Chemical Process Equipment (2023) DOI: 10.23977/chepe.2023.

010101
Clausius Scientific Press, Canada ISSN 2616-2539 Vol. 1 Num. 1

Application of Synthesized Metal Organic Frameworks of

Silver Benzene-1, 4-Dicarboxylate on Crude Oil Spill
Orodu Victor Enearepuadoh*, Abasi Cyprian Yameso, Dikio Ezekiel Dixon
Chemical Sciences Department, Faculty of Science, Niger Delta University, Wilberforce Island,
Bayelsa State, P.M.B 071, Nigeria
*
Corresponding author: [email protected]

Keywords: Synthesis; Crude oil; Spillage; Remediation; Composites

Abstract: This research synthesized, characterized, and applied the metal organic framework
of silver benzene 1, 4-dicaboxylate for crude oil adsorption on water, which was simulated.
Silver-metal organic frameworks (Ag-MOFs) were synthesized by reacting hydrated silver
nitrate, AgNO3.6H2O, with 1, 4-benzenedicarboxylic acid (BDA) in N, N-
dimethylformamide as a solvent. Solvothermal method was utilized for the process. The
MOFs obtained were studied by Fourier transform infrared spectroscopy (FTIR), scanning
electron microscopy (SEM), and energy dispersive x-ray spectroscopy (EDX). The
adsorbent surface had large pores, and SEM micrographs revealed a mixture of particles
with tetrahedral, flat, or plate-like shapes. Ag, C, and O, had an elemental composition of
50.9%, 29.6%, and 19.5%, according to EDX respectively. An adsorption research was done
using 1 mL, 2 mL, 3 mL, and 4 mL of crude oil at adsorbent (Ag-MOF) doses of 0.2 g, 0.4
g, 0.6 g, 0.8 g, and 1 g for the adsorption of the crude oil from 50 mL of distilled water. The
data obtained revealed that 0.2 g adsorbed 0.7 mL, 0.4 g adsorbed 0.8 mL, 0.6 g adsorbed
0.9 mL, and 0.8 g and 1.0 g of Ag-MOF adsorbed 1 mL. 1g of Ag-MOF applied to different
volumes of the crude oil, showed an adsorption of 100% of the 2 mL, 2.9 mL (96.67%) of
3 mL, and 3.7 mL (92.5%) of 4 mL. The result of the effect of pH, showed an excellent
adsorption at the pH used. Composites with clay and charcoal were used for the adsorption
of the crude oil. The composite with clay was good, but not as good as charcoal for
adsorption of crude oil. These results imply that an optimized quantity of Ag-MOF can be
utilized in crude oil spill remediation in our environment.

1. Introduction

Metal Organic Frameworks (MOFs) are crystalline complexes made up of organic multidentate
linkers and metal ions. Organic magnets made of crystalline coordination polymers appear to be a
potential alternative (Lopez, 2018). By turning their organic ligands into metal centers and inserting
functional inorganic molecules in porous MOFs, these materials exhibit magnetic characteristics that
may be tailored to the molecular scale (Zhou and Kitagawa, 2014). Hosting guest molecules in MOFs
has been discovered to dramatically increase electrical conductivity (Talin, 2014). Degayner, Jeon,
Sun, Dinca, and Harris discussed the linking of redox-active ligands (2017). According to Darago,
Aubre, Yu, Gonzalez, and Long, pyrrazine can cause long-range charge transfer, intense magnetic

