The Progress and Roadmap of Metal-Organic Frameworks For High-Performance Supercapacitors

The progress and roadmap of metal-organic frameworks
for high-performance supercapacitors

P. E. Lokhande1, Sahana Kulkarni2, Sandip Chakraborty2*, H. M. Pathan3, Deepak Kumar4*, Jashanpreet
Singh4, Anupam Kumar5, Yogendra Kumar Mishra6, Mikael Syväjärvi7, Dana Cristina Toncu7, Ajit
Sharma4,7* and Ashutosh Tiwari7*
1Department of Mechanical, Manufacturing and Biomedical Engineering, Trinity College Dublin, Ireland.
2Amity Institute of Nanotechnology, Amity University, Noida, UP 201303, India.
3Advanced Physics Laboratory, Department of Physics, Savitribai Phule Pune University, Pune 411007, India.
4Department of Chemistry, School of Chemical Engineering and Physical Sciences, Lovely Professional
University, Phagwara 144411, India.

5Department of Biotechnology, School of Bioengineering and Biosciences, Lovely Professional University,
Phagwara 144411, India.

6Mads Clausen Institute, NanoSYD, University of Southern Denmark, Alsion 2, 6400 Sønderborg, Denmark.
7Institute of Advanced Materials, IAAM, Gammalkilsvägen 18, Ulrika 590 53, Sweden.
*Corresponding authors. E-mail: ajitsharma2003@gmail.com (AS) deepak.sharma99967@gmail.com (DK),

schakrabarti@amity.edu (SC) and director@iaam.se (AT), Tel: (+46) 1313 2424
Abstract
The ever-increasing energy demand has led to the need to develop new smart materials to
overcome the present crises in the energy generation and storage sector. Amongst various
cross-functional platforms, metal-organic framework (MOF) has turned up as an efficient class
of porous organic-inorganic ordered structure owing to their flexibility, tunable structures, and
compositions, that can play an important role as building blocks for synthesizing highly
efficient energy materials for advanced applications. Recently, progress in metal organic
framework derived materials have revealed impressive efficiency in the energy conversion and
storage sector by overcoming the challenges facing the counterparts of the individual
compound and/or materials used in fabricating the electrodes for supercapacitors. In this
review, we discuss the performance of different types of nano/micro hybrid structures derived
from the metal-organic framework as electrode materials for supercapacitor applications. For
a better understanding, we have divided the derived energy materials based on the MOF
precursors used in building electrodes. Further, the emerging feasibility of large-scale
production, challenges and future perspectives are systematically discussed. The MOF-based
supercapacitors could accomplish high energy density with better electrical conductivity
including increase of the power density in comparison to using conventional electrode
materials.
Electronic copy available at: https://ssrn.com/abstract=4098683

Keywords: Electrode materials, Metal-organic frameworks, Supercapacitor, Energy density,
and Electrical conductivity.
Table of Contents
1. Introduction
2. MOF building blocks
2.1. Co-MOF templates
2.2. Cu-MOF templates
2.3. Mn-MOF templates
2.4. MOF-5 functional derivatives
2.5 Nickel-based MOF
2.6. Rare MOF templates
3. ZIF templates for electrode materials
4. Bimetallic MOF derivatives
5. MOF materials-based electrode state-of-the-art challenges and way forward
6. Roadmap: MOF materials for supercapacitors
7. Conclusions
List of Abbreviations. MOF-Metal organic framework, ZIF-Zeolitic imidazolate

framework, EDLC-Electrochemical double layer capacitor, ASC-Asymmetric supercapacitor,
HSC-Hybrid supercapacitor, FHSC-Flexible hybrid supercapacitor, FASC- Flexible
asymmetric supercapacitor, LED-light emitting diode, LEP- light emitting phosphor, CNT-
carbon nanotubes, GO- Graphene oxide, rGO- Reduced graphene oxide, AC-Activated carbon,
CC- Carbon cloth, APC- Activated porous carbon, NPC-nanoporous carbon, OD- Quantum
dots, CNS- Carbon nanospheres, PCP- Porous carbon polyhedrons, HMS-Hollow
microspheres, MO-Metal oxide, HITP = 2,3,6,7,10,11-hexaiminotriphenylene, DMF-
Dimethylformamide, PANI-Polyaniline, PPy-Polypyrrole, PVDF-Polyvinylidene fluoride,
PVA-Polyvinyl alcohol, PDA-Polydiacetylene, PDAC- Poly(diallyldimethylammonium
chloride), H2ipa-Isophthalic acid KOH-Potassium hydroxide, GPE-Gel polymer electrolytes,
PVA-KOH- polyvinyl alcohol based gel electrolyte, SSA- specific super area, ED- Energy
density, PD-Power density, SC- specific capacitance, ASA- Active surface area, SEM-
Scanning tunneling microscopy, and TEM-Tunneling electron microscopy.

