A Project Report

on
Zn-Based Metal-Organic Frameworks
and Their Application

submitted in partial fulfilment of

master of science in chemistry

For the session of the 2024-25

Submitted by

Shyamli Singh
[Link]. IV Sem
Enrolment no.: U2375365

Supervisor
Dr . Girijesh kumar

1
 Department of Chemistry
University of Allahabad, Prayagraj
Uttar Pradesh, India, 211002
( Central University )

Certificate
This is to certify that the project on paper review on “Zn -Based Metal-Organic
Frameworks and Their Application” is submitted by Shyamli Singh (Enrolment
Number: U2375365) of [Link]. IV semester under the supervision of Dr. Girijesh
Kumar , Department of Chemistry, University of Allahabad, Prayagraj in partial
fulfilment of the requirements for the award of the degree of Master of Science
(Chemistry) in the Department of Chemistry, Faculty of Science, University of
Allahabad, Prayagraj. The work is comprehensive, complete, and fit for final
evaluation.

Prof Dinesh Mani Dr. Girijesh Kumar

Head of the Department (Supervisor)
Department of Chemistry Department of Chemistry
Prayagraj-211002 University of Allahabad
Uttar Pradesh Prayagraj-211002
India India

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 Table of content
S. No. Content Page no.
1 Introduction 5
2 Review of literatures 6-13
3 Conclusion 13
4 Reference 14

3
 Acknowledgement
I would like to express my deepest appreciation to my parents who give me
opportunity to study in this university and I would like to extend my deepest
gratitude to my supervisor Dr. Girijesh Kumar who gave me this project and I
am highly grateful to my supervisor for the cooperation and encouragement
during this project it’s great opportunity for me to enhance my knowledge about
this field.
Finally, a special thanks to all the faculty members of the chemistry
department for there constant encouragement and support throughout my post
graduate career and special thanks to my friends for support.

Shyamli Singh

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Introduction
Metal-Organic Frameworks (MOFs), is a coordination polymer (or alternatively coordination
network) with an open framework containing potential voids. MOFs are self-assembled metal
clusters with organic ligands, are well known for their structure , permanent porosity and
tuneable properties and have shown great prospect for various applications. MOFs are
structures made up of inorganic nodes which can either be single ion or cluster of ions and
organic linkers. They contain potential voids which can be used for various application very
low density ,Crystalline, Large voids ,Significant Van der Waal interaction ,Complex unit cell.
Properties of MOFs The backbone of the compound is constructed from metal ions which act
as connected and organic bridging ligands as linkers ,Readily accessible porosity ,The co-
existence of inorganic hydrophilic and organic hydrophobic moieties and structure main
influence on adsorption properties, All the most of the marks are electrical insulator several
materials in this class every recently demonstrated excellent electrical conductivity at high
charge mobility , The thermal stability of mocks are determined by the coordination number
and local coordination involvement instead of framework topology , In general marks are poor
thermal conductor with thermal conductivity that is similar to concrete. Synthetic processes:
Different methods of synthesis of MOFs have been described .Traditional synthesis doesn’t
require complex equipment 1) non-solvo thermal 2) Hydro thermal or solvo thermal. Non-
traditional synthesis 1) microwave method 2) electrochemical method 3) mechano chemical
method 4) Sono chemical method 5) micro emulsion method. Metal organic framework are
crystalline materials composed of metal ions or clusters coordinated to organic ligands . This
combination results in a highly porous structure with remarkable surface area. History :1965
birth year of MOFs ,Omar Yaghi synthesised first MOF : MOF -5, 1997 Kitagawa reported 3D
MOF .High porosity , Tunability , Crystallinity , Robust , large surface area. Unparallel
structural versatility , tailor made porosity , synthetic modularity , responsive and
multifunctional applications , environmental and energy implications. Advantages of using
Zinc as a metal centre : Abundance : 24th most abundant element , 4th most produced metal (
after Fe , Al , Cu ) ,Low toxicity :LD50 =2150 mg/ Kg , oral in rats ,Versatile coordination
:Variable oxidation states ( +2 , +1 , 0 ), multiple coordination geometries ( tetrahedral ,
octahedral , square planar ), soft and hard ligand compatibility. Stability; e.g. :ZIF -8 ,Thermal
stability ( decomposition temperature exceeds 300˚ C ), Hydrolytic stability (retain structure
in humid environment ), Chemical stability ( stable in neutral , acidic as well as basic
environment ), Structural stability. Key parameters : Solvent types : polar aprotic solvent
(DMF, DMA), mixed solvents or water , Impact :drive the formation of different MOF
topologies. Reaction temperature : affect the kinetics of MOFs formation ,generally
solvothermal conducted at the range of 100˚C to 250˚ C. Impact: low temperature leads to
amorphous structure and high temperature could collapse the structure. Time: short reaction
time – smaller crystals , prolonged reaction time – crystalline large structure. Concentration of
reagents ( modulators) :fine tune the crystal growth process , reduce defects. Characterization
Techniques Single Crystal X – Ray Diffraction (SC-XRD), Powder X-ray Diffraction (PXRD),
Fourier Transform Infrared Spectroscopy (FTIR), Scanning / Transmission Electron
Microscopy, BET Surface Area Analysis.

