate, (c) LBL synthesized Ru- undoped films have shown insulating behavior, while the doped
MOF films on glass, and (d) doctor blade TiO2 films on FTO coated glass substrate films exhibited p-type conductivity caused by charge transfer-
after LBL Ru-MOF films deposition. Patterns demonstrate that prominent peaks of
induced hole doping into the framework. The SEM images demon-
developed layers are coincided well with the powder data concerned. Reprinted
with permission from Ref. [119]. Copyright (2014) Royal Society of Chemistry. strated rod like morphology and the EDX spectra confirmed pres-
12
ence of all the elements in the composite. An absorption peak was MIL 125 was used as the precursor and 7.20% PCE was achieved
obtained in the UV–Visible absorbance spectra owing to the d-d [126]. The RuDCBPY[Ru(II)L2L’(L = 2,20 -biphyridyl, L’=2,20 -biphyri
transition. Initially, without Iodine doping, MOFs showed insulat- dine-5,50 -dicarboxylic acid)]-ZrMOF based thin films were pre-
ing behavior but as the Iodine doping was done, the MOFs allowed pared onto TiO2 coated FTO as a sensitizing material and the
the passage of current under external bias. The Hall measurements obtained rate to the energy migration indicated that RuDCBPY cen-
revealed to insulating behavior of undoped and conductive behav- tres located at MOF-TiO2 interface were sensitized either directly
ior of the Iodine doped MOFs which led to the enhanced device upon absorption of the incident irradiation or indirectly via reso-
performance [123]. nance energy transfer process initiated up to 15 nm away from
To apply Titanium-based MOF in DSSCs, the MIL-125 (Ti) MOFs the interface. Fig. 11 represents conventional DSSCs and Ru-MOF
were prepared using solvothermal method followed by converting sensitized solar cells (MOFSCs) [127].
the synthesized MIL-125 (Ti) into mesoporous hierarchical TiO2 To apply MOF as counter electrode, the ZIF-8 MOF based porous
(hier TiO2). The conversion of MIL-125 (Ti) into mesoporous hier carbonaceous material was applied without any template as coun-
TiO2 was done by delibrated calcination and XRD pattern showed ter electrode to DSSCs. The ordered crystalline structure, easy fab-
crystalline phase of the hier TiO2. On applying this hier-TiO2 on rication and high specific surface area provided superficial and
nc-TiO2 as the scattering layer, the fabricated DSSCs achieved efficient way for the carbonaceous material to make it as a suitable
PCE of 7.1% [124]. To implicate the MOF thin films as absorber layer material for CE to the DSSCs. The developed ZIF-8 MOF based
to the solar cells, the Co-MOF thin films were synthesized using the device achieved the PCE of 7.32%. The XRD patterns confirmed
LBL technique where the as-prepared MOF films showed insulating the successful preparation of porous carbonaceous material from
behavior which changed to p-type conduction after hole doping. ZIF-8 MOF. The surface morphology of porous carbonaceous mate-
The developed layers were successfully applied as light harvesting rial was observed using SEM and TEM analyses which showed
absorber films to the TiO2-based solar cells and demonstrated spherical and faceted particles in a narrow size distribution. The
power conversion efficiency of 1.12%. Both the cobalt (II) benzendi- Brunauer-Emmett Teller (BET) analysis showed that initially the
carboxylate (Co-BDC) and cobalt (II) 2,6-naphthalenedicarboxylic surface area was increased and then decreased which was due to
acid (Co-NDC) were employed as reference materials to character- conglomeration of the particles. These findings were comparable
ize the MOF thin films. To undertake the SEM analysis, the films with the Platinum CE and provided facile and efficient way for
were deposited on amine functionalized glass substrates, these the preparation of the CE using carbonaceous ZIF-8 MOF based
Co-NDC films were visible like nanorod assembly and structure like materials for the DSSCs [128].
fused plate. The XRD patterns confirmed that films were composed The Chemistry of the organic and inorganic compounds could
of Co-NDC and Co-BDC frameworks. The bulk MOF XRD patterns be tailored to design MOF sensitizer-based devices with configura-
were applied as finger-print characterization which revealed that tion FTO/TiO2-bl/TiO2-mp/Co-MOF/Au as shown in Fig. 12 where
the films were comprised of typical mesoporous crystalline 3D the MOF films were grown by LBL technique. As per architecture,
solids. Electrochemical impedance spectroscopy and photolumi- the electrons were collected at the FTO electrode and holes at
nescence quenching results demonstrated that hole doping facili- the Au-electrode, the efficient collection of holes at the Au-
tated the charge transfer across the TiO2/MOF interface [125]. To electrode enhanced the performance of the device. The SEM and
enhance the power conversion efficiency, hierarchical porous ana- TEM images revealed to the single crystalline nature of MOF thin
tase TiO2 photoanodes were developed for the DSSCs where the films. The XRD measurements confirmed the crystallinity of the
Fig. 11. Illustration of conventional DSSC (top) and Ru-MOF sensitized (bottom) solar cell devices. Reprinted with permission from Ref.[127]. Copyright (2016) Royal Society
of Chemistry.
13
challenges for the same to demonstrate its existence for industrial

