Advances in Halloysite Nanotubes HNTs

Advances in Halloysite Nanotubes (HNTs)-Based Mixed-
Matrix Membranes for CO2 Capture

Sikander Rafiq[1,2],*, Muhammad Saeed[3], Asif Jamil[1], Muhammad Imran Rashid[1], Muhammad Irfan[1],
Tanveer Iqbal[1], Abrar Inayat[4], Farrukh Jamil[5], Jibran Iqbal[6], Muhammad Shahzad Khurram[5],
Muhammad Shozab Mehadi[7]
Abstract
Membrane technology promises a highly economic- attention in gas separation technology and due to
al and efficient solution for CO2 separation. Many their tubular structure have been used in a variety of
polymeric membranes have been reported in the applications in biomedical, coating, composite, and
past for the separation of gases specially to remove electronic industries. However, very little but con-
CO2 from natural gas and low-pressure flue-gas clusive literature and reviews are available to indi-
streams. The performance of membranes can be tai- cate that functionalized and non-functionalized
lored by dispersing nanofillers in a polymeric ma- HNTs can improve the performance of MMMs for
trix to produce mixed-matrix membranes (MMMs). efficient CO2 capture. The current status and gaps
This not only adds mechanical strength to mem- for potential applications of HNTs-based mem-
branes but also reduces compaction of the poly- branes for gas separation are identified and re-
meric layer at high pressure and maintains high per- viewed.
formance. Halloysite nanotubes (HNTs) gained
Keywords: CO2 capture, Gas separation, Halloysite nanotubes, Mixed-matrix membranes
Received: August 10, 2022; revised: October 13, 2022; accepted: March 02, 2023
DOI: 10.1002/cben.202200041
1 Introduction trolled, and eventually the atmospheric CO2 concentration will

reach 1000 ppm [3–7]. Under ‘‘business-as usual’’ emission sce-
CO2 emissions are steadily increasing due to an ever growing nario, atmospheric temperatures can rise by 5 °C by 2130 [8, 9].
energy demand and combustion of fossil fuel to meet these Billions of tons of soil carbon will release if warming proceeds
needs. Global warming phenomena due to these unchecked to 2 °C [2, 10].
CO2 emissions are one of the greatest environmental concerns There are different technologies which are currently used for
of the current era. Since the industrial revolution the amount CO2 capture and storage. These techniques involve three major
of CO2 has increased in the atmosphere from 280 to 419 ppm steps, namely, capturing, transportation, and storage (Tab. 1).
[1, 2]. A rise in temperature by 1 °C has been reported as com- Ocean and geo sequestration are two of them. These have dis-
pared to pre-industrial revolution and it is expected to observe advantages of high transportation cost and danger of leakage
a rise in temperature up to 6 °C if CO2 emissions are not con- [12, 13]. Public anxiety is also one the shortcomings associated
[4]
————— Prof. Abrar Inayat https://orcid.org/0000-0003-3945-4926
[1]
Prof. Sikander Rafiq, Prof. Asif Jamil, Prof. Muhammad Imran Ra- Department of Sustainable and Renewable Energy Engineering,
shid, Prof. Muhammad Irfan, Prof. Tanveer Iqbal University of Sharjah, Sharjah, United Arab Emirates.
[5]
([email protected], [email protected]) Prof. Farrukh Jamil https://orcid.org/0000-0001-9901-4258,
Department of Chemical, Polymer and Composite Materials Engi- Prof. Muhammad Shahzad Khurram
neering, University of Engineering and Technology, Lahore New Department of Chemical Engineering, Comsats University Islama-
Campus, 54000 Lahore, Pakistan. bad, Lahore Campus, Lahore, Pakistan.
[2] [6]
Prof. Sikander Rafiq Prof. Jibran Iqbal
Department of Food Engineering and Biotechnology, University College of Natural and Health Sciences, Zayed University, P.O. Box
of Engineering and Technology, Lahore New Campus, 54000 La- 144534, Abu Dhabi, United Arab Emirates.
hore, Pakistan. [7]
Prof. Muhammad Shozab Mehadi
[3]
Dr. Muhammad Saeed Ghulam Ishaq Khan Institute of Engineering Sciences and Tech-
Aker Solutions, Renewable Fornebu, Oslo, Norway. nology, Khyber Pakhtunkhwa, Pakistan.
www.ChemBioEngRev.de ª 2023 Wiley-VCH GmbH ChemBioEng Rev. 2023, 10, No. 7, 1–12 1
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with these methods due to increasing ocean acidity and future CO2 removal by absorption in a liquid and CO2 capture by
risks [14, 15]. There is no chance of CO2 leakage in mineral selective membranes are the two most studied techniques.
carbonation technology as it permanently fixes CO2 into stable Membrane technology is a relatively new but promising techni-
mineral carbonates [11]. que in the field of CO2 capture. A semi-permeable membrane
The other methods used for dual benefit are absorption and can selectively remove CO2 from a gas stream containing a
desorption [16], enhanced coal bed methane and oil recovery mixture of gases. Membrane separation technology is a vigo-
(ECBM and EOR). These have disadvantage of leakage of CO2 rous substitute to conventional CO2 capture techniques with
but at the same time have the advantage of enhanced methane efficient energy. Compared to a standard absorption, a mem-
and oil recovery. Cryogenic and gas permeation (membrane brane-based CO2 capture plant is much simpler with a signifi-
separation) processes are also used for CO2 capture (separa- cant difference in footprint.
tion) from its mixture with different gases [17]. The emerging The modular configuration of membranes ensures a linear
technique of hydrate-based gas separation is also useful in this scale-up and makes it easy to maintain [13, 14]. The use of a
respect [18]. When talking about different sequestration tech- hybrid facilitated transport membrane to selectively separate
niques technically and economically, it becomes clear that these CO2 from a gas stream and gas-liquid contactors is relatively
have some disadvantages as well as high operating cost. new, but in the field of gas separation there are many promis-
The alternative to CO2 storage is to use it for making some ing innovations by membrane technology [15, 16]. The mem-
useful chemicals which can be termed as utilization of CO2. It brane technology for CO2 capture is considered as a low-cost
has the advantages of CO2 reduction from the environment and highly efficient solution for the current global scenario of
and formation of the valuable chemicals. It is also economical CO2 emission [17, 18].
and environmentally suitable. Three techniques applied for In literature several polymeric membranes have already been
CO2 utilization are the use in different indirect applications for reported, which show significant CO2/N2 or CO2/CH4 separa-
enhancements, and chemical and biological conversion of CO2 tion. However, these membranes lack mechanical strength and
into useful chemicals. Chemical conversion techniques employ suffer from compaction at higher pressure, which declines the
chemical catalysts, and sufficient amount of energy is required. separation performance [19]. To overcome this problem, nano-
It has further three categories, i.e., thermochemical, photo- fillers/spacers are spread in a polymer matrix to improve the
chemical, and electrochemical conversion. Indirect applications mechanical strength along with maintaining high performance.
are to employ CO2 in the formation of products which can be An appreciable progress has been observed in both permeabil-
further used as energy carrier, and to take it as a solvent in dif- ity and selectivity of CO2 by addition of nanoparticles to
ferent applications. Examples in this respect include using it in mixed-matrix membranes (MMMs). Moreover, these nanopar-
beverages, solvent extraction process, fire extinguishers, and ticles help to improve membrane plasticization by CO2 and
beverage industries [19]. avoid membrane compaction at high pressures [20, 21].
Biological CO2 conversions convert CO2 into useful chemicals Saeed et al. [22] reported the effect of surface-modified mul-
such as biofuels. These are energy-efficient as compared to chem- tiwalled carbon nanotubes (MWCNTs) on the swelling behav-
ical conversion techniques and different innovative concepts and ior of a polyvinyl alcohol (PVA) membrane and suggested that
modification to existing plants are easy to incorporate into these. at optimal loading of CNTs the membrane swelling degree is
The utilization of CO2 is a hot topic but here according to the almost doubled. Saeed and Deng [23] described a mimic
scope of this article is not discussed in detail [12]. enzyme-promoted facilitated membrane embedded with non-
Table 1. CO2 sequestration techniques (comparison) [1].
Name Advantages Disadvantages
Mineral carbonation Permanent storage Low magnesite yield
Sequestration (geo) Massive storage capacity, mature technology, long Leakage danger, high cost, public trust
retention time
Sequestration (ocean) Storage potential, increased Harmful for sea life