1
conversion, high conductivities, and magnetic arrangement (2015). According to Dong (2018)
conjugated MOFs with multilayer formed with electrical conductivities of 105 Sm-1 have been created.
Kambe, (2013) developed MOFs by linking N, O, S of ligands with transition metal ions, which
showed π-d conjugation in 2-dimentional planes. Many metal ions proffer diverse coordination and
geometries, (Lingjuan, 2012).
MOFs are the most current compounds that may be used as alternative adsorbents in a variety of
industrial and environmental studies, according to Ferey, Draznieks, Serre, and Millange (2005).
MOFs may be used to remove pollutants from gas and separate it, (Mueller,2006), and gas storage
(Gallo and Glossman 2007). Both Wu, Hu, Zhang, Lin (2005) and Chen, Yang, Zapata, Lin, Qian,
and Lobkovsky (2005) reported on drug delivery and catalysis applications of MOFs. According to
Rowsell, Spencer, Eckert, Howard, and Yaghi (2005), MOFs contain a number of characteristics that
enable them to be precisely prepared, rigid, and flexible. Philip, Christopher, Erling, Alexander,
Michael, Jürgen, Bernhard, Warnan, and Fischer (2021) described how they employed a molecular
catalyst contained in a metal-organic framework (MOF) to improve the performance of a molecular
catalyst. YameiSun, Xue, Liu, Jia, Li, Liu, Lin, Liu, Liu, Li and Su., (2021) prepared NiRu0.13-BDC,
which they said exhibited noteworthy hydrogen emission activity at all pH. Hydrogen is used as a
fuel and its storing in MOF materials was presented by Yaghi, Eubank, Forster, (2009). Brandon,
Parker, Paley, Gonzalez, Biggins, Oktawiec, and Long, (2019), found that individually, Co2+(m-
dodbc) and Ni2+(m-bobdc) were useful to isolate 1-butene from 2-butene isomers.
In 2020, examined papers on MOFs by Giliopoulos, Zamboulis, Giannakoudakis, Bikiaris, and
Triantafyllidis offered a comprehensive overview of all MOF nanocomposites' applications in
biomedical devices. Andriotou, Diamantis, Zacharia, Itskos, Panagiotou, Tasiopoulos, and Lazarides
(2020) showed that lanthanide MOF materials they developed were effective for temperature sensing.
2D metal-organic framework created by chemical vapour accretion was studied by James Claire,
Solomos, Kim, Wang, Siegler, Crommie, and Kempa., (2020). They concluded that the devices might
be integrated into detectors and actuators based on their findings. Cameron, Carpenter-Warren,
Alexandra, and Slawin (2021) used Methanol/water (MeOH/H2O) reagent to make three coordination
polymers with varied dimensionalities, which were analyzed using single-crystal X-ray diffraction.
Posidona oceanica (L.) was employed as a biosorbent for crude oil spill cleaning in saltwater by Senda
and Amjad (2019). Oil is a key source of energy in contemporary industries, as raw materials for
chemicals and synthetic polymers, according to Senda and Amiad (2019). Mircea and Long (2008)
utilized MOFs in gas purifications of methane, which they said was fast. Andrea, Sudik, Adrien,
Wong-Foy, Keeffe, and Yaghi, (2006) applied MOFs for the detection of hydrophilic gases like
ethanol and methanol.
Silver is a group 11 element with atomic number 47, mass number 108, three major oxidation
states (0, +1, and +2), and two naturally occurring isotopes, (Egorova and Revina,2000). The
manufacture and uses of silver nanoparticles were reviewed by Kholoud, Abou, Ala, Abdulrhman,
and Reda. (2010). They claimed that noble metal nanoparticles, like silver, had noticeable physical,
chemical, and biological characteristics from their counterparts.
Metal-organic frameworks, according to Adedibu, Tella, and Isaac (2012), are a kind of porous
polymeric compounds comprising metal ions connected by organic bridging ligands of metal ions
and the organic component, and they perform best at extremely low temperatures. Hussein, Jin, Ha-
Ming and Wang (2013) investigated the adsorption of CO2 and CH4 on amino-functionalized Zr-
MOF nanoparticle.
Hiroyasu, Kyle, Michael, Yaghi (2013) investigated metal-organic framework chemistry and
applications. According to their review, reticular synthesis establishes connections, resulting in
crystalline metal-organic frameworks (MOFs).
According to JoséMara, Susana, Cherif, Youssef, and Alejandro (2016), their findings showed that

2
using MOF-5 has a lot of potential for use in environmental protection, particularly the removal of
lead present in tap water and industrial waste.
Xili Cui, Niu, Shan, Yang, Hu, Wang, Lan, Li, Wojtas, Ma and Xing. (2020), employed ZU-61
and it was used to separate isomers of xylene., Antypov, Shkurenko, Bhatt, Belmabkhout, Adil,
Cadiau, Suyetin, Eddaoudi, Rosseinsky and Matthew (2020), demonstrated that the progressive
activity of two framework-forming components, numerous atomic anions and pyrazines, influence
both diffusion and separation. MOFs are most favourable in storing gases, James Mitchell crow,
(2012). Cu-MOF was created by Orodu and Dikio in 2021 and utilized for crude oil adsorption. It
was established that Cu-MOFs were effective adsorbents. This research aim to synthesis, characterize
and apply metal organic framework of silver for crude oil adsorption on water in the Niger Delta
Region of Nigeria. The process was simulated in the laboratory.