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Review of Literatures:
Kumar and co-workers1 have prepared Zn- and Cd-MOFs with formulas;
[{Zn(L)(DMF)4}·2BF4]α (1) and [{Cd(L)2(Cl)2}·2H2O]α (2) using the solvothermal protocol.
A single crystal X-ray crystallography evaluation showed that Zn(II) ion displays a slightly
distorted octahedral geometry, wherein the four equatorial sites are occupied by four O DMF
moieties stemming from four different ligated DMF molecules while the apical sites are
occupied by Npyridyl atoms stanching from two different ligand L (Fig. 1a). In the crystal
structure of 2, the two pyridyl moieties of the ligand L occupy a syn–anti orientation to form a
cyclic loop with a Cd⋯Cd separation of 20.37 Å, to produce a 1D chain encapsulating the
lattice water molecule. The loop-chain structure of 2 demonstrates a cross-section of ca.
6.34×20.37 Å2 which is large enough to accommodate the guest molecules. Single-crystal
analysis reveals that both 1 and 2 display a one-dimensional chain and metalacyclic structure,
respectively. Discussed MOFs were exploited as multifunctional materials for the detection of
nitroaromatic compounds (NACs) in aqueous media and in the ipso-hydrox-ylation of
arylboronic acids using hydrogen peroxide as an oxidant to achieve desired phenols (Fig. 1b).
Due to there structural stability.

(a) (b)

Fig. 1. (a) Preparation of CP 1 and CP 2. (b) Catalytic reaction. Reproduced from ref.1

In 2016, Zhang and co-workers2 synthesised a porous luminescent zinc(II) metal−organic

framework (MOF) with a NbO net [Zn2(tptc)(apy)2−x(H2O)x]·H2O constructed using
paddlewheel [Zn2(COO)4] clusters and π-electron-rich terphenyl-tetracarboxylic acid, has been
solvothermally synthesized. One effective strategy to create MOFs with high iodine affinity is
the introduction of conjugated π-electron organic ligands or electron-pair donors’ pyridine,
ROH, R2O, RNH2 and which could produce stable charge-transfer (CT) complexes or halogen
bonds with iodine, thus increasing the adsorption amount for iodine (Fig. 2). For instance, a
double-walled MOF with a rigid organic ligand has been reported by Zeng’s group, who
presented the iodine loading and release dynamics. It also exhibited extremely high detection
sensitivity to nitrobenzene explosives (down to the ppm level).

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 (a) (b) (c)
Fig. 2. (a) Photographs of crystals before and after I 2 adsorption. (b) the three-dimensional
(3D) framework. (c) UV-vis spectra of I2 released over time in ethanol. Inset shows a plot
describing the controlled delivery of I2 ([I2] = Kt) in the first 1.5 h. Reproduced from ref.2

In 2018 , Sohail and co-workers3 prepared a water stable ZnMOF/ETH500/nafion GCE as an

electrode material for hydrazine [Link] Zn-MOF possesses good ability to electrocatalyze
the hydrazine oxidation reaction and a hydrophobic electrolyte, tetrakis(4-chlorophenyl)borate
tetradodecylammonium salt (ETH 500), during the fabrication of the Zn-MOF membrane.
After coating a thin film of the nafion-ETH500 supported Zn-MOF over a glassy carbon
electrode (GCE ) hydrazine oxidation improved. e Zn-MOF crystallizes in a triclinic crystal
system and the X-ray structure reveals that the asymmetric unit of the Zn-MOF consists of a
Zn(II) cation, two water molecules and half a unit of each 3-bpcda and bdc linker (Fig. 3).
MOFs can be used as an electrochemical sensing.