residence time
Adsorption (chemical) Efficiency around 90 % Solvent loss, thermal stability characteristics of solvent,
high cost
Separation (membrane) Easy to install, packing density Low efficiency at higher temperatures
Separation (cryogenic) Efficiency of 99.9 % Energy-inefficient, high cost, under development
Hydrate-based gas separation Environmentally friendly process, applicable for Equipment size, high cost, technological immaturity
flue gases, storage potential
EOR Enhanced oil recovery of 8–15 % Energy-intensive process
ECBM Enhanced methane recovery Energy-intensive process
functionalized CNTs and determined that by addition of CNTs of polyimide using tetrabutyltitanate as a precursor of TiO2,
the CO2/N2 separation performance is stabilized at higher pres- they synthesized nanocomposite membranes at variable filler
sure which indicates that nanofillers are helping to avoid com- loadings by uniform dispersion through blending. More than
paction of the selective layer and maintain high separation per- 20 wt % TiO2 in the polymer matrix showed great improve-
formance. MMMs comprising functionalized nanoparticles ment in gas permeabilities for H2 and O2 due to strong interac-
have been studied to facilitate CO2 transport and improve the tions among the membrane moieties as compared to pure poly-
CO2/N2 selectivity [24–26]. Several MMMs have been studied mer matrix (3.7–4.3 times higher). The increased selectivity of
recently that show appreciable improvement in separation per- the gas pairs was attributed to the uniform dispersion of the
formance. filler contents in the matrix as confirmed by optical measure-
ments and transmission electron microscopy (TEM). They sep-
arated two different gases from N2 and observed that the selec-
2 Mixed-Matrix Membranes for CO2 tivity and permeability were higher as compared to pure
Capture polyimide [37].
Few years ago, Cong et al. [38] synthesized a polymeric
2.1 MMM Fabrication membrane using the dispersion technique but with a new inor-
ganic material. They selected CNTs and observed that these
There are different types of processes to fabricate MMMs, e.g., improved the mechanical strength. Moreover, brominated poly
solution blending, in situ polymerization, and sol-gel. One of 2,6-diphenyl-1,4-phenylene oxide was used as base polymer
the most used techniques is solution blending, in which a poly- and developed single-walled carbon nanotubes (SWCNTs) and
mer solution is made by stirring with the dispersion of inor- multiwalled carbon nanotubes (MWCNTs) nanocomposites.
ganic filler. The removing of solvent is necessary during the Nanocomposites with different wt % of SWCNTs and
casting process. This is an easy method, and it deals with MWCNTs were developed. The observed permeability of CO2
almost every type of inorganic filler as they form aggregates at was increased with higher content of CNTs, which was attrib-
the membrane. uted to the enhanced gas diffusivity with filler contents. More-
The other technique is in-situ polymerization that avoids over, they examined that the selectivity of CO2/N2 was similar
formation of aggregates of nanoparticles in the membrane. by introducing CNTs as compared to pure BPPOdp. The maxi-
This technique includes mixing of monomer and nanoparticles mum permeability of CO2 was 155 Barrer at 9 wt % of SWCNTs
of an inorganic filler with each other and then the polymer is and 144 Barrer at 5 wt % of MWCNTs. The ductile module of
obtained as a result of the conversion of monomer owing to the polymer membrane was increased to 67 % by adding 5 wt %
high energy radiation or other situations for the commence- SWNTS, and at 5 wt % MWNTS its modulus was increased to
ment of polymerization. 44 %. The researchers concluded that CNTs saturation to the
In contrast, there is another technique called sol-gel, which polymeric membrane is highly attractive and feasible due to
comprises the mixing of components such as monomers, their robust mechanical properties without affecting the gas
oligomers, or polymers with precursors of inorganic particles separation performance.
followed by hydrolyzation of the precursor which then follows Hillock et al. [39] analyzed a cross-linked modified polymer
condensation to distribute the nanoparticles at the mixed with 1,3-propane diol and SSZ-13 zeolite MMM for gas separa-
membrane. It is a simple method and an even reaction is possi- tion. They evaluated cross linkable polymer 3:2 6FDA-DAM-
ble at appropriate conditions. Distribution of nanoparticles is DABA modified with 1,3-propane diol (PDMC polymer) and
performed properly at the membrane to form homogenized SSZ-13 was incorporated into this polymer. The performance
MMMs [27–35]. of this membrane surpassed the Robeson upper bond curve.
They proposed increased permeability of CO2 up to 89 Barrer
and its selectivity increased to 47.
2.2 CO2 Separation Performance Metal-organic frameworks (MOFs) are used in the field of
MMMs and are considered as a novel concept. Organic par-
Hu et al. studied nanocomposite membranes for gas separation. ticles are introduced in inorganic particles to develop a strong
They used the sol-gel method for developing poly(amide-imide) linkage for the synthesis of MOFs. On the basis of functionality,
membranes packed with TiO2 at lower loadings of 7.5 wt %. They shape, and size, more than 20 000 MOFs have been reported
observed that the membranes synthesized using the TiO2 poly- [40]. MOFs are termed as porous coordination polymers
mer were denser and more rigid compared with pure polymeric (PCPs) [41], porous coordination networks (PCNs) [42], mi-
membranes. It was observed that the permselectivities using croporous coordination polymer (MCP) [43], zeolite-like MOF
nanocomposites for a gas separation pair were high if matched (ZMOF) [44], zeolite imidazole framework (ZIF) [45], metal
with pure poly(amide-imide). This is due to the fact that TiO2 azolate framework (MAF) [46], biometal organic framework
represents strong specific intermolecular interactions with some (bio-MOF) [47], and covalent organic framework (COF) [48].
gases such as H2 and CO2. Furthermore, they suggested that the Usually MOFs possess a fine and definite arrangement along
possible improvement in the selectivity is due to the increasing with numerous advantages which include thermal mechanical
concentration of the ceramic component [36]. stability, high surface area, and high permeability. MOFs can be
Kong et al. found that the incorporation of TiO2 at high pro- designed for different gases to facilitate them by changing the
portions in polyimide membranes is up to 40 wt % for the gas organic linker. This feature makes MOFs favorable over other
pairs H2/N2 and O2/N2 and H2/CH4. By preparing a solution nanoparticles. For gas separation comprising mixtures of CH4,
H2, N2, and hydrocarbons at varying operating parameters,
several membranes have been discussed in literature [49–52].
Despite several advantages offered by MMMs, there are cer-
tain challenges reported by researchers working in the field of
MMMs. Formation of an interfacial layer between an inorganic
nanoparticle and polymer is widely observed in MMMs. Due
to poor adhesion between particles and polymeric matrix, voids
are created because of the poor interfacial interactions between
organic and inorganic phases that result in membrane channel- Figure 2. Schematic structure of an HNT [59].
Furthermore, the surface modification of the HNTs expands