2. Materials and Methods

2.1 Materials

Reagent used are; N,N-Dimethylformamide [HCON(CH3)2 DMF,99.8%; Silver nitrate,

AgNO3.6H2O,98%,Sigma-Aldrich],Methanol,CH3OH, 99.9%; Sigma- Aldrich, Magnetic stirrer,
Beaker (250 mL), Electronic Heating mantle, Measuring cylinder, Filter paper, Reflux kit, Electronic
weighing balance, Centrifuge machine, pipettes, thermometer, separating funnel, shaker. Crude oil
was collected from the Etelebou well 11T, Gbarain in Bayelsa State, and clay and charcoal were
procured from Warri in Delta State. Nigeria.

2.2 Methods

2.2.1 Synthesis Procedure

Silver metal organic framework (Ag-MOF): Silver MOFs were synthesized by solvothermal
method. 50 mL DMF was transferred into a round bottom flask, with 1.6897 g AgNO3 and 1.6613 g
benzene 1,4-carboxylic acid and mildly stirred. The solution was transferred into the 250 mL round
bottom flask, to reflux for 4 hours at 1200C while stirring, a silver coloured crystal was formed at
1200C in about 1 hour 29 minutes. The solution obtained was centrifuged and a solid Ag-BDA was
left behind; after decanting. Several methanol washes were performed before the crystals were
produced and oven-dried for 30 minutes at 40°C.
2.2.2 Characterization.
A Fourier transform infrared (FTIR) spectrometer (Perkin Elmer Instruments, USA) was used to
characterize the as-synthesised Ag-MOF for any existing functional groups. The scanning range was
400–4000 cm-1. An energy dispersive x-ray (EDX) detector attached to a scanning electron
microscope (SEM) was used to analyze the surface morphology.
2.2.3 Adsorption Study.
Adsorption studies was carried out using the as- synthesized Ag-MOF. The adsorbate was crude
oil. For the adsorbent dose investigation, the masses of 0.2 g, 0.4 g, 0.6 g, 0.8 g, and 1.0 g of Ag-
MOF were weighed and placed in various conical flasks with 50 mL distilled water. Afterwards, 1
mL of crude oil was added to every sample that had been weighed. After that, the mixture was shaken
for 30 minutes. Volume concentration variation was used to determine the adsorbent capacity for
crude oil in water with respect to a constant mass of adsorbent. This was done by altering the amount

3
of crude oil utilized, using 1.0, 2.0, 3.0, and 4.0 mL, and utilizing 1 g of Ag-MOF. The composite
was prepared by weighing 1:1 ratio of both MOF/clay and MOF/charcoal. MOF and charcoal and
MOF were weighed in a 1:1 ratio to create the composite. For the batch adsorptions, 1 g of MOF,
clay, and charcoal were utilized in total. The study used pH values of 4.4, 6.85, and 9.0 to examine
the impact of pH on adsorption.

3. Result and Discussion

Plate 1. Oven dried silver - MOF sample obtained from synthesis.

Figure 1 below, gives us an idea of how the coordinated-polymer chains looks like on production
within the molecule that was obtained during the synthesis.

Figure 1: Ag-MOF conceivable bonding and repeating units.