production and long-term operation. Although the dye sensitized
solar cells are the origin for the same, yet it has shown remarkable
PCE of about 26% to the date.
The perovskite solar cells (PSCs) are developed using thiol func-
tionalized 2D MOFs where the thiol functionalized 2D MOFs was
implicated as an electron extraction layer. Along with the improve-
ment in operational stability, the devices showed PCE of 22.02%
[133]. In order to minimize the Pb-absorption problem and to
enhance PCE of PSCs, the MOFs polymer composite of Iron (III) ben-
zene tricarboxylic acid/ poly (dopamine) was employed as seques-
ter [134]. In order to apply the MOFs as electron transport layer
(ETL), Cobalt doped Ti-MOFs were synthesized using trimesic acid
as an organic linker. The synthesized material possessed surface
area of 135.95 m2g1. The UV–Vis. spectroscopy measurements
demonstrated that the Co doping improved the absorption ability
Fig. 12. Schematic representation of Co-MOFs based solar cell device where Co- of Ti-MOF. The PCE of the developed PSCs using 1 wt% Co-doped
MOFs act as absorber, TiO2 as an optical window, and FTO and Au as front and rear TiO2 as an ETL was found to be 15.75% [135]. The Carbon dots/
electrodes. Reprinted with permission from Ref. [129]. Copyright (2017) American ZnO based photoanode were employed to enhance the power con-
Chemical Society.
version efficiency of the DSSCs, where the Carbon dots/ZnO were
fabricated by Carbon dots incorporated ZnO using hydrothermal
method. The achieved PCE for these DSSC devices was 7.85%
MOF thin films, and these patterns for both the MOFs bulk and [136]. The heterojunction solar cell device was developed with
MOF thin films were well matched with a dominant peak at device architecture Au/NH2-MIL-125/p-Si/Al employing spray
10.86°. The p-type conductivity with hole concentration and pyrolysis technique. The obtained solar cell parameters viz. short
mobility of 3.35 108 cm–3 and 0.017 cm2v-1s1 were evaluated, circuit current density and PCE were 4.96 mAcm2 and 3.51%,
respectively employing the Hall measurements. In addition, the respectively [137]. The Cu-Ni bimetallic framework (CuO@NiO
electrical resistivity of 28.62 X cm suggested its potential applica- nanosphares MOFs) was developed to implicate as a hole transport
tions as hole transport sensitizer. After optimizing various TiO2- layer (HTL) in perovskite solar cells [138]. To reduce the recombi-
mesoporous films thickness and LBL cycles, the PCE of 2.10% was nation of photo generated electron-hole pairs and to get better per-
obtained with 15 LBL cycles with performance parameters as formance of PSCs, the Ti-based MOFs were synthesized where
VOC: 0.67 V, JSC: 4.92 mAcm2 and FF: 0.57 [129]. In view of the developed MOF was used as an ETL in Carbon based PSCs [139].
prevalent solar cell technologies, these parameters and efficiency The above discussed work is summarized and presented in Table 3.
need further improvement which could be achieved by suitable Thus a plenty of MOFs, their derivatives and composites have
experimental optimization along with simulation modeling. been successfully applied in different roles to various solar cell
In order to implicate the Zn-based MOF crystal as sensitizer in technologies and the obtained performance seems satisfactory till
DSSCs, the Zinc(II) meso-tetrakis (4-carboxyphenyl) porphyrin date. Further investigation, optimization and improvement in
MOFs were prepared employing solvothermal method which pro- properties of MOFs for solar cells are necessary in order to achieve
vided key evidence that efficient photocurrent could be generated the expected breakthrough in device performance and
when MOFs served as the sensitizer in solar cells [130]. To apply commercialization.
MOF based CE in bifacial DSSCs, the Cobalt-metalloporphyrin
MOF thin films were fabricated by liquid-phase epitaxy (LPE) 4.1.2. Fuel cells
method using a computer-controlled automated dip coater and A fuel cell is an electrochemical device that converts chemical
this first step was termed as PIZA-1 followed by the second step energy into electrical energy. It usually has high energy density
where the transparent CoS1.097@N-doped Carbon films were fabri- and efficiency and pertaining harmless emission virtue. The classi-
cated by sulfidation process using Cobalt-metalloporphyrin (PIZA- fication and working procedure of fuel cells depends on the nature
1) MOF thin films where template, Cobalt and Sulfur powder were of electrolyte, migrating ions and the range of operating tempera-
used as precursors. These transparent films were used as counter ture. The typical structure of fuel cell is demonstrated in Fig. 13
electrode (CE) in bifacial DSSCs which exhibited higher power con- comprising of anode, electrolyte and cathode. The MOFs proved
version efficiency of 9.11% and 6.64% from the front and rear irra- their potential role as an electro-catalyst and electrolyte mem-
diance, respectively. The XRD findings revealed to the crystalline brane in fuel cells. The outstanding flexible porosity, high surface
nature of composite and the SEM images demonstrated uniform area, uniform structured cavities, suitable thermal conductivity
dispersion of CoS1.097 nanoparticles on the substrate concerned. and tunable properties of MOFs help to increase the reaction mech-
The EDX pattern confirmed the deposition by presence of all the anism and the migration of charge carriers from anode to cathode.
constituent elements. The HRTEM images showed good crystalline The MOFs are appreciable nanomaterials for fuel cells as the MOFs
nature with inter-planar spacing of 0.25 nm. This work on the help in enhancement of oxidation reduction reaction (ORR) activity
counter electrode (CE) was done in an efficient manner [131]. which ultimately enhances the power generation of fuel cells. The
The [email protected] composite was applied as counter elec- MOFs could also be potentially applied as proton conducting poly-
trode in DSSCs which was prepared using hydrothermal method. mer electrolyte membrane to enhance the performance of fuel cells
The Tafel and cyclic voltammetry analysis were performed on the concerned. The expensive catalyst used in fuel cells such as Plat-
prepared composite which showed that the [email protected] pos- inum (Pt) could also be replaced by MOFs to reduce the cost. The
sessed higher catalytic behavior than that of the Platinum as the major part of the existing research on the fuel cells employing
counter electrode. The devices with [email protected] composite the MOFs is devoted to the polymer electrolyte membrane fuel
achieved a PCE of 7.86% [132]. The recently invented perovskite cells (PEMFCs) [25,140–144].
solar cell technology is now a rivalry to the champion technology The H2/O2 PEM fuel cells are based on two electrochemical reac-
in view of PCE, while stability and degradation are still existing tions wherein firstly, the oxidation of Hydrogen is occurred at the
14
Table 3
A summary on the metal organic framework (MOF) based solar cell devices.
Type of MOF(s) Comment(s) Ref.

ZIF-8 Thin layer of ZIF-8 was deposited on TiO2 to improve Voc of the DSSCs. [113]
Cu-MOF Thin films of Cu-MOF were deposited on TiO2 to improve Jsc and power conversion efficiency of DSSCs. [117]
MOF precursor Hierarchical ZnO parallelepipeds were synthesized and used as light scattering layer in DSSCs. [118]
Ru-MOF Thin films of Ru-MOF were deposited and used as a sensitizer in DSSCs. [119,127]
MOF precursor Porphyrin sensitizer was used to improve light harvesting in DSSCs. [120]
ZIF-67 CoS nanoparticles were used as a CE in DSSCs. [121]
Al-MOF Used as a gel electrolyte in solid-state DSSCs [122]
Co-MOF Iodine doped Co-MOF thin films were deposited on TiO2 to improve interfacial charge transfer in DSSCs. [123]
MIL-125(Ti-MOF) Hierarchical TiO2 was prepared and used as scattering layer in DSSCs to improve power conversion efficiency (PCE). [124]
Co-MOF Co-MOF thin films were deposited on TiO2 to improve light harvesting in DSSCs. [125]
MIL-125 Used as a photoanode to improve power conversion efficiency of DSSCs. [126]
ZIF-8 ZIF-8 used as a CE to improve efficiency of DSSCs. [128]
Co-MOF Co-DAPV thin films were deposited on TiO2 which acted as a sensitizer in DSSCs. [129]
PPF-MOF PPF-MOF was used as a sensitizer to improve power conversion efficiency of DSSCs. [130]
Co-MOF Co-MOF thin films were deposited on FTO substrate and used as a CE in bifacial DSSCs. [131]
Co-MOF Co-MOFs nanostructure was used as a CE in DSSCs. [132]
Thiol Functionalized 2D MOF Used to improve operational stability of PSCs. [133]
Polymer-MOF Used in Lead sequestration from PSCs. [134]
Co-MOF Co-MOF was used as an ETL to improve efficiency of PSCs [135]
ZnO-nanosheet Used as a photo anode to improve efficiency of DSSCs. [136]
MIL-125 Used to improve electrical and photovoltaic performance of SCs. [137]
Cu-Ni-MOF Used as hole transport layer in PSCs. [138]
MIL-125(Ti-MOF) Used as electron transport layer in PSCs. [139]
[147]. In PEM fuel cells, improvement in proton conduction is also