the range of applications. The coated surfaces, e.g., possess a
diverse set of electrical, chemical, and physical properties, mak-
ing them suitable for electronic production and other high-tech
ceramic composite applications, such as fillers in radiation
absorption materials. They may be utilized as molecular sieves
in several applications, including liquid and gaseous mixture
separation, water purification in the refining industry, and acid
amine drainage remediation [54].
4 Polymer-HNT Morphology
HNTs are low-cost, widely accessible one-dimensional nano-
particles that are environmentally benign, mechanically robust,
Figure 1. MMM containing nanofillers dispersed in a polymeric and biocompatible. Subsequently, HNTs are often utilized in
matrix, adapted from Aroon et al. [53]. polymer nanocomposites, and their application in biocompati-
ble and biodegradable composites has proven to be substantial.
Fig. 3 shows the uniform distribution and compatibility of
ing which eventually leads to low selectivity. A schematic dia- HNTs in polysulfone (PSf) films as depicted by scanning elec-
gram of MMMs for CO2 capture is presented in Fig. 1. tron microscopy (SEM) and TEM images. HNTs are readily
available in large quantities and can be dispersed in water as
well as a wide variety of organic solvents. As a result, halloysite
3 Halloysite Nanotubes polymer nanocomposites can be produced by diverse methods,
including solution mixing, melt blending, in situ polymeriza-
Halloysite nanotubes (HNT) are earthy and naturally occurring tion, and spinning [60]. These methods make halloysite
aluminosilicates (Al2Si2-O5(OH)4nH2O) [54]. HNTs exist in polymer nanocomposites simple to process and ensure uniform
various morphologies, e.g., platy, spheroidal, and tubular, de- dispersion. In general, halloysite is hydrophilic, but, in compar-
pending on the crystallization conditions, but the hollow tubu- ison to nanosilica and other layered silicates, it is more hydro-
lar structure having high aspect ratio in the submicrometer phobic. This is because halloysite has a lower density of surface
range is the dominant morphology as illustrated in Fig. 2. The hydroxyl groups at the outer surface; thus, the tube-tube inter-
length of the hollow tube structure varied from 0.2 to 1.5 m, action of a halloysite is not as strong. As a result, it is reason-
while the inner and outer diameters range from 10–30 and able to anticipate that halloysite may be readily disseminated in
40–70 nm, respectively [55]. HNTs, like graphene and MXenes, a wide variety of polymers even when it is not modified.
are investigated as one-dimensional fillers that are readily dis-
persed in water because of their high hy-
drophilicity and smaller size. Water disper-
sion characteristics indicate that HNTs are
utilized for polymer nanocomposites via
solution mixing technique [56].
Since HNTs have a large lumen width,
they may accommodate a wide variety of
molecules, from larger proteins to light gas
molecules including CO2, CH4, O2, and N2
[57]. Due to the tubular structure, HNTs
are often utilized in bioreactors, time-
release capsules, polymer degradation cata-
lysts, template materials, and high-tech
ceramic applications [58]. Figure 3. TEM and SEM picture of halloysite nanotubes in a PSf film.
Liu et al. developed polylactic acid-incorporated HNTs com- to other related inorganic fillers. Chen et al. [68] have devel-
posites by adopting the melt blending method and reported the oped aerogel composites consisting of poly(vinyl alcohol)
thermophysical properties of the composite. In comparison to (PVOH) and nanoscale silica, montmorillonite (MMT), lapon-
neat Poly (lactic acid) (PLA), the HNTs are uniformly dissemi- ite, and HNTs. According to their findings, the HNTs-based
nated and orientated in the host matrix, resulting in better me- aerogel has a significantly improved capability to withstand
chanical attributes such as tensile, flexural, and impact proper- flames than conventional flame retardants.
ties. Moreover, the storage modulus as well as the glass HNTs were also used in the development of MMMs with
transition temperature of PLA-HNT nanocomposites were also water separation characteristics. The insertion of HNTs into
enhanced. Authors also speculate, though the interactions were polymeric membranes altered their physicochemical character-
not developed between PLA and HNTs, but HNTs act as nucle- istics and morphological structure [69]. When 3 wt % of HNTs
ating agent and decreased the cold crystallization temperature. were added to polyacrylonitrile (PAN) membranes, both the
Consequently, not only the crystallinity increased but the vicat pore volume and specific surface area doubled compared to an
softening as well as the thermal degradation temperature of the unmodified membrane. Furthermore, membranes were also
developed composite follows the increasing trend of crystallin- found to be more hydrophilic owing to the presence of hydrox-
ity [55]. yl groups on the surface of HNTs. In general, with increased
It is generally accepted that the level of crystallinity has an HNTs concentration, the water static contact angle (SCA)
effect on the mechanical behavior of nanocomposite mem- decreased. Subsequently, the incorporation of HNTs to polye-
branes. The amorphous phase is strengthened by the crystalline thersulfone (PES) MMMs influenced not only the SCA, but
phase [61], which occurs when the macromolecules are packed also the advancing (ACA) and retreating (RCA) contact angles,