Fig 3. A view of the crystal structure of the Zn-MOF. Reproduced from ref.3

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In 2020, Ehzari and co-workers4 synthesised PABA -MOF which could chemically interact
with a metal ion Cu2+ , further used in detection of Cu2+ in milk and milk powder as real
samples. A Zn-based MOF , (Zn-TMU -24) prepared through solvothermal method . Then, the
Zn-TMU -24 is conjugated with PABA via electrochemical polymerisation to form PABA-
MOF on surface glass electrode. In FT-IR spectrum of TMU-24 (fig 4. a) , the appeared peaks
at 1378 and 1427 cm−1 are attributed to the stretching vibration absorption peak of the C=C
bonds of the benzene ring while the peaks at 2750 and 2850 cm−1 can be attributed to the
stretching vibration of the C–H bond in the benzene ring . The sensing of Cu2+ ion is done
through differential pulse adsorptive stripping voltammetry (DPAdSV) method which is
generally used in trace analysis. The PABA-MOF/GCE expresses high adsorption ability and
good electrochemical responses for Cu2.

(a)
(b)

Fig 4. (a) SEM images of PABA-MOF/GCE. (b) DPV of different concentration of Cu2+ (from
bottom to top: 0.05 to 250 nM) at modified PABA-MOF/GCE. Reproduced from ref.4

In 2021 , Ehsani and co-workers5 synthesised a distinct IRMOF produced by utilizing zinc
oxide octahedral clusters (Zn4O(CO)2) as the metal corners connected by varied organic
dicarboxylate linkers . The free and fixed pore diameters of IRMOf-16 range from 3.8 to 19.1
and 12.8 to 28.8 respectively (fig 5.) . Which was significantly used in hydrogen adsorption.
These were prepared by microwave technique which was considered ideal approach .They are
applicable in Drug delivery/nanoencapsulation , as an anti-cancer drugs , also in monitoring
antimicrobial activities , as an anti-inflammatory drug as a vitamins source in some of the MRI
agents , chemo/bio sensors .

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Fig 5. Varying IRMOFs and difference in the size of pores. Reproduced from ref 5.

In 2022 , kumar and co-workers6 prepared two MOFs [{Zn(L)(oba)}·4H2O]α (Zn-MOF-1)

and [{Cd1/2(L)1/2(nipa)1/2(H2O)1/2}·(DMF)1/2(H2O)]α (CdMOF-2) through solvothermal
protocol using mixed ligand approach, having a uninodal sql topology and 2D + 2D, parallel
polycatenation. And they are characterized by analytical, spectroscopic techniques and single-
crystal X-ray crystallography The FT-IR analyses of Zn-MOF-1 and Cd-MOF-2 exhibited
prominent bands between 1642−1612 and 1539−1533 cm−1, which are ascribed to the amidic
groups Their applications are noted in two respective fields as their luminescence intensities
increase in most of the solvents while it decreases in the case of aniline which shows it is highly
sensitive towards trace number of amines. Cycloaddition reaction was set up between CO2 and
styrene oxide without Zn-MOF-1 or Cd-MOF-2 (fig. 6a.)under our optimized reaction
protocol.

(a)
(b)

Fig 6. (a). synthetic pathway. (b) catalysis. Reproduced from ref. 6

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In 2022 , Nobakht and co-workers7 synthesised Sensitive Fluorescent Zn-Based
Metal−Organic Framework Sensor for Cimetidine Monitoring in Biological and
Pharmaceutical Samples .A highly fluorescent [Zn2(btca)(DMSO)2]n (Zn-MOF) was prepared
via in situ ligand formation by the solvothermal reaction of Zn(NO3)2·6H2O and pyromellitic
dianhydride (PMDA) in DMSO solvent. It exhibits a 3D porous structure (fig. 7b.)with open
tetragonal channels running along the crystallographic c-axis. The characteristics of this sensor
were investigated by field-emission scanning electron microscopy, dynamic light scattering,
energy-dispersive X-ray analysis, powder X-ray diffraction, Fourier transform infrared and
UV−vis spectroscopy as well as thermogravimetric, and elemental analyses. Further, the
proposed sensor has been successfully conducted for cimetidine detection in the human plasma,
urine, commercial ampule, and tablet. Luminescence turn-on sensor illustrates good sensitivity
and selectivity over two linear ranges of 1.0−10.0 and 20.0−80.0 ng mL−1 , respectively.