3.1 Fourier Transform Infrared Spectroscopy (FTIR) Analysis.

The Fourier transform infrared spectrum of BDA is presented in figure 2. Fourier transform
infrared studies provide information in respect of the functional groups and various metal ions present
in the as-synthesized material. The expected functional groups are C=O, C-H, C=C, C-C, C-O, and
O-H, and their assignments are presented in table 1.
The reaction of the metal with BDA is expected to give a similar spectrum to the functional groups
present in the BDA.
An absorbance vs wavenumber plot of the Ag-MOF values in Figure 2's FTIR spectrum is shown
(cm-1). A ring in-plane C-H stretch at the 3091 cm-1 wavenumber location reveals the presence of
alkanes with robust bond strengths. At the 1514 cm-1 wavenumber position, a bending is present
which has medium to strong bond strength. At 1356 cm -1 wavenumber position, C-O stretch is present
which has a weak bonding strength. At 1086 cm-1 wavenumber position, a ring in- and out-of- plane
bending is present which has a variable strength. At the 736 cm-1 wavenumber C-H bending aliphatic
is present which has a weak strength. At the 528 cm-1 wavenumber a C-H bending in C=C-H is present
which has a medium to strong strength. Figure 3, below is the original ftir spectrum of the BDA used
for the synthesis. When compared with the wavenumber gotten in figure 2 as shown in table 1, it

4
showed variations in the wavenumbers confirming that there a reaction and a new product formed.

100
90
80
70
3091
Absorbance

60
50
40
1089
30
20
816
528 1514
10
1356
0 736
350 850 1350 1850 2350 2850 3350 3850
wavenumber

Figure 2: FTIR spectra of as-synthesized of Ag-MOF.

100

90
Absorbance (a. u)

80 1160
3160
70
674 965
60

50 518
751 822 1390 1530
40
350 850 1350 1850 2350 2850 3350 3850 4350
Wavenumber (cm-1)

Figure 3: FTIR spectrum for bezene-1,4-dicarboxylic acid.

Table 1: Comparison of FTIR wavenumbers (cm-1) of Ag-MOF and BDA after synthesis.
Sample Wave number (cm-1)
BDA 3160 1530 1390 1160 1020 965 822 751 674 518
Ag-MOF 3091 1514 1356 1145 1089 1011 888 816 736 528
Table 1 shows the wavenumbers for the peaks that appeared for the metal organic framework of
silver MOF and 1,4-benzene- dicarboxylic acid. The observed change in wavenumbers from the
FTIR spectrum has shown that, there was formation of the Ag-MOF. The absorption band of silver
and 1,4-benzenedimethylcarboxylic acid lies in the region of 528 and 518 cm-1 in the spectra. The
assigned aromatic C-H stretching vibration originates from 1,4-benzenedicarboxylic acid. The weak
and strong bands at 736 and 748 cm-1 separately are assigned residues of C=C stretching vibration
beginning from the C=C bonds of the 1, 4 benzenedicarboxylic acid and C-C skeletal vibration of the
ring.

5
3.2 Scanning Electron Microscopic (Sem) Spectrum.

Using a scanning electron microscope, the surface morphology of the as- synthesized metal
organic framework materials was investigated (SEM). Figures 4(A) and 4 (B) show the SEM of the
as-synthesised material at two magnifications.

Figure 4(A): SEM image of Ag-MOF (x20 µm). (B): SEM image of Ag-MOF (x10 µm).
The SEM images on all the magnifications show an adsorbent surface with spacious pores and an
assemblage of particles having tetrahedral, flat or plate-like structures.
The porous surface morphology revealed by SEM image may be responsible for high adsorption
of the crude oil.by the Ag-MOF adsorbent.

3.3 Energy Dispersive X-Ray. (Edx) Spectroscopy

The metal components in the as-produced material are disclosed by EDXS, a powerful
characterization technique. This is a perfect indicator of the substance's efficient manufacture and,
unmistakably, its purity. In the silver MOF EDXS, just the elements oxygen, carbon, and silver are
visible (figure 5). Silver's elemental makeup is 50.9 percent silver, 29.6 percent carbon, and 19.5
percent oxygen. At 3.0 keV, the Ag peak occurred. It is isotope-free and pure. The carbon and oxygen
are evidences of the metal - CO linkages in the as-synthesized materials.

Figure 5: Benzene-1,4-dicarboxylic acid (BDA) (Terephthalic Acid) Linker of Silver Metal Organic
Framework (Ag-MOF) using Energy Dispersive X-ray Spectroscopy (EDX).