closely together. Therefore, the elastic modulus of a polymer in as well as contact angle hysteresis. ACA is a measure of how
its glassy form rises with increasing crystalline degree. The hydrophobic the membrane surface is overall, and RCA is a
crystalline material’s structural order inhibits the relaxing of its measure of relative hydrophilicity.
macromolecular chains. Therefore, up to a plateau in the rub- HNTs, on the other hand, have a beneficial effect on the per-
bery state, the storage modulus marginally decreases with the meability of MMMs due to their hydrophilic nature and tubu-
glass transition temperature Tg. Amorphous polymers are more lar form. Hydrophilic materials have the tendency to develop a
sensitive to temperature changes in terms of the modulus. For hydration layer, acting as a physical and energetic barrier
temperatures around Tg, the storage modulus of the amor- against foulant adhesion. Additionally, the presence of negative
phous polymer drops dramatically. When the temperature of changes on the surface of HNTs contributes in the resistance to
polymer rises above the Tg, cold crystallization begins, which fouling. HNT is also an excellent absorbent of dyes and heavy
causes an increase in the modulus. In cold crystallization, the metals due to its high surface area and porous microstructure.
polymeric matrix chains are quenched to a disordered struc- Buruga et al. [1] found that a 10 % HNTs loading (in casting
ture. After being heated above the Tg, these chains mobilize dope) increased the pure water flux (PWF) from 144 to
enough to realign into crystallites. This results in a significant 1236 L m–2h–1 in microfiltration (MF) membranes and from 84
increase in the modulus’s magnitude. to 996 L m–2h–1 in polystyrene (PS) membranes. Electrospun
On the other hand, gels such as hydrogels, aerogels, and nanofibrous PAN membranes were shown to have increased
ionic gels, are polymers with potential uses in a variety of disci- permeability by 13 % by the 3 wt % HNTs. In the presence of
plines. Poor mechanical characteristics and increasing brittle- HNTs, the water permeability of polyvinyl chloride (PVC),
ness following swelling were two well-known disadvantages PES, and Polysulfone (PSU) ultrafiltration (UF) membranes
that hindered their practical applicability. The incorporation of was also increased.
nanoparticles into the hydrogel network has been reported to It was also discovered that modifying polymeric membranes
improve stiffness, dimensional stability, and thermal stability with HNTs improved their fouling resistance. In the case of
[62, 63]. Haraguchi et al. used HNTs as cross-linking agent for PVC UF membranes, the sample containing 2 wt % HNTs
the development of poly(N-isopropylacrylamide) hydrogels. compared to the pure PVC membrane [1] had the best anti-
Compared to poly(N-isopropylacrylamide) hydrogels with fouling performance, but in the case of PES/HNTs membranes
organic cross-linkers, the presence of HNTs has shown superior the maximum resistance to fouling was found following the
mechanical stability [64]. A similar trend was reported by Liu introduction of 0.5 wt % HNTs vs. PES. Fig. 3 presents the SEM
et al. when they prepared an aerogel by using 1,4-phenylene and TEM images of HNTs dispersion in PSf films.
diisocyanate-modified HNTs [65].
Flame redundancy and heat resistance are two outstanding
characteristics that make HNTs versatile fillers. Flame-retard- 5 Performance of HNT-MMMs for CO2
ant materials can inhibit or retard the combustion process, Separation
which makes them suitable in the defense, aerospace, and fire
industries, among others [66]. The tubular structure and in- Hashemifard et al. modified HNT with N-(aminoethyl)-amino-
organic nature of HNTs induced heat resistance characteristics. propyltrimethoxysilane (AEAPTMS), which was then inte-
The presence of hydroxyl groups in tubular structures, on the grated into a polyetherimide (PEI) matrix to study dispersion
other hand, would undergo a dehydration condensation proc- and CO2 permeance [57]. The HNT/PEI MMM selectivity ini-
ess at high temperatures, allowing them to produce water tially dropped, but after optimizing the priming procedure and
vapors and therefore provide a cooling effect [67]. The flame sonication, HNT platelet selectivity and dispersion increased. It
retardant properties of the HNTs are even superior compared is also revealed that a higher concentration of silane molecules
leads to a greater extent of tortuosity and, as a result, improved performance in the humidified condition as compared to
selectivity. Furthermore, the inclusion of an amine group in SPEEK/HNTs MMMs, exceeding the Robeson’s upper bound
AEAPTMS/HNT/PEI MMMs improves CO2 permeability and stated in 2008. In a mixed gas test, for more than 120 h, the
selectivity through the membrane by increasing CO2 adsorp- PANI-d-HNTs-0.9 % MMM displayed long-term performance
tion. When compared to a pristine PEI membrane, the optimal stability with a high CO2 permeability of 1250 Barrer and a
results attained with 0.5 wt % silylated HNT exhibited a 28 % high CO2/N2 selectivity of 82. PANI-d-HNTs with an abun-
increase in permeance and 7 % improvement in selectivity, re- dance of amine groups enabled the transfer of CO2 at a high
spectively. rate via multilayer-assisted transport channels.
Due to its durability, rigidity, good strength, and thermal In another study [74], HNTs Pebax nanocomposite mem-