a key challenge and therefore, significant improvement in proton
conduction using Ni-MOF with hexagonal pours was achieved
[68]. To enhance the durability of the PEMFCs, the Fe/N/C catalyst
was prepared by ball milling of ZIF-8 and chloroiron-tetramethoxy
porphyrin MOF composite and then volumetric activity and dura-
bility of the PEM fuel cell were performed. The pyrolysis of pre-
pared catalyst has been done in the presence of the Argon and
NH3, and consequently, an improvement in the durability was
observed by the catalyst NC Por_0.8–1150 Ar + NH3 [148]. To
undertake the mechanical and thermal stability, the poly (ether
sulfone) MOF membrane was synthesized followed by performing
the ion exchange capacity, durability and proton conductivity of
the PEM fuel cells. The proton conductivity of MOF anchored sul-
fonated poly (ether sulfone) was 0.041 S cm1 at 160 °C which
was analogous to that of the polymeric PEMs [149]. Similarly, sul-
fonated (polyether ether ketone) Cu-MOF membrane was also syn-
Fig. 13. The basic architecture of a typical fuel cell comprising of constituent
thesized for fuel cells [150]. To improve the proton conductivity
components.
and thermal stability, the polysulfone based electrolyte membrane
was synthesized using silica and MOF nanoparticles for the PEM
anode and secondly, the reduction of Oxygen takes place at the fuel cells. The obtained results showed an increase in the proton
cathode. In a PEM fuel cell, the Oxygen reduction reaction (ORR) conductivity by 17 mS cm1 and enhancement in the thermal sta-
at cathode is happened slower as compared to Hydrogen oxidation bility [151]. A polymer membrane was synthesized for fuel cells
reaction at the anode which could be overcome by replacing the Pt using Fe-MOFs where water molecule was applied as the coordi-
catalyst with a non-Pt group metals like M/N/C where M is the nated linker between bistriazolate-p-benzoquinone and Iron. This
metal like Fe or Co, N is the Nitrogen and C is the Carbon, but Fe-MOF membrane showed higher proton conductivity at 22 °C.
the Fe/Co-based catalysts have lower power density vis-à-vis to The chemical properties of Fe-MOF were tuned to enhance the pro-
the Pt-catalyst. To maintain high power density to the fuel cells, ton conductivity [152]. To apply Carbon framework as cathode,
MOFs have been potentially introduced as an electrocatalyst in porous Carbon framework was synthesized using salt recrystalliza-
the fuel cells. In the year 2011, MOF based Fe acetate/ tion process taking HKUST-1 as template and the fuel cell con-
phenanthroline/ZIF-8 electrocatalyst was synthesized where ZIF- cerned gained a higher power density of 780 mW/cm2 which
8 served as a host material for Fe acetate and phenanthroline. A supported highly efficient PEM fuel cells [153]. In order to under-
rise in volumetric activity was observed along with and mass take simulation modelling, the density functional theory (DFT)
transfer properties [145]. was employed to study the cathode electrocatalyst for fuel cells.
Later, the porous organic polymer (POP) Polyporphyrin MOF The X3(HITP)2 MOF was used as a template, where X is Cr, Mn,
was introduced as an electrocatalyst for the PEM fuel cell which Fe, Co, Rh, Os, and Ir, and HITP is 2,3,6,7,10,11-hexaiminotripheny
achieved gravimetric and volumetric current densities of 39.4 lene. The work showed that all the simulated MOF showed good
Ag1 and 20.2 Acm3, respectively at 0.8 V [146]. The MOF based ORR volumetric activity except Ir3(HITP)2 and Rh3(HITP)2 [154]. A
electrocatalyst for the PEM fuel cell was also reported with an long-range proton conduction membrane was synthesized using
effect of furfuryl alcohol which fertilized the MOF that was used Zr-MOF (UIO-66) where 40 wt% UIO-66 incorporated into highly
as the micro porous host for Fe acetate and phenanthroline conductive poly [2,20 -(p-oxydiphenylene)-5,50 -benzimidazole]
15
(OPBI) membrane that exhibited the proton conductivity 0.092 S 4-(p-dimethylaminostyryl)-1-methylpyridinium and acriflavine
cm1 at 160 °C. A 40% UIO-66@OPBI membrane was optimized into a blue emitting anionic luminescent MOF ZJU-28 which
for the high-performance PEMs [155]. To develop urea fuel cell increased the emission of white light and showed enhancement
using the potential Ni-MOF, the Ni@C and NiO@C electrocatalysts in quantum efficiency [168].
were synthesized by applying Ni-MOF as an anode material [156]. The WLEDs are capable to replace the conventional light
To the date, extensive efforts have been made continuously for sources due to their lesser power consumption and long-life vir-
new porous Carbon materials with tremendous configuration like tues. A WLED was designed with combination of the Strontium-
Carbon nanowires, Carbon nanotubes, and MOF derived Carbon based MOF, inorganic semiconductor and graphene, and the
materials. These materials have been used with a range of strate- unique properties of these materials led to produce white light
gies to control the structure of pores and surface defects, the design around 555 nm [169]. Similarly, another material was synthesized
model of electrocatalysts and the theoretical calculation. The novel by encapsulating Eu3+/Tb3+ hybrid ions into a robust MOF [170].
trustworthy paths have been continuously developed for further The dye@MOF was demonstrated as a fluorophore in WLED where
improvements in the performance of electrocatalysts and explor- the combination of blue and red lights emitted from 9,10-
ing the catalytic mechanism in the fuel cells [157]. Thus, various dibenzoate anthracene and encapsulated Rhodamine B respec-
MOFs have been investigated for potential electrocatalyst applica- tively generated the white color. The developed WLED device pos-
tions in different fuel cells especially in PEMFC and provided new sessed a modulating frequency of 3.6 MHz for visible light
expectations to the research community concerned. communication which was six times greater than that of the com-
mercial WLEDs [171]. The MOF based organosulfonate compound
4.1.3. White light emitting diodes was synthesized that possessed 1D chain (-Cl-Cd-) and the DFT cal-
The invention of the transistor during 1948 opened a new way culations at different temperature revealed to self-trapped
for the introduction of different electronic devices which are com- electron-hole pairs generated the electron–phonon coupling in
prised of several layers and by the due course of time, the technol- the 1D chain. This additional property showed a significant
ogy is revolved by the development of various kinds of improvement in performance of WLED as compared to the conven-
nanomaterials. By applying band gap engineering and novel mate- tional LEDs [172].
rials, cost effective technologies are existed and dominated the The unique properties of the MOF viz. high porosity and surface
market. In this order, the white light emitting diodes (WLEDs) have area provide a host matrix to MOF [173]. To apply MOF composites
become a demanding light source due to their long lifetime, envi- in WLEDs, the bio-MOF-101–1,2-bis(4-(4-carboxyphenyl))-1,2-di
ronmentally friendly nature, high efficiency and miniaturization of phenylethene (BCPPE) fluorophore was encapsulated into bio-
hardware. Generally, the white light produces by fusion of blue MOF-101 which emitted white light at 375 nm wavelength and
LED chip and yellow phosphor like Cerium-doped Yttrium Alu- provided a way to other MOF composites for WLEDs [174]. Another
minum garnet. Another approach uses to produce white light approach using Zn-based MOF was evolved which showed emis-
includes combination of red, green and blue emitting phosphors sion of white light at 260 nm excitation wavelength along with
collectively on the top of an LED chip. Sometimes the device com- 32.5% quantum yield [175]. Similarly, carbazole derived Zn-based
plication, thermal quenching, high cost and low visible range are MOF obtained intense blue light which combined with red and
the major issues in the development of the WLEDs. The MOFs are green dyes in the host MOF and generated white light with 39.4%
found promising nanomaterials in field of light emitting diodes quantum yield [176]. A graphene quantum dot (GQD) based
owing to their assorted structural configurations and variable GQD@ZIF-8 composite was synthesized using ZIF-8 as MOF tem-
luminescence virtues. In MOFs based light emitting diodes, the nat- plate which was used as a yellow phosphor in WLED and provided
ure of metal ion and its concentration, organic ligand’s structure white light with high color rendering index [177]. To demonstrate
and excitation wavelength decide the color of emission. The nature color tunability of dye-encapsulated MOFs, another composite
of energy transfer between the organic ligand and metal ion con- Rhodamine@bio-MOF-1 was synthesized which possessed high
cerned affect the intensity of emission. The luminescent behavior intrinsic luminescent efficiency, tuned white light from 550 nm