3.4 Adsorption Results

Table 2 and Figure 6 illustrate the impact of adsorbent dosage on the adsorption of crude oil by
Ag-MOF.
The result shows that the adsorption of crude oil by Ag-MOF increased with an increase in the
dosage of samples until an equilibrium was established at 0.8 g for gold and 1.0 g for silver. The

6
percentage adsorption for silver MOF ranged from 70–100%. The high percent adsorption indicates
the as-synthesized Ag-MOF could pass for a good adsorbent for crude oil.
Table 2: Effect of adsorbent dose on crude oil adsorption by Ag-MOF
Mass of Ag-MOF in gram(g) Volume of crude oil Adsorbed (mL)
0.2 0.7
0.4 0.8
0.6 0.9
0.8 1.0
1.0 1.0

1.2 4
3.5

volume of crude oil

1
Adsorbance (mL)

3
0.8

adsorbed
2.5
0.6 2
0.4 1.5
1
0.2 0.5
0 0
0 0.5 1 1.5 0 2 4 6
mass of Ag-MOF adsorbent volume of crude oil/1g of Ag-MOF

Figure 6: Effect of adsorbent dosage on the Adsorption of crude oil by Ag-MOF. And Figure 7:
Volume of Crude oil in (mL)/1g of Ag-MOF respectively given above.
Based on the outcome of the effect of dosage, a variation of volume concentration was performed
in order to know the extent to which the crude oil can be adsorbed by a constant mass of Ag-MOF.
The volume of the crude oil was increased to 2.0, 3.0, and 4.0 mL, with Ag-MOF remaining constant
at 1 gram. The result obtained is given in Table 3 and Figure 7.
Table 3: Volume of Crude oil in (mL)/1g of Ag-MOF.
Volume of Crude oil in (mL)/1g of Ag- Volume of crude oil Adsorbed (mL)
MOF
2.0 2.0
3.0 2.9
4.0 3.7
The result from the variation of adsorbate volume to a constant adsorbent mass shows an inclining
linear correlation which indicates that adsorption at constant mass of adsorbent increased with
increasing adsorbate volume. The capacity for adsorption of crude oil by Ag-MOF increased with
increase in volume at constant mass. From the EDX result, the percentage of the silver metal (50.9%)
may have increased the amount of charges on the surface of the Ag-MOF, which get bettered its
adsorptive property.
Table 4: Result of crude oil adsorption by composite of Ag-MOF/clay
Composite of Ag-MOF/clay in gram(g) volume of crude oil Adsorbed (mL)
0.2 g 0.9
0.6 g 0.9
0.8 g 1.0

7
 Adsorption with composites: The composites of the Ag-MOF/clay and Ag-MOF/charcoal were
also applied for crude oil adsorption. The result for Ag-MOF/clay adsorption is presented in Table 4
and Figure 7. The result of the adsorption with Ag-MOF/charcoal is presented in Table 5 and Figure
8.
1.2
1
0.8
0.6
0.4
0.2
0
1 2 3
composite of Ag-MOF/clay volume of crude oil adsorbed

Figure 7: Combination chart for the Ag-MOF/clay composite (blue) and the volume of crude oil
adsorbed (orange).
The results indicated that the adsorptive performance of Ag-MOF/clay and Ag-MOF/charcoal
composites was very effective, as the quantity of crude oil (1 mL) was completely taken up with
increasing composite dosage: the exception being that it was better with the Ag-MOF/charcoal than
the Ag-MOF/clay composite. At 90-100% adsorption by the Ag-MOF/clay with a varying mass of
the adsorbent, the composite is an effective adsorbent for crude oil. The adsorption result for all is
100%. The charcoal composite had greater influence in the process because of better physical
properties such as, large surface area, pores of different sizes which enhances the adsorption.
Table 5: Result of crude oil adsorption by composite of Ag-MOF/charcoal
Composite of Ag-MOF/charcoal in volume of crude oil Adsorbed (mL)
gram(g)
0.2g 1.0
0.6g 1.0
0.8g 1.0
Figure 8, below is a combo chart used to describe the efficacy of the adsorption of crude oil by the
composite of the silver MOF and charcoal. The blue colour represent the masses of adsorbent used
and the orange colour represent the amount of crude oil adsorbed. The proved that composite of silver
MOF/charcoal is an outstanding adsorbent.
1.5