properties, PSf is frequently employed to produce a continuous branes were synthesized at various loadings up to 15 wt % and
matrix phase in the production of MMMs. Gunasakaran et al. compared with modified HNTs by treating it in basic solution
developed PSf membranes with activated carbon and HNTs as at pH 11. The results showed improved porosity, pore volume,
fillers and evaluated their thermophysical properties, as well as and specific surface area of the modified membranes. CO2/
CO2/CH4 permeance and separation performance [70]. In CH4 permeation tests results indicated that the modified HNTs
terms of gas separation performance, the MMM containing nanocomposites possessed higher separation performances
HNTs outperformed the plain membrane and PSf-AC MMMs. with upper limits of CO2 permeability of 144.4 Barrer and se-
At 2 bar pressure, the addition of HNTs to the PSf matrix en- lectivity of 27.2 than the raw HNTs nanocomposite membranes
hances the selectivity to 15.83, compared to 11.93 for the neat with 132.1 Barrer and 18.6, respectively. It was concluded that
membrane and 7.06 for PSf-AC MMMs. Furthermore, incor- this increased separation performances (selectivity by two-fold)
porating HNTs into the PSf polymeric matrix enhances not on- were due to better dispersion of modified HNTs in the polymer
ly the membrane’s tensile strength and morphological charac- matrix which provided better CO2 interaction with the matrix
teristics, but also its CO2/CH4 gas separation performance due to the presence of significant –OH groups on nanofillers
when compared to activated carbon. surfaces. Modified HNTs membranes approached Robeson’s
In another work, Pebax-1657 was used as the base polymer upper bound without surpassing it.
for manufacturing pristine and HNT-loaded MMMs. The For comparison between the functionalized and non-func-
permeability of pure gases (CH4 and CO2) across developed tionalized HNTs, the incorporated nanocomposite membranes
neat and MMMs were measured experimentally, at room with some modifications on HNTs structural properties con-
temperature and various pressures. The acquired results indi- siderably enhance membrane separation performances. This is
cated that the MMMs had increased CO2 permeability when due to the strong affinity for CO2 with membrane moieties
compared to the pure Pebax membrane. For instance, such as amine groups, silanes having better dispersion and in-
increasing the integrated HNTs loading from 0 to 2 wt % teractions with the matrix. The improved selectivities attained
increased the CO2 permeability from 76 to 101 Barrer at a with functionalized HNTs may be a result of the more tortuous
pressure of 4 bar [71]. nature of their penetration pathway, the rigidified polymer
Afshoun et al. developed poly(ether-block-amide) Pebax/ chains, or the primarily partial pore blockages of the fillers.
PEI thin-film composite membranes and examined their
CO2/CH4 gas separation performance using pure as well as
mixed gas permeation experiments [72]. HNTs were also in- 6 Quantitative Survey of HNT-Based
corporated in a Pebax layer to synthesize Pebax-HNT/PEI Paper Publications
MMMs. It was reported that HNTs loading enhanced the
CO2 permeance, however, the selectivity rose initially till A literature survey was carried out using scopus to determine
2 wt % HNT loading and thereafter the opposite trend pre- the total publications on the topic of halloysite and MMMs up
vailed. Additionally, the gas sorption test revealed that adding till now. The search result for the word "mixed-matrix mem-
HNT enhanced the quantity of CO2 adsorbed. Mixed gas branes" resulted in 2781 documents till 2021. The trend of pub-
permeation (CO2, CH4), on the other hand, demonstrated lications in the last decade is presented in Fig. 4.
that the separation factor was always lower than the optimal Among these documents only 296 contained the concept of
selectivity value. Interestingly, increasing the feed CO2 con- membrane and halloysite. A trend of publications in this field
centration enhanced the CO2/CH4 selectivity for the control for the last 15 years is presented in Fig. 5.
Pebax/PEI composite membrane. Conversely, with increased Furthermore, the number of publications containing halloy-
CO2 concentration in the feed stream, the selectivity of the site MMMs for CO2 capture is very few (22) as indicated in
Pebax-HNT/PEI membrane dropped. Fig. 6.
Wang et al. reported the inclusion of polyaniline-decorated Similarly, patent-based search was conducted on halloysite-
halloysite nanotubes (PANI-d-HNTs) into sulfonated MMMs. It was found that a significant number of patents for
poly(ether-ether ketone) (SPEEK) to yield high-performance halloysite-MMMs are reported each year out of which few pat-
MMMs for CO2/N2 separation [73]. Electrostatic interaction ents without any considerable direct relevance in the field of
and hydrogen bonding were employed to improve the inter- halloysite-MMMs for CO2 capture are reported; however, the
facial compatibility of the SPEEK matrix and PANI-d-HNTs, data is still summarized in Fig. 7.
resulting in MMMs with superior mechanical properties
when compared to pure SPEEK membranes. SPEEK/PANI-d-
HNTs MMMs showed considerably improved CO2 separation
450 7 Conclusions
400
Membrane technology especially in the
350 area of gas separation promises high
300 efficiency of removal at low cost, small-
PUBLICATIONS
er footprint, and compact equipment.