(a)
(b)

Fig 7. (a). Crystal structure of [Zn2(btca)(DMSO)2]n (Zn-MOF). (b) Increase of Fluorescence

Intensity of the Zn-MOF in the Presence of Cimetidine (turn-On Mode). Reproduced from ref.7

In 2022 , M. Ramish and co-workers8 synthesised Zn-MOF as an efficient catalyst for the
Hantzsch synthesis of polyhydroquinolines . A three-dimensional walnut-like Zn-based MOF
microsphere (fig. 8b.)system created via hydrothermal reaction of zinc salt with 4,6-diamino-
2-pyrimidinethiol as a tridentate ligand.

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 (a)

(b)

(c)

Fig 8. (a). FT-IR Spectrum of Zn-MOF microspheres. (b) SEM images of three-dimensional walnut-like,
hierarchically nanoporous Zn-MOF microspheres. (c) he synthesis of Zn-MOF microsphere. Reproduced from
ref. 8

In 2023 , Hosseini and co-workers 9 prepared a Zn MOF , [Zn2(DPTTZ) (OBA)2] (IUST-2),

via solvothermal method d by the reaction of 2, 5-di (4- pyridyl) thiazolo [5, 4-d] thiazole
ligand (DPTTZ), the “V-shape” 4,4’-oxybis (benzoic acid) ligand (OBA) and zinc nitrate
(Zn(NO3)2.6H2O). (fig. 9a.)With the thiazole sites for fast and efficient removal of heavy metal
ions Pb2+ and Hg 2+from water . And the noted removal efficiency was 97% and 87%
respectively. Maximum adsorption capacity is 1450 mg g−1 for Pb2+ and 900 mg g−1 for Hg2+
ions. The removal of metal ions by the IUST-2 is a monolayer adsorption by the interaction
between the active adsorption sites of the IUST-2 and Pb2+ and Hg2+ ions.

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Fig 9. (a) The Zn2+ ion Coordination environment in IUST-2. (b) The removal efficiency of
heavy metal ions for the IUST-2: on single solutions. (c) Influence of pH on the removal of
lead and mercury ions using the IUST-2. Reproduced from ref. 9

In 2024 , Ismail and co-worker10 Zn-based MOF [Zn(IP)(H2O)] using ultrasound irradiation,
with the linker being isophthalic acid (IPA) (1,3-benzene dicarboxylic acid) )] has a tetrahedral
structure, consisting of a Zn atom bonded to three carboxylate groups and one water molecule.
Act as a potential antimicrobial, anti-inflammatory and antitumor agent . The FTIR spectrum
of the synthesized Zn-MOF sample revealed characteristic features. The O – H stretching
modes of water molecules typically appear above 3000 cm−1. Furthermore, DNA fragmentation
of P. aeruginosa supported the efficacy of Zn-MOF (Fig. 10b.) as an antibacterial agent. Zn-
MOF demonstrated potential as an efficient anti-inflammatory agent compared to the standard
ibuprofen drug. Moreover, it showed promise as an anticancer agent against liver and colon
cancer types with minimum adverse effects observed on human normal lungs. The antioxidant
efficiency of Zn-MOF further supported its anticancer activity. DNA binding studies suggested
that Zn-MOF could be promising in gene therapy by generating more supercoiled DNA vectors.
DFT and docking, provided insights into the geometric stability of Zn-MOF and its interaction
with active amino acids in selected proteins associated with the investigated diseases.