of MOF increases its applications in the field of white light emitting to 610 nm and showed huge color tunability [178]. Persistent
diodes (WLEDs) [158–160]. The guest molecules in the MOF tune efforts have been made to implicate MOF as a host and to encapsu-
the emission of visible light and the phenomena of photolumines- late dye molecule to generate intense white light and accordingly
cence occurred. The [Ag (4-cyanobenzoate)]nnH2O MOF was tuned the rhodamine B was encapsuled into Gadolinium-based MOF for
with the photoluminescence caused by irradiance of yellow to the development of efficient WLED [179]. The R-phycoerythrin flu-
white light [161]. orescent was encapsulated into Blue-MOF-hydrogenated Schiff
To introduce Lanthanides in MOFs for extending lightening base that exhibited both the green and red lights fluorescence
applications, metal ions were replaced in MOFs by two lanthanides emissions [180]. In these ways, MOF derivatives have been per-
(Ln), Terbium (Tb) and Europium (Eu) ions which provided addi- formed excellently in WLEDs where research is in progress to
tional green and red light with a wavelength of 543 nm and improve efficiency and intensity to the date.
614 nm, respectively [162]. Similarly, an interesting and novel
luminescent Ln-MOF was synthesized which showed chemical 4.2. MOFs applications in electrochemical energy storage devices.
similarities of Ln ions with organic ligands [163]. The Strontium
based MOFs were synthesized which provided the white light from There is a variation in power consumption and generation as
single element and showed continuous band emission at about renewable energy resources generate power under specific condi-
550 nm [164]. In continuation, by varying excited wavelength of tions, for instant solar irradiance incidents during day time and
Eu0.0878Tb0.9122L, the emission of white light took place [165]. The accordingly conversion into electrical energy is possible which
luminescent MOF from Iridium complex with encapsulation needs storage devices. Modern electronic devices at all scale also
namely NENU-524 was synthesized that possessed permanent need efficient storage and back up, and in order to cater the society
porosity along with the high stability in air and existed as a poten- need, persistent efforts have been made so far with introduction of
tial material for the lightening [166]. The Dy(III)-based MOF was newer, functional and advanced materials to develop efficient con-
reported which tuned yellow to blue photoluminescence on wave- version and storage devices. The emergence of MOFs has also pro-
length excitation [167]. To achieve higher efficient white light, an vided the advanced roadmap to enhance the performance of the
ion exchange process was used which encapsulated organic dyes energy storage devices in view of the modern world of cutting-
16
edge technology. The MOFs put forward a vigorous structure with redox-active metal centers for multiple electrons accommodation
the high surface area along with open metal center sites which and can release the channels in order to ensure the passage way
straightforwardly undergo the reversible redox reaction without for electrolytes for simple access and transportation of Li+ ions,
harming the framework and therefore, the MOFs are enthusiasti- and consequently, high energy density and reversible capacity of
cally considered as an electrolyte, an anode or a cathode for the LIBs concerned could be achieved employing the MOFs. Thus, the
electrochemical energy storage devices [181]. As so far available highly porous nature of MOFs can induce huge Li-ions accommo-
literature, the batteries (Lithium-ion, Sodium-ion, Zinc-air, dation space and appropriate Li-ions pathway [184].
Aluminum-air batteries) and supercapacitors are frequently used Most of the current research on LIBs is based on the insertion
as the electrochemical energy storage devices where the MOFs compound such as cathodes, anodes and organic liquid elec-
are employed to improve their performance to cater energy need trolytes. The basic component materials for batteries comprise
of the world for the portable electronic devices which are dis- electrode materials and electrolytes. The properties like unique
cussed in this section. The typical device structures of MOF based morphology, high energy density, functional linkers, metal sites,
batteries which have been discussed in this review are shown in high specific area and higher power density would be the neces-
Fig. 14. sary parameters for the development of high performance energy
storage electronic devices. The MOF materials possess all such
4.2.1. Lithium-ion batteries properties for electrochemical energy storage devices [26]. In addi-
The rechargeable Lithium-ion batteries (LIBs) are promising tion, MOFs have better thermal stability vis-à-vis to the pure
energy storage devices owing to their high storage capacities, organic materials. The inner pores of MOFs may speed up the
long-term life, high energy density, light mass and good cycle per- migration of the Li-ions and electrons and therefore, more efficient
formance as well as environmentally friendly nature. The LIBs have use of metal ions is favorable that scrutinizes the MOFs materials
broad applications in portable electrical devices due to their light as an electrolyte, anode and cathode materials for the LIBs [185].
weight, small volume and environmental benignity [182–183]. The MOFs structure offers three-dimensional bonding with inter-
The MOFs have potential to introduce extraordinary properties in stitial/extraction space for the insertion of metal cation. The speci-
LIBs due to their structural diversity, tunable morphology, easy fic capacity of LIBs could be strengthened by inserting the redox
synthesis method and low cost. The LIBs have three imperative active sites at metal clusters and organic linkers. An improved sur-
components viz. an anode, a cathode and an electrolyte sand- face morphology of MOFs can induce appropriate active sites, high
wiched between the electrodes. During the charging process, Li- surface area and ion kinetics of LIBs concerned where high surface
ions deintercalated from cathode and then intercalated to the area is needed for optimum exposure of electrolytes [186].
anode, passing through the electrolyte, and LIB stores energy dur- For better performance of LIBs, various nano materials are intro-
ing this process i.e. gets charged while on moving Li-ions back to duced for electrodes too. The variation in physical and chemical
the cathode, the LIBs discharge. The porous MOFs can proffer the properties of MOFs by varying dimensions is also focused so far
Fig. 14. The device architectures of MOF based energy storage devices (a) Lithium-ion, (b) Sodium-ion, (c) Aluminum-air, and (d) Zinc-air batteries.
17
and moved initially from three-dimension (3D) to two-dimension analysis showed face-centered cubic (FCC) phase with Fm-3 m
(2D) structures such as nanoplates, nanosheets and nanomem- (2 2 5) space group. The thermal stability analysis employing TGA
branes, and then towards one dimension (1D) structures like demonstrated it as adequate electrode materials in batteries for
nanoribbons, nanowires and nanotubes to enhance performance both the stationary and portable applications [191]. The promising
of energy storage and conversion devices by designing MOF high performance anode material for LIBs by using MOFs was syn-
derived micro/nano-structures [187–188]. thesized where a Carbon cage coated bimetallic sulfide (Fe2Zn3S5/
Owing to the excellent electrochemical properties of the Iron, Fe1-xS@C) composite with heterogeneous structure was focused
several reports are available on the Iron-based MOFs for LIBs appli- by taking (FeIII-MOF-5) as a self-sacrificial template. The cyclic
cations. The spindle-like porous a-Fe2O3 was synthesized using Fe- voltammetry findings indicated occurrence of conversion reaction
based MOFs as a template by two steps calcination process of MIL- during the charging and discharging processes and on varying
88 Fe where the porous a-Fe2O3 showed significant improvement the current density from 100 mAg1 to 10,000 mAg1, the compos-
in capability of Li storage with a retain capacity of 911 mAhg1 ite capacity was ranged from 851.4 mAhg1 to 397 mAhg1. This
after cycles at a rate of 0.2 C. The XRD findings showed rhombohe- synthesized composite showed enhanced performance as anode
dral phase and BET analysis showed surface area of 75 m2 g1. The material for the LIBs [192].
spindle porous a-Fe2O3 showed enhanced performance for anode The dual-ion battery was developed by synthesizing the Cu-
material in LIBs [189]. based MOFs with an organic linker 7,7,8,8- tetracyanoquin-
The Fe-based metal organic polyhedral nanorods of MIL-88B odimethane (TCNQ) where the battery mechanism involved rever-
structure was designed as promising anode materials for LIBs. On sible reaction between Cu-MOF and PF 6 anions of the electrolyte
testing the nanoporous Fe-MIL-88B polyhedral nanorods at 60 [193]. To utilize the Cu-based framework as an anode material