250 Conventional polymeric membranes
200 lack high selectivity, permeability, and
mechanical strength. MMMs produced
150
by incorporating nanoparticles in a
100 polymeric matrix improve mechanical
stability, prevent compaction at high
50
pressure, and enhance its separation
0 performance but sometimes voids in
2007 2008 2009 2010 2011 2012 2013 2014 2015 2016 2017 2018 2019 2020 2021 the polymeric matrix are created.
YEAR Among the several MMMs, halloysite
MMMs exhibit high separation perfor-
Figure 4. Publications on the topic of MMMs (2007–2021).
mance and good tailor ability. Because
of their unique tubular shape, HNTs
have found applications in various sec-
60
tors, including biomedical, composites,
electronics, and related areas.
50 Among various HNTs morphologies,
the hollow tubular structure having a
high aspect ratio of < 1 mm is domi-
40
nant. They provide better dispersion
PUBLICATIONS
characteristics due to high hydrophilic-

30 ity to be utilized for polymer nanocom-
posites along with larger lumen width
necessary to accommodate a wide vari-
20
ety of molecules including proteins and
gas molecules of CO2, CH4, O2, and
10 N2. Polymer nanocomposites contain-
ing HNTs have been the subject of ex-
tensive studies. Previous studies indi-
0 cated that in contrast to conventional
2007 2011 2012 2013 2014 2015 2016 2017 2018 2019 2020 2021 composites the HNTs nanocomposites
YEAR exhibited much better mechanical per-
Figure 5. Publications on the topic of halloysite MMMs (2007–2021). formance, thermal stability, and flame
retardancy coefficient of thermal ex-
pansion.
The uniform dispersion of HNTs is a
7 consequence of the co-coagulation
process as well as the strong interfacial
6
network that is brought about by the
5 hydrogen bonding among the moieties
of the matrix. Gas permeation results
PUBLICATIONS
4 indicated increased CO2 separation