0.5

0
1 2 3

composite of Ag-MOF/charcoal volume of crude oil adsorbed

Figure 8: Combined chart of efficiency of the different masses of the composite (Ag-
MOF/charcoal) and volume of oil adsorbed

8
 pH effect on the adsorbent (Ag-MOF): The pH effect is given in table 6 below. The pH levels used
were 4.4, 6.85, and 9.0.
The effect of pH results for Ag-MOF on its adsorption capacity is presented in Figure 9. For each
of the pH used, Ag-MOF showed a very good adsorption by adsorbing 100% of the crude oil. In other
words, the pH of the water on which the crude oil was floating did not affect the uptake of the oil by
the Ag-MOF adsorbent.
Table 6: Volume of Crude oil 1 mL/1 g of Ag-MOF/pH
Volume of Crude oil 1mL/1g of Volume of crude oil
Ag-MOF/pH Adsorbed (mL)
pH 4.4 1.0
pH 6.85 1.0
pH 9.0 1.0

1.2
Volume of crude oil

1
Adsorbed (mL)

0.8
0.6
0.4
0.2
0
0 2 4 6 8 10
Volume of Crude oil 1mL/1g of Ag-MOF/pH

Figure 9: Result of pH effect on the adsorption property of Ag-MOF.

Adsorption Equilibrium and Isotherm Study: The adsorption of crude oil by Ag-MOF was
subjected to equilibrium study and some isotherm models to ascertain the prevailing type of
adsorption. The results are shown in figures 10 and 11. The result in Figure 10 shows that quantity of
oil adsorbed increased with increase in initial volume of crude oil, while percent adsorption increased
with initial volume of oil used to a maximum. On isotherm study, the Freundlich and the Redlich-
Peterson models were the closest and best correlated with the experimental data, thus it may be
suggested that physisorption may have been the prevailing process of the adsorption of the crude oil
by Ag-MOF.

9
 qty ADS % ADS

Quantity of oil Adsorbed (g/g) 3 80

2.5 70
60

% adsorbed
2 50
1.5 40
1 30
20
0.5 10
0 0
0.5 1 1.5 2 2.5 3 3.5 4 4.5

0 1 2 3 4 5
Initial volume of oil (mL)

Figure 10: Effect of initial volume of crude oil on the quantity of oil adsorbed by Ag-MOF

ADSORPTION ISOTHERMS
Experimental Langmuir Freundlich Temkin R-P

2.5
Qe (g/g)

1.5

0.5

-0.5 0 . 1 0.6 1.1 1.6 2.1 2.6

Ce(g/mL)

Figure 11: Isotherm plots for the adsorption of crude oil by Ag-MOF

4. Conclusion

Ag-MOF was successfully synthesized by a solvothermal protocol. FTIR, SEM, and EDX were
used to characterize the as- synthesized Ag-MOF. Characterization results revealed chemical
functional groups and porous morphology that could enhance adsorption of crude oil by Ag-MOF.
Sorption analysis showed that the silver MOF could absorbed 100% volume of the crude oil for all
measurements except for the 4 mL, where about 92.5% was adsorbed. Forming a composite of Ag-
MOF and charcoal has been shown to be innovative and cost effective for adsorption. The composite
with clay was good, but not as good as charcoal for adsorption of crude oil. Quantity of oil adsorbed
increased with increase in initial volume of crude oil, while percent adsorption increased with initial
volume of oil used to a maximum. Isotherm study showed that physisorption may have been the
prevailing process of the adsorption. An optimized quantity of Ag-MOF can be utilized in crude oil
spill remediation in our environment.

Acknowledgement

The authors wish to acknowledge the management of the Niger Delta University for making their
laboratory available for us to carry out this research. We appreciate it.