Fig 10. (a) IR spectra of isophthalic acid (IPA), Zn-MOF and Ag/Zn-MOF. (b) SEM image of
Zn-MOF. Reproduced from ref. 10
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Conclusion. Zinc-based metal-organic frameworks (Zn-MOFs) represent a significant
advancement in the field of porous materials, showcasing a unique combination of versatility,
tunability, and functionality. This review has highlighted the pivotal roles that Zn MOFs play
across various applications—ranging from catalysis and gas storage to drug delivery and
environmental remediation. Their highly ordered structures, large specific surface areas, and
adjustable pore environments offer a robust platform for tailoring properties to meet the
demands of diverse technological challenges. Despite considerable progress, several issues
warrant further investigation. Challenges such as enhancing long-term structural stability,
achieving scalable synthesis with consistent quality, and ensuring performance reproducibility
remain critical hurdles. Addressing these challenges will require innovative approaches,
including advanced post-synthetic modifications and the integration of computational
modelling techniques, which could further unveil new functionalities and applications.
Looking ahead, future research should emphasize the development of methodologies to
improve the durability and reusability of Zn MOFs under practical conditions. Moreover,
interdisciplinary collaborations, particularly those integrating AI-driven design and real-time
monitoring techniques, will be invaluable in accelerating the discovery and optimization of
next-generation Zn MOFs. Such efforts promise to not only deepen the scientific understanding
of these materials but also to broaden their applicability in addressing pressing global issues,
from clean energy challenges to environmental and biomedical innovations. In essence, Zn
MOFs stand at the intersection of material science and practical innovations, holding the
potential to revolutionize multiple sectors when challenges are systematically overcome.
Continued exploration and collaborative research are the keys to unlocking their full potential
in both academic and industrial domains. MOFs have been explored in diverse fields,
including: Gas storage and separation: Their porous structure allows for efficient storage of
gases like hydrogen and carbon dioxide, as well as separation of gas mixtures, Catalysis: MOFs
can be used as catalysts in various chemical reactions, with some researchers focusing on
improving their activity and selectivity, Environmental remediation: They are effective in
removing pollutants from wastewater and air, including heavy metals and organic compounds,
Biomedicine: MOFs are being explored for drug delivery, wound healing, and biosensing
applications due to their biocompatibility and ability to be modified for specific purposes, Food
packaging: MOFs can be incorporated into food packaging to improve shelf life and quality by
controlling moisture and oxygen levels.

References
1. P. Rani, A. Husain, K. K. Bhasin, and G. Kumar, Coordination Polymers as a Functional
Material for the Selective Molecular Recognition of Nitroaromatics and ipso-Hydroxylation of
Arylboronic Acids. Chem Asian J. 2021, 16, 1–15. [Link]

2. [Link], X. Cui, X. Jia, F. Zhang, and X. Zhang , A Luminescent Zinc(II) Metal–Organic

Framework (MOF) with Conjugated π-Electron Ligand for High Iodine Capture and Nitro-
Explosive Detection. Inorg. Chem. 2016, 55, 9270–9275.
[Link]

3. M. Sohail, M. Altaf, N. Baig, R. Jamil, M. Sherc and A. Fazald, A new water stable zinc metal
organic framework as an electrode material for hydrazine sensing. New J. Chem. 2018, 42,
12486—12491. [Link]

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4. H. Ehzaria, M. Amirib, M. Safaria and M. Samim , Zn-based metal-organic frameworks and p-
aminobenzoic acid for electrochemical sensing of copper ions in milk and milk powder
samples. Int. J. Environ. Anal. Chem, 2020, 104, 7791-7809.
[Link]

5. M. Moharramnejad, A. Ehsani, S. salmani, M. shahi, R. E. Malekshah, Z. S. Robatjazi ,

H. Parsimehr , Zinc-Based Metal-Organic Frameworks in Drug Delivery, Cell Imaging, and
Sensing. Molecules 2022, 27(1), 100; [Link]

6. P. Rani, A. Husain, K. K. Bhasin and G. Kumar , Metal−Organic Framework-Based Selective

Molecular Recognition of Organic Amines and Fixation of CO2 into Cyclic Carbonates . Inorg.
Chem. 2022, 61, 6977−6994. [Link]

7. Z. Afravi, V. Nobakht, N. Pourreza, M. Ghomi, D. Trzybinski, ́ and K. Woźniak, Novel Zn

metal–organic framework with the thiazole sites for fast and efficient removal of heavy metal
ions from water. ACS Omega. 2022, 7, 22221−22231

8. S. M. Ramish , A. G-Choghamarani and M. Mohammadi, Ultrasonic synthesis,

characterization, DFT and molecular docking of a biocompatible Zn-based MOF as a potential
antimicrobial, anti-inflammatory and antitumor agent. Sci. Rep. 2022, 12:1479.
[Link]

9. A. K. Hosseini & A. Tadjarodi, Zinc-based metal-organic frameworks: synthesis and recent

progress in biomedical application. Sci. Rep. 2023 13:11430. [Link]
022-02385-y

10. K. M. Ismail, F. B. Rashidi & S. S. Hassan, Design of a Sensitive Fluorescent Zn-Based Metal–
Organic Framework Sensor for Cimetidine Monitoring in Biological and Pharmaceutical
Samples. Sci. Rep. 2024, 14:21989. [Link] .

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