mAg1, the retain capacity was observed to be 744.5 mAhg1. An for LIBs, the polyoxometalate pillared MOF [Cu24(Trz)16(H2O)Cl4(-
organic ligand with p-p conjugation bond was chosen because p- HPMo12-O40)] was synthesized and characterized. The obtained
p stacking increased the electronic coupling of the stack of discrete reversible capacity was 525 mAhg1 at current density of 100
moieties. The XRD findings as demonstrated in Fig. 15 (a) were mAg1 after 100 cycles. The XRD findings showed the triclinic
consistent with that of the hexagonal MIL-88B and the TEM image space group where the presence of all the constituent elements
of Fe-MIL-88B nanorods electrode after 100 cycles is shown in was confirmed employing the XPS measurements [194]. The Cd-
Fig. 15 (d). A reversible capacity for half and full-cell Lithium bat- based MOFs with organic ligand H3TTPCA were synthesized which
teries after 400 and 100 cycles was obtained as 744.5 mAhg1 and showed remarkable thermal stability on pyrolysis. The evaluated
86.8 mAhg1, respectively. The FTIR spectroscopy and the XPS discharge capacity before pyrolysis was 300 mAhg1 while after
measurements (Fig. 15 (b) and (c)) showed high reversible specific pyrolysis, the capacity was increased to 741 mAhg1. On pyrolysis,
capacity of the transition metal cluster and organic ligand [190]. the cyclic stability was also increased which demonstrated that the
In order to implicate the MOF derivative as cathode in LIBs, the Cd-based MOF could be used as an anode material in LIBs. The
border-rich Iron hexacyanocobaltate (FeHCCo) MOFs were synthe- pyrolysis of MOF facilitated the transportation of electrons and
sized via facile and low-cost co-precipitation method. The lithia- Lithium ions in the battery which consequently improved the cyc-
tion capacity of 116 mAh g1 was maintained at 1.25C with lic stability [183]. The composite of Silicon nanoparticles with
99.6% coulombic efficiency. The TEM and SEM findings demon- Ni3(2,3,6,7,10,11-hexaiminotriphenylene)2 structure was devel-
strated approximately 200 nm nanoparticle size and the XRD oped as an anode for the LIBs. This composite increased the
Fig. 15. Evolutions of (a) ex-situ XRD patterns of the Fe-MIL–88B electrodes, (b) FTIR spectra and (c) Fe 2p XPS core spectra, and (d) TEM image of the Fe-MIL–88B electrode
after 100 cycles. Reprinted with permission from Ref. [190]. Copyright (2017) Elsevier.
18
electronic conductivity, Li-ion storage capability, rate capability combination of electrolyte with electrodes to enhance the cycle
and life cycle of LIBs [195]. The porous Co3O4 based anode materi- life, efficiency, reversible capacity etc. Since the basic components
als were developed for LIBs where the nanoparticles were prepared for SIBs are electrode and electrolyte materials and therefore, the
from precursor Co-MOF which possessed excellent electrochemical electrodes and electrolytes should have possessed properties like
properties. The XRD patterns revealed to the high crystalline nat- uniform morphology with high surface area, high energy and
ure of Co-MOF. The reversible capacity of MOF based LIB reached power densities which are the necessary parameters for crucial
upto 924.1 mAh g1 at 200 mA g1 after 100 cycles and 838.6 power supply in future energy conversion and storage electronic
mAh g1 at 1000 mA g1 after 300 cycles [196]. The Cu1.8Se@C devices as stated earlier. In view of the above, the MOFs materials
was synthesized using Cu-BTC template and obtained composite are investigated which possess these properties for the SIBs [209].
material was implicated as an anode for the LIBs. The XRD patterns In order to apply MOF composite as an anode material for SIBs, the
revealed to the crystalline nature of the Cu-MOF and the synergis- rational design to the MOF composite was expended which
tic effect of Cu1.8Se@C enhanced the reversible capacity (cyclic sta- showed specific capacity and retention of about 269 mAh g1
bility) even after 1000 cycles [197]. The Sodium-Tin (Na-Sn) MOF and 79.0%, respectively after 1000 cycles. The Co-MOF composite
was synthesized using simple reflux method to apply as an anode was also explored for an electrode material for the SIBs [210].
material for the LIBs. This work overcomes the problem of volume In response to the demand for significant improvement in
expansion occurred during the Lithium insertion and extraction kinetics and capacity retention of SIBs, the FeFe(CN)6/carbon cloth
process and the synthesized anode material possessed specific composites were synthesized as a potential host for Na ion inser-
capacity of 523 mAhg1 [198]. In order to improve interfacial sta- tion. The composites showed good electrochemical performance
bility in LIBs, the Co-MOF-74 was designed and synthesized as an with a reversible specific capacity of 82 mAhg1 at 0.2C with good
advanced additive for Ni-rich cathode in LIBs with a surface area rate capability and long-term cycling life. This low cost and scal-
of 1122 m2 g1 and pore size of 0.4–0.9 nm. As a result, high sur- able synthesis provided assistance to design many more flexible
face area and small pore size provided a suited barrier to surpass MOF composites as electrode materials for the SIBs [211]. In order
the outflow of Ni-ions from the cathode which consequently to obtain long term cycling capacity of the SIBs, a novel Ca-organic
resulted into an improvement in the cycle retention [199]. framework was synthesized using Calcium ions and an organic
In this way, the MOFs, MOFs composites and MOFs derivatives ligand 1,2,4,5-benzenetetracarboxylic acid. The synthesized mate-
have been potentially applied as cathode, anode and additives for rial was implicated as an anode material for the SIBs. The work
LIBs. The elevated research using MOFs has been continuously car- showed that framework composite for electrode and electrolyte
ried out for the development of higher power density and highly could achieve high capacity and good capacity retention [212]. A
efficient LIBs which ensure rapid progress in the field concerned. highly graphitized porous Carbon framework was synthesized to
There are certain drawbacks of LIBs viz. high cost of Lithium and apply as a cathode material for SIBs that showed well capacity
Cobalt elements, energy restricted to lesser than 100 Wh, and high retention and good rate performance [213]. The hierarchical por-
impact on environment. These all factors encourage the develop- ous TiO2 nanopills were synthesized by employing MIL-125 (Ti)
ment of new and innovative energy storage devices and, therefore and this porous composite was used as an anode material for SIBs.
Sodium-ion batteries (SIBs) became the novel energy storage The excellent capacity retention of 90% after 3000 cycles was
devices incompetence with the clean power storage devices obtained and the results specified that this type of porous material
[200–201]. Taking advantage of MOF composites in SIBs, the derived from the MOF possessed potential to be used as electrodes
numerous reports are available so far and therefore next part for the SIBs [214]. The core/shell CoP@C polyhedrons were
describes applications of the MOF nanostructures for the SIBs. synthesized using ZIF-67 to implicate as an anode material for SIBs.
The synergistic effect of core/shell CoP@C and 3D reduced
4.2.2. Sodium-ion batteries graphene oxide (RGO) showed an admirable specific capacity of
The Sodium-ion batteries (SIBs) possess a potential for commer- 473.1 mA h g-1 at a current density of 100 mA g1 over 100 cycles
cialization due to low cost and enormous abundance of the [215]. To improve electrochemical performance of the SIBs, MOF-5
Sodium. The lower melting point of Sodium ensures the safety of templated Sulfur-doped mesoporous Carbon material was used as
the SIBs. The SIBs have three essential components viz. an anode, an anode material that promoted the intercalated/deintercalated
a cathode and an electrolyte. The Na-ions deintercalated and inter- process of Sodium storage [216]. Hierarchical Ni-MOF composite
calated between electrodes (anode and cathode) through the elec- NiS2 was synthesized to use as an anode in SIBs which
trolyte during the charging and discharging process. The charging/ demonstrated improved reversible capacity and capacity retention
discharging mechanism, structure and component of SIBs are iden- of the SIBs [217].
tical to that of the LIBs while in SIBs, the migrating ions are Sodium To improve the functionality and electrochemical performance
ions instead of Lithium ions [200–202]. In the beginning, Carbon is of SIBs, a shuttle skeleton of vanadium oxide using MIL-88B (V)
emerged as the suitable electrode material for the SIBs that showed was prepared. The layered structure and metallic behavior of V-V
the mechanism of intercalation and deintercalation of Sodium sim- bond of shuttle like vanadium oxide existed even after the inser-
ilar to that of the Lithium [203–204]. On replacing the Carbon elec- tion of the Sodium ions. This nature showed that the synthesis of