10
References
[1] Lopez J. (2018). Isoreticular two-dimensional magnetic coordination polymers prepared through presynthetic ligand
functionalization. Nat. Chem, (10), 1001-1007.
[2] Zhou H. C., Kitagawa S. (2014). Metal –organic frameworks (MOFs). Chem. Soc. Rev, (43), 5415-5418.
[3] Talin A. A. (2014).Tunable electrical conductivity in metal-organic framework tin-film services. Science, (343), 66-
69.
[4] Degayner J. A., Jeon I. R., Sun L., Dinca N., Harris T. D. (2017). 2D conductive iron-quinoide magnet ordering up
to Tc 105K via heterogenous redox chemistry. J. An. Chem. Soc, 139, 4175-4184.
[5] Darago L. E., Aubre M. L., Yu C. J., Gonzalez M. I. and Long J. R. (2015). Electronic conductivity, ferri magnetic
ordering, and reductive insertion mediated by organic mixed-valence in a ferric semiquinone metal. Organic-framework.
J. Am. Chem. Soc, (137), 15703-15711.
[6] Dong R. (2018). High-mobility band-like charge transport in a semiconducting twodimensional metal-organic
framework. Nat. mater, (17), 1027-1032.
[7] Kambe T. (2013). Pi-conjugated nickel bis (dithiolene) complex nanosheet. J. Am. Chem. Soc. (135), 2462-2465.
[8] Lingjuan S. (2012). Synthesis, characterization and application of metal organic frameworks, 1-3.
[9] Ferey G., Draznieks C.M., Serre C., Millange F. (2005). Crystallized frameworks with giant pores: Acc. Chem. Res,
(38), 217-225
[10] Mueller U., Schubert M., Teich F., Puetter H., Schierle-A. K., Pastre J. (2006). Metal–organic frameworks -
Prospective industrial applications, J. Mater. Chem. (16), 626–636.
[11] Gallo M., Glossman M. D. (2009). Fuel gas storage and separations by metal-organic frameworks: Simulated
adsorption isotherms for H2 and CH4 and their equimolar mixture, J. Phys. Chem. C. (113), 6634–6642.
[12] Wu C.D., Hu A., Zhang L., Lin W. (2005), A homochiral porous metal-organic framework for highly enantioselective
heterogeneous asymmetric catalysis, J. Am. Chem. Soc. (127), 8940–8941
[13] Chen B., Yang Y., Zapata F., Lin G., Qian G., Lobkovsky E.B. (2007).Luminescent open metal sites within a metal-
organic framework for sensing small molecules, Adv. Mater. (19), 1693–1696.
[14] Rowsell J.L.C., Spencer E.C., Eckert J., Howard J.A.K., Yaghi O.M. (2005). Gas adsorption sites in a large-pore
metal-organic framework, Science (309), 1350–1354.
[15] Philip M. Stanley, Christopher Thomas, Erling Thyrhaug, Alexander Urstoeger, Michael Schuster, Jürgen Hauer,
Bernhard Rieger, Julien Warnan, Roland A. Fischer. (2021) Entrapped Molecular Photocatalyst and Photosensitizer in
Metal–Organic Framework Nanoreactors for Enhanced Solar CO2 Reduction. ACSCatalysis, 11 (2), 871-882. https://
doi.org/10.1021/acscatal.0c04673
[16] Yamei Sun, Ziqian Xue, Qinglin Liu, Yaling Jia, Yinle Li, Kang Liu, Yiyang Lin, Min Liu, Guangqin Li & Cheng-
Yong Su(2021), Modulating electronic structure of metal-organic frameworks by introducing atomically dispersed Ru for
efficient hydrogen evolution. NatureCommunications 12:1369
[17] Yaghi O. M., Eubank J. F., Forster P. (2009). Chem. Soc. Rev, (38), 1213-1214
[18] Brandon R. Barnett, Surya T. Parker, Maria V. Paley, Miguel I. Gonzalez, Naomi Biggins Julia Oktawiec and Jeffrey
R. Long. (2019,) Thermodynamic Separation of 1-Butene from 2-Butene in Metal–Organic Frameworks with Open Metal
Sites J. Am. Chem. Soc., 141, 45, 18325–18333
[19] Giliopoulos D., Zamboulis A., Giannakoudakis D., Bikiaris D., Triantafyllidis K. (2020) Polymer/Metal Organic
Framework (MOF) Nanocomposites for Biomedical Applications. Molecules, 25, 185-189. https://doi.org/10.3390/
molecules25010185
[20] Andriotou D., Diamantis S.A., Zacharia A., Itskos G., Panagiotou N., Tasiopoulos A.J., Lazarides T. (2020) Dual
Emission in a Ligand and Metal Co-Doped Lanthanide-Organic Framework: Color Tuning and Temperature Dependent
Luminescence. Molecules, 25,523. https://doi.org/10.3390/molecules25030523
[21] James F.Claire, Marina Solomos, Jungkil Kim, Gaoqiang Wang, Maxime A. Siegler, Michael F. Crommie & Thomas
J. Kempa (2020), Structural and electronic switching of a single crystal 2D metal-organic framework prepared by
chemical vapor deposition. Nature Communications, 11, 5524-5526
[22] Cameron I, Carpenter-Warren, Alexandra M.Z, Slawin (2021), One pot,three dimensionionalities:1D, 2D and 3D
Zinc Coordination polymers with both N- and O- linkers produced in same reaction. Elsevier, Journal of Solid State
Chemistry, 293, 121717.
[23] Senda Ben Jmaa and Amjad Kallel (2019), Assessment of Performance of Posidona oceanica (L.) as Biosorbent for
Crude Oil-Spill Cleanup in Seawater. Hindawi BioMed Research International, Article ID 6029654, 9 pages
https://doi.org/10.1155/2019/6029654
[24] Mircea D., and Long J. R., Angew and Chemie T. E. (2008). International Ed, 47(36), 6766-6779.
[25] Andrea C., Sudik P., Adrien C., Wong-Foy A. G., Keeffe M. O., and Yaghi O. M. Angew (2006). Chem. Int. Ed., (45),
2528-2533.
[26] Egorova E., Revina A., (2000). Colloids Surf. Physicochem. Eng. Aspects, (168), 87.
[27] Kholoud M. M., Abou E., Ala E, Abdulrhman A., Reda A. A. (2010). Synthesis and applications of silver nanoparticles.
Arabian Journal of Chemistry, (3), 135–140.
[28] Adedibu C., Tella Isaac Y., A. (2012).) The synthesis and application of metal organic frameworks materials: a