1. Introduction
The dramatic increase in the usage of fossil fuels has raised the greenhouse effects which are
causing serious threat to the human lives and environment [1,2]. There is an imperative necessity
to develop renewable and clean energy sources that will help in fixing the present crises of
energy shortage and pollution [3,4]. As a result, it is critical to establish adequate technologies
related to net-zero energy conversion and climate neutral storage systems [5]. In the past
decennium, there has been a symbolic rise in interest in embellishing new technologies and a
considerable amount of effort has been inlaid in reinforcing more effective energy storage
devices such as batteries and capacitors [6]. However, the low power density and limited
charge/discharge cycles of batteries as well as low energy density of conventional capacitors
have restricted their use in high-handed technologies which gave rise to the concept of
supercapacitors[7]. Energy conversion and storage systems with exceptional stabilization and
efficiency have fascinated researchers in both industry and academia. Therefore, the
construction and designing of these systems had remained a major challenge for them.
The elementary form of supercapacitor is made up of two electrodes that are segregated
from electrical contact with the help of a semi-permeable membrane known as a separator[8].
The membrane is partially porous to permit the ionic charge movement along with high ionic
conductance, high electrical obstruction, and low thickness to accomplish the work most
efficiently. Electrodes are then drenched in electrolytic solution along with separator, i.e.,
prevent discharging of cells by enabling the flow of current between electrodes. This enables
the flow of ionic current between the electrodes and prevent the electronic current from
discharging the cells[9]. Based upon the charge storage mechanism, supercapacitors are grouped
into three different classes, namely, electrochemical double-layer capacitors (EDLCs),
pseudocapacitor and hybrid capacitors [10]. The electrochemical double-layer capacitors, also
known as EDLCs, stores charge electrostatically at the interface of a solid electrode and

electrolyte forming a double layer of positive and negative ions on the interface. In EDLC,
capacitance highly relies on the ASA of the electrode whereas the charge is physically stored
in the interface of the electrode when ions of electrolyte react. Thus, EDLCs show greater
cyclic stability than pseudocapacitors as degradation of active material is reduced due to
physical interaction[11]. Carbon materials are used in the fabrication of EDLCs such as AC,
CNT, GO, rGO, carbide-derived carbons, and mesoporous carbons [12]. Whereas in
pseudocapacitor charge storage takes place by the Faradic reaction between electro-active
species, thus helping them to provide greater charge density. There can be two types of
capacitance in pseudocapacitance material namely, intrinsic and extrinsic
pseudocapacitance[13].
The energy materials with wide range of particle size and morphologies show intrinsic
pseudocapacitive conductance characteristic whereas extrinsic pseudocapacitance is shown by
nano-sized particles[9]. Dynamically, pseudocapacitive materials can be recognized from the
battery-type materials through electroanalytical performance with their energy being cramped
by a surface-related interaction rather than dissemination-controlled responses administering
the electrochemical reaction of battery anodes[14,15]. Pseudocapacitors are known to have 10-
100 times higher capacitance than EDLC’s where it generally uses metal oxides such as
ruthenium oxide, manganese oxides nickel oxide and conducting polymers[16]. By combining
both the properties of EDLC’s and pseudocapacitor, hybrid capacitors were developed from
the composite of the materials that can be used separately for fabricating EDLC and
pseudocapacitor, thus the properties of both types of supercapacitor are bestowed[17,18]. They
are generally referred to as asymmetric supercapacitors as one electrode is made of carbon
material (EDLC’s) whereas the other will be of metal oxide or polymer which refers to
pseudocapacitors behavior[19].

Supercapacitors, also referred as electrochemical capacitor or ultracapacitor, have sought the
interest of many researchers due to their long cycle lifetime, high power density, excellent
reliability, large number of charging-discharging cycles, and a robust thermal operating range,
giving them an upper hand over the other conventional energy storage devices[17].
Supercapacitors can be used in various energy generation and storage applications, either
unaided or accompanied by fuel cells or batteries[20]. Although supercapacitors can store a huge
sum of charge which can be used to supply a higher power-rating than that of replenishable
batteries, they have a lower energy density than batteries and other fuel cells[21]. Hence,
researchers are trying to design electrode with various materials to revamp the competence of
the supercapacitor, as the current material used in supercapacitors provide low power density
and charge cycles due to poor specific surface area (SSA) and deficient porosity[22,23]. Though
these drawbacks are only partly overcome by the use of carbon materials as electrode, as they
still lack high capacitance and energy density[24]. Further, to meet their proficiencies a new
class of porous material namely metal-organic framework or hybrid organic-inorganic
framework was introduced, which was first constructed in 1995 by developing a coordination
bond between the metal node and organic linker by Yaghi and co-workers[25].
The utility of various types of metal ions and organic linkers have led to diverse
structures of MOF: there are more than 20,000 MOF’s discovered with different compositions
till date[26]. Metal-organic frameworks are typically microporous structures having pore size
less than 2 nm diameter. They have a high crystallinity and more tunable composition which
make them more efficient than other porous structures like activated carbon and zeolite which
lack in selectivity and absorption limit[27]. Metal organic frameworks have shown potential
involvement in applications like drug delivery, gas storage, separation, metal ion detection,
sensing, energy storage device, catalysis, and adsorption[28]. In addition to the high surface
area, porosity, multiple redox activity, chemical and mechanical stability with multiple