trode with the transition metal oxide-based electrodes, the porous Vanadium-based materials possessed capability to improve
reversible discharge capacity lied close to 300 mAhg1 [205]. Later, the functionality of the SIBs [218]. The MgFe2O4 microboxes using
to increase the reversible capacity of SIBs, the inorganic composite- MOF purssian blue microtubes were prepared and used as an
based electrodes were replaced by the combination of organic anode material in SIBs. This material provided an additional liberty
compounds viz. formaldehyde and resorcinol, but the obtained of volume expansion to the Sodium ions during intercalated/dein-
reversible capacity was still found 285 mAhg1 [206]. In continua- tercalated process which showed an improvement in the conduc-
tion, the Chromium doped composites NaV1xCrxPO4F (x = 0, 0.04, tivity and rate performance of the SIBs [219]. For long life and
0.08) were prepared as cathode materials for the SIBs, but still, the high stability, the MnO@C nanorods were fabricated using Mn-
results were far away from the expectations [207]. For better cycle based MOF and applied as an anode material in SIBs. Even after
life of the SIBs, the hierarchical porosity in anode materials was 100 cycles, the battery showed high reversible specific capacity
introduced which showed reasonable cycle life, but reversible [220]. The MOF materials have been attracted potentially for inno-
capacity was found unsatisfactory [208]. Due to the unsatisfactory vative work in energy storage devices and in this continuation, the
result of SIBs, many issues need to be overcome such as the right Co-based MOF was used as a precursor to prepare yolk shell CoSe/C
19
mesoporous dodecahedra structure. The prepared CoSe/C dodeca- been made to mitigate these drawbacks using MOF materials, but
hedra structure showed admirable cycling stability and rate capa- still the results are far away from the expectations. In continuation,
bility [221]. Similar to the Porous cake structure, TiO2 derived from still the work with an effective strategy has not been ended to
Ti-based MOF was used as an anode material in SIBs. Using this develop and design efficient electrode and electrolyte materials
material, the SIBs showed higher current density of 1 Ag1 and and even after that, excellent cycling and rate properties for the
capacity of 173 mAhg1 even after 2500 cycles which opened an SIBs are still far away and therefore, extensive research is further
additional progress scale for the SIBs [222]. To develop high perfor- required to achieve the demanding breakthrough in device perfor-
mance device, the Cu-MOF was pyrolyzed under microwave irradi- mance. The need of energy storage device with high-power output
ation to make porous CuO/ RGO composite which was applied as and stable performance emerged too as the Zinc-air batteries
an anode material for the SIBs. The composite CuO/RGO showed which are described in the next sub-section.
higher specific capacity of 466.6 mAh g1 after 50 cycles at current
density of 100 mAg1 [223]. Similarly, porous CoFe2O4 nanocubes 4.2.3. Zinc-air batteries
were derived from Co-MOF as high-performance anode material The Zinc-air batteries (ZABs) are better energy storage devices
for the SIBs which considerably affected the electrochemical per- due to their nonpolluting nature, high safety, economic viability,
formance of the SIBs [224]. The yolk-shell structure with high energy and power density, high reduction potential of Zinc
Nitrogen-doped Carbon composite (Co9S8/MoS2-CN) was synthe- flat discharge profile etc. The ZABs are predicted to have high
sized by ZIF-67 and used as an anode material in SIBs [225]. The energy density which consist of a Zinc anode, air cathode, an elec-
2D porous Cobalt sulfide nanosheets were developed using Co- trolyte and a separator. Their performance depends on the Oxygen
based MOF and demonstrated that h-Co4S3 nanosheets achieved reduction reaction (ORR) during discharge and Oxygen evolution
reversible capacity of 571 mAhg1 at 0.1 Ag1 with long life cycle reaction (OER) during the charging where both the reactions
stability [226]. Rod-like Carbon coated MnS was prepared from required a strong electrocatalyst. The MOFs demonstrate superb
Mn-based MOF to make anode material in order to improve the reactivity towards ORR and OER, tune the conductivity and
electrochemical performance of the SIBs [227]. The CoTiO3 meso- improve the ionic and gas diffusion, thus lead to advancement in
porous was derived from the bimetal organic framework (BOM) performance of ZABs [241].
as a micro-prism anode for the stable SIBs [228]. The MOF materi- The bifunctional metal catalyst improved the kinetic mecha-
als potentially and continuously fulfill the requirements for the nism of ORR and OER, but these have the disadvantage of high cost.
structural novelty in the SIBs. The MOF-199 was employed as a The low-cost, bifunctional and super flexible catalysts are highly
sacrificial template to make nanoporous CuxS with a large surface required to replace the costly metal catalysts. The formation of a
area. A uniform Carbon layer was coated on CuxS and found an 3D network is undertaken by metal cation, and the organic linkers
excellent specific capacity of 372 mAhg1 after 110 cycles [229]. in MOF gain significant attention as catalysts in ZABs. The MOFs as
The poor acceptance with reversible accommodation of the an electrocatalyst make interaction between the catalyst, elec-
large surface area of the Sodium ions in electrode material afflicted trolyte, and reactant which enhances the mass transfer and the
the flexibility of Sodium-ion Chemistry. The Bismuth nanodots kinetics of the ORR and OER in ZABs [242]. The Nitrogen-doped
were synthesized by substituting Co in Co-based MOF that porous Carbon nanorods (N-CNR) were synthesized using Co-
increased the kinetics of the SIBs and presented an extra capacity MOF as a precursor and the synthesized composite acted as a
and rate performance [230]. The Zn and Co based MOFs enhanced bifunctional catalyst in the ZABs. Owing to the significant proper-
the Sodium storage and improved the long-term performance of ties, the Co@N-CNR showed fast kinetics of the ORR and OER [243].
the SIBs [231]. To ensure the structural stability, Molybdenum Similarly, a Co-MOF based electrocatalyst for the ZABs was devel-
disulfide was synthesized using Mo-MOF which ensured good oped which showed bifunctional activities by reducing potential
structural stability of the SIBs during Sodium ions intercalation gap and increasing the stability and provided a new approach for
and deintercalation processes [232]. The porous Co-C nanocom- advanced mechanism of the rechargeable ZABs [244]. In addition,
posite was prepared using Co-MOF which possessed retention a new bifunctional elctrocatalyst was reported by the growth of
capacity over 80% with specific capacity of 200 mAh g1 [233]. ZIF-67 polyhedrons onto Ba0.5Sr0.5Co0.8Fe0.2O3 (BSCF) particles.
The materials to the SIBs have been suffered from low conductivity, The BSCF acted as a catalyst to support the Carbon graphitization
high volume variation during the charging and discharging pro- and optimized the transition from metal to Carbon ratio that
cesses with poor life cycle. The CoSx-Carbon composite was syn- enhanced the ORR activity with potential gap of 0.83 V at
thesized from a Sulfur MOF for the SIBs where obtained specific 5 mA cm2 [245]. The intermetallic Pt-Fe electrocatalyst was syn-
capacity was 664 mAh g1. This composite improved the electro- thesized using ZIF MOF, known as Zn/Fe bimetallic ZIFs which
chemical properties of the SIBs [234]. The MOFs derivative showed the long-term durability and larger mass activity vis-à-
approach was used to synthesize porous yolk-shell microcages vis to the conventional Pt/C catalyst [246]. The bifunctional Oxygen
MoP/Cu3P@C as anode material for the development of a highly electrocatalyst Co-Nx-C possessed honeycomb structure which
performance SIBs [235]. Nowadays, advanced porous materials smoothed the exhale/inhale kinetics of ORR/OER in the ZABs
using MOFs as templates are synthesized for the SIBs [236]. The [247]. The trimetallic nitride electrocatalyst was synthesized for
Fe-N-C nanostructures were utilized as an anode material in SIBs the ZABs using metallic titanium carbide sheets. The catalyst
which resulted into fast and superficial electrochemical properties showed excellent catalytic activities towards ORR and OER that
of SIBs [237]. A Carbon encapsulated Cobalt sulfide material was opened a novel avenue for further utilizing the 2D sheets in energy
prepared using polyacrylonitrile MOF composite which possessed storage device applications [248]. The ultrathin 2D electrocatalysts
specific capacity of 546.3 mAh g1 after running 2095 cycles [238]. were synthesized employing Co-MOF. This electrocatalyst showed
Thus, numerous MOFs and their derivatives have been exten- outstanding durability due to the presence of the synergistic effect
sively investigated for anode materials to SIBs concerned and of the N-coordinated single Co atom [249].