performances of the modified HNT
3 membranes compared with unmodified
filled/unfilled membranes. Various rea-
2
sons were reported which mostly high-
1 lighted the increase in absorptive ca-
pacities due more active sites of bond
0 formation apart from improved disper-
2007 2014 2015 2017 2018 2019 2020 2021 sion and favorable interfacial interac-
YEAR tions among the membrane moieties
with CO2 and efficient gas transport
Figure 6. Publications on the topic of halloysite MMMs for CO2 capture (2007–2021).
8
6
PUBLICATIONS
0
Figure 7. Patents in the field of halloy-
2007 2008 2011 2012 2013 2014 2015 2016 2018 2019 2020 2021
site MMMs for CO2 capture (2007–
YEAR 2021).
through channeling, i.e., formation of high-speed road-like

pathways for efficient separation. Muhammad Saeed is currently
In most of the studies the membranes were unsuccessful to working as Subject Matter Ex-
surpass Robeson’s upper bound which provides a prospecting pert (SME) CCUS and Hydro-
challenge for improvement. Literature and reviews on MMMs gen in Aker Solutions ASA. He
containing halloysite for CO2 capture are still scarce but con- has participated in several con-
clusive to state that halloysite nanotubes-based MMMs are cept studies, FEED and EPC
promising candidates for CO2 capturing. projects in the field of CO2
capture, storage, and utiliza-
tion. He completed his Ph.D.
Conflicts of Interest in chemical engineering at the
Norwegian University of
The authors declare no conflict of interest. Science and Technology
(NTNU), Trondheim, in 2015.
The topics of his research work
Sikander Rafiq is Professor in were membranes and membrane contactors for post com-
Chemical Engineering and bustion CO2 capture.
Chairman, Food Engineering
& Bitotechnology Department Asif Jamil holds a Ph.D. in
at University of Engineering Chemical Engineering. He is
and Technology, Lahore, New currently associated with Uni-
Campus, Pakistan. He received versity of Engineering and
Ph.D. in Chemical Engineering Technology, Lahore (New
from Universiti Teknologi campus) and actively involved
PETRONAS, Malaysia in 2013 in ‘‘Membrane based Separa-
and Post Doctorate from Nor- tion Processes’’ research group.
wegian University of Science and Technology, Norway in His research interests are in
2016. He has a strong focus on the development of mem- the fields of polymeric materi-
branes for various applications including CO2 capture for als and membrane technology.
gas separation, wastewater treatment, modeling, and renew- His current recent research ac-
able energy. tivities focus on membrane
processes for carbon dioxide
separation, biogas enrichment, water treatment, as well as
mechanical characteristics of polymeric composites.
Muhammad Imran Rashid Abrar Inayat is an Associate
has worked in Dawood Her- Professor of Sustainable and
cules Fertilizer Limited for four Renewable Energy Engineering
years. He earned his Ph.D. de- at the University of Sharjah,
gree from the University of UAE, where he has been since
Newcastle, Australia. He is As- 2015. He received a B.Sc. in
sociate Professor at the Uni- chemical engineering from the
versity of Engineering and University of the Punjab,
Technology, Lahore. He tea- Pakistan, and M.Sc. in energy
ches Health, Safety and Envi- engineering (sustainable ener-
ronment classes and his re- gy systems) from the Mälardalens University of Sweden. He
search interests include coal received his Ph.D. in chemical engineering from the Univer-
utilization, process safety man- siti Teknologi PETRONAS, Malaysia. His main research
agement, renewable energy, fields are biomass and bioenergy, process system engineer-
and chemical engineering. ing, hybrid energy systems, CO2 capture and utilization.
Muhammad Irfan is currently Farrukh Jamil is working as