crystalline structures and diverse scaffold structure, they contain active sites for charge storage.
The tunability of MOF can be done by acid−base and metal−ligand reactivity where addition
of acidic ligand helps in controlling the size of pore[29]. This in turn help in fast conveyance of
electrons and electrolytic ions in supercapacitors, thereby overwhelming the drawbacks of
commercially used materials[4,30–33]. The reason behind this is the improved charge transfer
mobility, redox stability, and charge accumulation on surface of electrode through the reduced
path length, which in turn provides high capacitance, power density and greater stability to the
electrode[34]. Fig. 1 demonstrates various MOF and its derivatives used for supercapacitor
application.
This review focuses on the current advancements in MOF derived electrodes for
supercapacitor applications, where the derived functional micro/nano structures have been
segregated based on the MOF precursors used in building blocks of the electrode materials.
The review will further help to understand and differentiate the impact of various precursors
on the synthesized electrode materials. Furthermore, this study will offer a deep insight into
the current challenges and future prospective of MOF’s to be used as efficient commercial
electrode materials.
2. Metal-organic frameworks building blocks
Metal-organic frameworks are well known for their porosity, crystallinity, flexibility, and
structural diversity. These frameworks include uniformly organized 3-dimensional geometry
assembled by linking inorganic nodes by organic linkers through co-ordination bonds that
imparts high porosity and tenability. This is attributed to the interlayer adjustment of linkers
between adjacent metal nodes, but metal nodes other than MOF’s itself can also act as
secondary building units to form more robust structures by replacing one metal nod with the
other or creating polynuclear sites via chelation[35]. Thus, the metal ions chelation and charge
on the linker element helps to improve the stability of the complex, which favors its use in

harsh ambiance. With such extraordinary properties, MOF’s have shown their potential
application in various fields, such as drug delivery, gas storage, separation, metal ion detection,
sensing, energy storage device, hydrogen generation, catalysis, and adsorption[36]. Generally,
carbonaceous materials are synthesized through thermal heating of coordinated frameworks in
the inert ambiance to transform MOF into carbonaceous elements, owning intrinsic properties
with or without using secondary carbon precursors[22]. Thus, the carbonization of MOF imparts
tunable porosity, structural rigidity, crystallinity, and conductivity to the derived material.
Furthermore, derived materials can be modified accordingly by chemical doping of
elements in carbonaceous matrix. Recently, carbonization of MOF has been adopted broadly
due to the single step calcination process, which leads to many diverse structures from zero-
dimensional to three-dimensional material. Moreover, MOFs also act as an efficient template
to generate metal oxides when treated thermally[37]. Due to the thermal decomposition of metal
nodes and organic linkers present in the framework, metal ions undergo oxidation forming
oxygen species, whereas linkers form carbon dioxide and nitrogen oxide (depending on the
linker used). These derived transition metal oxides have the nanoporous structure with high
surface area, porosity, and stability as of MOF which can withstand the harsh environment of
electrolytes. Apart from producing single metal oxides, the MOF can also be used to produce
bivalent, multivalent and mixed metal oxides by using different types of MOF such as MOF-
74, bimetallic MOF, ZIF etc.[38]. Therefore, MOF can act as an extraordinary precursor with
multiple surface functionalities and tunable porous structures for synthesizing various
functional materials for super capacitor application.
2.1. Co-MOF templates
Fabrication of electrode material for energy storage devices by the template-assisted method
has been widely used. The Co-MOF has shown tremendous application in the storage sector
due to their facile synthesis, thermal stability, low toxicity and flexibility, and they have been