achieved suitable results to develop new zeal in the community The requirement of a stable and highly effective electrocatalyst
for further advancement [239–240]. to improve the efficiency of ZABs is still far from the expectations
The SIBs are suffered from sluggish kinetics of ion transport and therefore, further investigations are extremely required to
across the electrodes, high-rate capability and fast charge/dis- develop the high performance ZABs. In view of the environmental
charge rates. The large ionic radius of Sodium ion (Na+) is the main aspects, increase in pollution due to rapid requirements of
cause for slower diffusion kinetics. A number of attempts have petroleum-based vehicles require amelioration. The solution com-
20
prises production of large capacity batteries which could be regularized by similar basic equations as conventional capacitors
applied in electricity-based applications to reduce dependency on but to achieve greater capacitance, these make use of higher sur-
the petroleum. Accordingly, the Aluminum-air batteries have been face area electrodes and thinner dielectrics. The supercapacitors
considered as promising devices for next-generation energy stor- possess greater energy and power densities vis-à-vis to the con-
age applications which are discussed in next sub section. ventional capacitors and batteries as well as favorable charging-
discharging rates and a longer cycle life [260]. The supercapacitors
4.2.4. Aluminum-air batteries are considered as attractive electrochemical energy storage devices
The Aluminum-air batteries (AABs) emerge as a promising owing to faster charging/discharging, stable cyclability, huge
energy storage device having 8100 Wh Kg1 energy density and power density and outstanding safety virtues. The supercapacitors
2980 mAh g1 theoretical electrochemical equivalent. In AABs, function on mechanism of adsorption/desorption of the ions in the
electrical energy is produced when the Aluminum (Al) reacts with electrolyte concerned. Based on the working mechanism, the
Oxygen at the anode, and reduction of Oxygen takes place at the supercapacitors are classified into two categories viz. electrochem-
cathode. The emission of electrons in AABs is three times greater ical double layer capacitors (EDLCs) and pseudocapacitors. The
than that of the emission of electrons in the LIBs and therefore, EDLCs store charges via reversible ion adsorption at anode-
the AABs are more efficient as compared to the LIBs. With several electrolyte and cathode-electrolyte interface, but while the psedo-
advantages, the self-corrosion and slowed down the electrochem- capacitors store charges via redox reaction at the surface of the
ical reactions by the obtained byproducts are the drawbacks of the electrodes. Persistent efforts have been made to enhance cycle sta-
AABs [250–252]. The performance of AABs was improved with an bility, rate capability and specific capacitance of the supercapacitor
additive electrolyte which is known as Nonoxynol-9 and behaved devices. The phase change, side reactions and dissolution are the
as a cathodic-type inhibitor [253]. Similarly, Aluminum chloride main reasons which cause the instability in cycles and therefore,
based EMImCl ionic liquid was used as an electrolyte for the AABs improvement in mechanical and chemical stabilities of the elec-
that showed high current during OER and ORR, but decrement was trode materials is required to enhance the performance of superca-
observed in the energy efficiency [254]. Herein, challenges incor- pacitors. The rate capability depends on the ionic and electronic
porate enhancement in the current and energy efficiencies of AABs conductivities where high ionic and electronic conductivities help
concerned. to keep the rectangular character of cyclic voltammetry which
As far available literature, well-organized porous MOF is consid- drawn attention to work on ionic and electronic conductivities
ered as an attractive platform for the fabrication of porous C-based along with the optimization of electrodes with the higher surface
materials as active sites electrocatalysis for the AABs. To improve area which could lead to an improvement in the specific capaci-
the ORR in AABs, an electrocatalyst was prepared using N-doped tance [261–262]. To achieve high power and energy densities,
Carbon which showed ORR activity with an on-set potential of the Carbon and activated Carbon materials-based electrodes are
0.981 V along with better stability in alkaline conditions and the employed [263]. The Carbon and activated Carbon materials (com-
work opened new prospects to enhance the inside mechanism of pounds) are essentially different due to the difference in their sur-
AABs using MOF [255]. Similarly, N-doped carbon framework face area where higher surface area demonstrated higher specific
(CoNi-NCF) was also reported for AABs that increased the long- capacitance. However, besides this, activated Carbon material with
time durability and high flexibility and demonstrated as a promis- a surface area of 3000 m2 g1 has a small specific capacitance
ing material for potential applications in AABs [256]. of less than 10 lF cm2. This happens because with the surface
The performance of AABs depends on the ORR of electrocatalyst area, other parameters such as pore shape, pore size distribution,
which includes Pt-based catalysts, transition metal oxides, car- pore structure, electrical conductivity and accessibility of elec-
bonaceous nanomaterials, Carbon nanotubes, Graphene based trode–electrolyte also affect the specific capacitance of the super-
nanocomposites, metal Nitrogen Carbon and heteroatom doped capacitors [262].
Carbon, Carbon quantum dots, single atom catalysts and MOFs As the conventional electrodes such as Carbon and transition
types of electrocatalyst. Among these, for last two years, the MOFs metal oxide cannot possess this standard due to high cost, low sta-
become potential composite to enhance performance of the AABs. bility and capacitance, and therefore, MOFs have been recognized
The lesser but efficient work has been carried out using MOFs as potential candidature for the electrode materials to the superca-
which enhanced the stability and mechanism of the AABs. The pacitors owing to their higher surface area and adjustable pore size
Cobalt Nickel sulphide nanoparticles were encapsulated in graphi- [263]. The MOFs are regarded as sacrificial templates or precursors
tic layers and the synthesized composite worked as an electrocat- for development of transition metal or Carbon based electrode
alyst for the ORR in the AABs [257]. The ZIF-67 MOF is used to functional nanomaterials owing to regular morphologies, large sur-
synthesize the ZnO/ZnCo2O4/C@rGO electrocatalyst in order to face area, adjustable composition, controllable porosity and flexi-
enhance the kinetics of ORR in AABs [258]. Similarly, the Fe2O3@- ble structures due to presence of both the metal and Carbon
rGO, CoFe2O4@rGO and Co3O4@rGO composites are also demon- sources. The flexible porous structures of MOFs are very useful
strated as electrocatalysts in the AABs. Among these, for supercapacitor applications since such structures enhance the
CoFe2O4@rGO exhibited stable charge/discharge cycle with an ion diffusion, active surfaces and Faradic reactive sites which ulti-
excellent Coulombic efficiency of 99.6% where MOF showed its mately improve the energy storage of supercapacitors concerned
potential candidature in the AABs [259]. Hence, the MOFs and their [264]. The Ni-based two-dimensional MOF layers were synthesized
composites concerned played a vital role as a suitable electrocata- for electrode materials in supercapacitor applications. These layers
lyst in development of Aluminum-air batteries (AABs) too. were used in an aqueous alkaline solution and the electrochemical
properties were found in correlation with the intrinsic properties.
4.2.5. Supercapacitors The synthesized material possessed higher cyclic stability and
In response to the present scenario, energy has become a prime large specific capacitance [265]. Similarly, the Ni-based MOFs with
focus of the major scientific community and world power. There 2D layered structure was prepared to use as a positive electrode in
has been huge attention for the development and refinement of supercapacitors which resulted into high power and energy densi-
more efficient and capable energy storage devices like supercapac- ties as 7000 W kg1 and 55.8 W h Kg1, respectively. The surface
itors which have been grown considerably over the last decade and area of synthesized Ni-MOFs was 295.7 m2g1. The Hydrogen
emerged with the possibility to smooth the progress of foremost bonding between Ni-coordination compound and water molecules
advances in the energy storage. The supercapacitors are in the crystal structure [Ni3(OH)2(C8H4O4)2H2O)4]2H2O showed
21
the structural stability and smooth surface as revealed by the XRD consequently the Sodium metal ions have potential to increase