working as Assistant Professor Assistant Professor at the De-
at the University of Engineer- partment of Chemical Engi-
ing and Technology, Lahore, neering, Lahore Campus,
Pakistan. He completed his Pakistan, having more than
Ph.D. studies at the East China eleven years professional ex-
University of Science and perience in academia and
Technology, Shanghai, China industry. Specifically, his re-
in 2020. His research interests search focuses on the engineer-
include CO2 utilization, bio- ing of agricultural waste for
mass densification, sustainable the production of renewable
environment, greenhouse gas energy, biofuels, and mem-
mitigation technologies, bioenergy, and biofuels production, brane technology.
microbial enhanced oil and energy recovery, and biotrans-
formation of waste. Jibran Iqbal received his Ph.D.
degree in analytical chemistry
Tanveer Iqbal worked on sur- in 2012 from the School of
face mechanical characteristics Chemistry and Molecular En-
of polymers with Prof. B. J. gineering, East China Univer-
Briscoe at the Imperial College sity of Science and Technology
London. His principal area of (ECUST), Shanghai, China.
research is surface mechanical During his Ph.D. he developed
characterization/tribological novel green and sustainable
studies of polymers and their chemistry tools and techniques
composites at micro- as well as for highly sensitive environ-
nanoscales. In particular, he mental pollutants analysis.
has worked on the surface me- Currently he is an Associate
chanical properties based on Professor at the Zayed Univer-
indentation and scratching re- sity, United Arab Emirates. His
sponse of amorphous and research is focused on the interface between environmental
semicrystalline polymeric surfaces and their composites. chemistry, analytical chemistry, materials, and nanotechnol-
Surface deformation mechanisms and hardness determines ogy for the development of sustainable water solutions and
product life and usage and hence play a vital role in material trace analysis of heavy metals and emerging organic pollu-
selection and design. He has expanded his research domain tants. He has keen interest in developing nanocomposite,
to include tribology of surfaces, polymeric nanocomposites, nanoporous, and 2D materials for potential applications in
biomaterials synthesis and applications, energy and envi- catalysis, separations, SERS, sensing, and clean energy.
ronment.
MOF metal-organic framework
Muhammad Shahzad Khur- MWCNT multiwalled carbon nanotube
ram is an Assistant Professor PANI-d-HNT polyaniline-decorated halloysite nanotube
at the Chemical Engineering PCN porous coordination network
Department of COMSATS PEI polyetherimide
University Islamabad, Lahore PES polyethersulfone
campus, Pakistan. He obtained PSf polysulfone
his Ph.D. degree from the PVA polyvinyl alcohol
Konkuk University, Republic PVC polyvinyl chloride
of Korea, in 2015. His main PVOH poly(vinyl alcohol)
area of research is renewables, PWF pure water flux
waste to energy, and CO2 cap- RCA retreating contact angle
ture. SCA static contact angle
SEM scanning electron microscopy
SPEEK sulfonated poly(ether-ether ketone)
SWCNT single-walled carbon nanotube
Muhammad Shozab Mehdi
Tg glass transition temperature
earned his B.Sc. in chemical
TEM transmission electron microscopy
engineering from NFC IET,
UF ultrafiltration
Multan, Pakistan in 2004. He
ZIF zeolite imidazole framework
completed his Ph.D. in chemi-
ZMOF zeolite-like metal organic framework
cal engineering from PIEAS,
Pakistan in 2013. During his
Ph.D., he also got a chance to
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The incorporation of halloysite Advances in Halloysite Nanotubes
nanotubes (HNTs) in mixed-matrix (HNTs)-Based Mixed-Matrix
membranes presents an opportunity for Membranes for CO2 Capture
more efficient carbon dioxide capture.
The current status for potential Sikander Rafiq*, Muhammad Saeed,
applications of HNTs-based membranes Asif Jamil, Muhammad Imran Rashid,
for gas separation is reviewed. Further Muhammad Irfan, Tanveer Iqbal,
research is needed to bridge the Abrar Inayat, Farrukh Jamil, Jibran Iqbal,
knowledge gaps and optimize the Muhammad Shahzad Khurram,
future application of HNTs-based Muhammad Shozab Mehadi
membranes for gas separation.
ChemBioEng Rev. 2023, 10 (X),
XXX L XXX
DOI: 10.1002/cben.202200041

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Advances in Halloysite Nanotubes (HNTs)-Based Mixed-

Matrix Membranes for CO2 Capture

1 Introduction trolled, and eventually the atmospheric CO2 concentration will

Table 1. CO2 sequestration techniques (comparison) [1].

Name Advantages Disadvantages

Mineral carbonation Permanent storage Low magnesite yield

Sequestration (ocean) Storage potential, increased Harmful for sea life

Separation (cryogenic) Efficiency of 99.9 % Energy-inefficient, high cost, under development

EOR Enhanced oil recovery of 8–15 % Energy-intensive process

ECBM Enhanced methane recovery Energy-intensive process

Furthermore, the surface modification of the HNTs expands

er footprint, and compact equipment.

characteristics due to high hydrophilic-

4 indicated increased CO2 separation

through channeling, i.e., formation of high-speed road-like

Muhammad Irfan is currently Farrukh Jamil is working as

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