11
review. Acta Chim. Pharm. Indica, 2(2), 75-81.
[29] Hussein R. A., Jin S., Ha-Ming Ang & Shaobin Wang (2013), Amino-functionalized Zr-MOF nanoparticles for
adsorption of CO2 and CH4, International Journal of Smart and Nano Materials, 4:1, 72-82.
[30] Hiroyasu F., Kyle E. Cordova, 1, 2 Michael O’Keeffe Omar M. Yaghi. (2013). The Chemistry and Applications of
Metal-Organic Frameworks. Science, 34.1
[31] JoséMarí a R., Susana, R., Cherif B., Youssef Alejandro Z. (2016). Highly Efficient Adsorption of Aqueous Pb(II)
with Mesoporous Metal-Organic Framework-5: An Equilibrium and Kinetic Study. Journal of Nanomaterials, 1-10
[32] Xili Cui, Zheng Niu, Chuan Shan, Lifeng Yang, Jianbo Hu, Qingju Wang, Pui Ching Lan, Yijian Li, Lukasz
Wojtas, Shengqian Ma & Huabin Xing.,(2020), Efficient separation of xylene isomers by a guest-responsive metal–
organic framework with rotational anionic sites. Nature Communications 11: 5456
[33] Dmytro Antypov, Aleksander Shkurenko, Prashant M. Bhatt, Youssef Belmabkhout, Karim Adil, Amandine
Cadiau, Mikhail Suyetin, Mohamed Eddaoudi, Matthew J.Rosseinsky & Matthew S. (2020), Differential guest location
by host dynamics enhances propylene/propane separation in a metal-organic framework. NatureCommunications 11:
6099
[34] James Mitchell crow, (2012)-MOFs smashes gas storage ceiling. Royal Society of Chemistry
[35] Orodu Victor Enearepuadoh and Dikio Ezekiel Dixon., (2021), Synthesis, Characterization and Adsorption Study of
Metal Organic Framework of Copper (II) benzene-1, 4dicarboxylate (Cu-MOF) on Crude oil. Progress in Materials
Chemistry and Physics 2: 1-14.

12