and SEM findings, respectively. The presence of synergistic effect the stability of supercapacitors [272]. The porous Nickel Cobalt lay-
provided a special structure to the MOFs with excellent power ered double hydroxide (NiCo LDH) nanotubes were prepared using
and energy densities. The reaction rate could be increased by using MOF precursor. The NiCo LDH was used as an electrode in superca-
redox additive K4Fe(CN)6 in the electrochemical mechanism. The pacitors and the developed device has demonstrated an excellent
synergistic effect, Hydrogen bonding, and redox additive enhanced performance without any loss in the capacitance [273].
the performance of the supercapacitors [266]. In this way, various MOFs and their composites have been syn-
To implicate the Ni-based MOFs as an electrode in supercapac- thesized and investigated for electrode applications for superca-
itors, it was synthesized using the ultrasonication method with the pacitors and opened new opportunities and healthy competition
consideration that the structure might enlarge or improve the dif- for further innovations.
fusion of ions or offer a stable skeleton for ions intercalation-
extraction where the synthesized Ni-MOF exhibited the accordion
structure. The energy and power densities were achieved to be 5. Challenges and opportunities
4.18 mWhcm3 and 231.2 mWcm3, respectively. The XRD peaks
were well indexed with [Ni3(OH)2(C8H4O4)2H2O)4]2H2O structure The present review concisely described the relationship
whereas the FESEM and TEM images demonstrated the nanosheets between metal ions and organic ligands coordinated inorganic
structure. The electrochemical measurements showed cyclic sta- Chemistry with organic Chemistry by means of finest MOFs, their
bility which was 96.5% after 5000 cycles while poor conductivity derivatives and composite materials. The carefully selected rele-
was the main drawback. The findings demonstrated that the Ni- vant potential applications of the MOFs those encouraged to design
based MOFs might fulfill the expectations to achieve high energy and synthesis of the efficient MOFs in energy storage and conver-
and power densities as required for high performance supercapac- sion devices are discussed with science concerned. The molecular
itors [263]. Similarly, the Ni-based pillared DABCO-MOFs were linkage in MOFs offers provocative new directions in the significant
reported as an electrode material in supercapacitors which have areas of porous materials and MOFs manage their functions by
structure as [Ni(L)(DABCO)0.5] where L is organic linkage (1,4- integration of organic and inorganic components. The improve-
benzene dicarboxylic acid) and DABCO is 1,4-diazabicyclo [2.2.2]- ment in MOFs performance parameters could be achieved by
octane [267]. In order to implicate the MOF derivatives in asym- mechanical properties concerned which are highly capable to tailor
metric supercapacitors, the metal–organic xerogels (MOXs) with the hybrid organic–inorganic nanoporous structures. These charac-
high surface area and unique properties, were synthesized employ- teristics generate exciting applications scenario and simultane-
ing the solvothermal method where the physical interactions like ously also attributes the challenges those require to overcome
Van der Waal’s forces, Hydrogen bonding, p-p interaction are the and to make these amalgamations of the MOFs with the upcoming
benefits of these MOXs which showed good capacitance retention technologies. In this review, an impressive number of MOF-based
up to 500F/g at 8 A/g [268]. To increase the charge storage capacity energy conversion and energy storage devices are compiled where
of asymmetric supercapacitors, Co-based MOFs were developed most of these are reported within the past decade. The most influ-
with crystal structure [Co(2-ATA)2(4-bpdb)4]n (NH2-TMU-53) enceable parameters to the MOFs-based materials are high poros-
which possessed specific capacitance of 325 Fg1 with cyclic stability, large surface area and tunable chemical and physical
ity 92.03% at current density of 5 Ag1 [269]. The poor conductivity properties. These parameters somehow depend upon the synthesis
limits the use of supercapacitors which could be overcome by route of MOFs which are also explained. For numerous, advanced
developing Zr-based MOF/Conductive polymer (polypyrrole) and potential applications, various routes are existed to build
hybrid-based fiber supercapacitors using one-pot electrodeposi- well-defined MOF thin films with thickness evolution, but still,
tion method. The fibrous supercapacitors exhibited good proper- there is a need for rapid development in the field of MOF thin films.
ties viz. specific capacitance of 10 mFcm1, power density of 132 Considering an enormous flexibility of the MOFs and MOF com-
lWcm1 and energy density of 0.8 lWhcm1 and recognized as posites, further there is a need to enhance the performance of the
promising potential energy storage device in wearable textile elec- existing and to develop new devices with novel structure through
tronics that can be conveniently woven into common cotton cloth unexpected functionalities. For the implementation of MOFs based
[264]. nanomaterials to solar cells concerned, still numerous challenges
The TPDA-1 porous polymer was synthesized using two mono- need to be overcome those include improvement in the thin film
mers viz. 2,4,6-trihydroxyisophthalaldehyde and 1,3,5-tris(4- quality, understanding and learning the thin films growth mecha-
aminophenyl) triazine for highly efficient capacitive energy storage nism, controlling and effective passivation of the defects occur in
devices. The synthesized TPDA-1 material has specific capacitance thin films concerned, improvement in the interface stability,
of 469.4 Fg1 at 2 mVs1 and high surface area of 545 m2 g1 and enhancement in carrier concentration and electrical conductivity,
better specific capacitance where the presence of p-p conjugation charge carrier mobility and improvement in charge separation
and ion conduction made this porous polymer as a potential candi- and collection efficiency. The energy conversion devices or solar
date for the supercapacitors [270]. An electrode for supercapacitors cells need optimization of device architecture employing MOF
was developed with Cu, Co and Ni as metal cations and tereph- based constituent layers and simulation modeling.
thalic acid as an organic linker. Using one-step facile hydrothermal In electrochemical devices, high ionic and electrical conductiv-
reaction, the ternary metal terephthalate was prepared on Ni-foam ities of materials are required and therefore, building the MOF
substrate where the evaluated specific capacity was found as 321.3 composites having high conductivities employing common organic
mAhg1 that was better vis-à-vis to the single MOFs component. linkers still remains a challenge. For the development of high per-
The ternary metal terephthalate on Ni-foam (Co/Cu/Ni-bdc/NF) formance fuel cells, the poor stability of pristine MOFs in elec-
demonstrated good electrochemical performance [271]. To trolyte at working potential should be rectified whereas the rate
increase the stability of the supercapacitors, Sodium/Cobalt capability of MOFs also requires enhancement in order to achieve
heterometallic MOF(Na/Co-MOF) was synthesized using slow dif- the appropriate power density. To improve the catalytic perfor-
fusion technique at room temperature where the XRD pattern of mance of batteries, dual or multi-metal sites in MOFs should be
the synthesized material showed good crystallinity. The electro- further developed. The pure MOFs have poor conductivity and
chemical impedance spectroscopy (EIS) showed rapid charge combine the MOFs with conductive materials such as Carbon
movement process at the electrolyte/electrode interface and material and conductive polymers need to be further investigated.
22
The challenges lie in the synthesis of highly porous solids which [32] M. Bosch, S. Yuan, W. Rutledge, H.C. Zhou, Acc. Chem. Res. 50 (2017) 857–865.
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Metal Organic Framework MOF

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Coordination Chemistry Reviews 446 (2021) 214115

Contents lists available at ScienceDirect

Coordination Chemistry Reviews

Metal organic frameworks as hybrid porous materials for energy storage

4.2.2. Sodium-ion batteries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19

Fig. 1. Typical structure representing formation of Metal Organic Frameworks (MOFs).

Fig. 2. An overview of MOFs synthesis, properties, and applications.

condensation reaction. It was noticed that the basicity of azine Table 2

Fig. 4. Classification of MOF thin films on the basis of deposition methods.

the electrochemical impedance spectroscopy and I-V characteris-

challenges for the same to demonstrate its existence for industrial

Type of MOF(s) Comment(s) Ref.

[147]. In PEM fuel cells, improvement in proton conduction is also

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