used as a template to derive functional material with the complimentary elements, which retain
intrinsic properties of MOF[39].
The co-doping of nitrogen improved the charge exchange property in a carbon matrix.
Incorporation of Co9S8 induced the redox couple attributing reverse electron moment, whereas
the carbon matrix enhanced the active surface area for the interaction and diffusion of ions by
reducing the path length and thereby increasing the conductivity. Cyclic stability of the
prepared material was tested with CV and GCD, which showed that at 10 A g-1 current density,
99.8 % capacitance was retained after 1,40,000 continuous cycles, also evident from the GCD
graph shown in Fig. 2 (a-c). When an asymmetric supercapacitor was built by taking
Co9S8/NS-C-1.5 matrix as an cathode and AC as an anode, it displayed specific capacitance of
75.59 F g-1 at 1 A g-1 with 99.5% retention of initial capacitance after 2000 cycles along with
14.85 W h kg-1 energy density at 681.82 W kg-1 power density and remained 6.63 even at
6818.18 W kg-1 [40].
Zou et al. synthesized three types of Co-MOF using the same elements and studied the
role of bdc2−linker in the derived material of Co-MOF, which revealed to be the backbone for
controlling the porosity and lattice dimensions in MOF and derived carbon matrix. Initially,
the precursor Co-MOF was calcinated at 900°C in N2 atmosphere, resulting in Co@CNT which
upon gas-sulfurization at 400°C for 3 hrs yielded CoS2@CNT through converting the turned
cobalt species into CoS2. Well dispersion of CoS2 nanoparticles in carbon matrix increased the
conductivity and stability, whereas Faradic reactions caused by multiple valance states of Co
enhanced capacitance up to 825 Fg-1 at 0.5Ag-1. Among the three MOF-derived composites,
(p)-CoS2@CNT showed greater surface area, pore diameter, and stability with 5000 cycles due
to the well aligned Co in lattice plane[41].

Elayappan et al. designed CoP–CoNC/CC by anchording Co-MOF on carbon cloth
(CC) through precipitation and subsequent pyrolysis in nitrogen atmosphere, yielding
CoNC/CC rooted with cobalt nanoparticles[42]. To enhance the electrochemical activity
furthermore, phosphate group was incorporated by using sodium hypophosphite monohydrate,
and through pyrolysis and phosphatization in argon atmosphere converted cobalt nanoparticles
into cobalt phosphide resulting CoP–CoNC/CC complex. Electrochemical property was
examined by bi- and tri-electrode setup, which, at 1 mA cm−2, displayed greater specific-
capacitance of 975 F g−1 for CoP–CoNC/CC complex. Such enhancement in the capacitance
was attributed to the increase in oxygen concentration in the positive side due to the interaction
of electrolytic ions with active elements, favored by strong anchorment of Co-species and C
based linker on the surface of CC. When ASC was formed with activated carbon, CoP–
CoNC/CC//AC cell displayed high energy and power density of 39.2 W h kg−1and 1960 W
kg−1 respectively analogous to the capacitance of 144 F g−1[43].
Xiao et al. fabricated ultrathin Co3O4 nanosheets for asymmetric supercapacitor cell by
a green method to reduce the costly organic ligands molecules and induce reusability. They
utilized the UPC-9 precursor as its ligands which can be recycled through acidization reaction
when dissolved in alkaline solution and 3,5,6-tetramethyl-1,4-disophthalate as linker element
to obtain Co(OH)2, which yields cobalt oxide nanosheets after calcination. The 2-D geometry
of Co3O4 and Cu-MOF nanosheets provided a large SSA for the electrolyte to enable the ionic
diffusion in solid electrode and absorb alkali ions to raise the capacitance and thereby reduce
internal resistance and enhance faster kinetics. The ASA of Co3O4 nanosheets enabled a Faradic
reaction from inside and outside the material by increasing the specific capacitance up to 1121
Fg-1 at 1 Ag-1. The unique morphology of Co3O4 nanoparticles reduces the structural blemish
due to the volume change achieved in multiple redox cycles, thereby keeping the skeletal

integrity, providing improved reversibility and power of 6000 cycles with 32.8 WhKg-1 energy
densityb[27].
Hosseinzadeh and his coworkers synthesized cobalt-based graphitic carbon by simple
pyrolysis of Co-MOF under nitrogen atmosphere at 700°C for 8h, which yielded CoxOy/C-700,
which showed excellent capacitance of 1372 Fg-1 at 10 mV/s scan rate when tested against
Ag/AgCl reference electrode using galvanostatic method. The ASC was assembled by taking
a positive electrode of cobalt-oxide carbon composite and activated carbon (AC) as a negative
electrode. The effect of carbon and oxide-induced capacitance was 136 Fg-1 for both EDLD
and pseudo-capacitive behavior. It showed relatively large energy density of 51.5 Whkg-1 with
167 Wkg-1 power density[45]. The CC/SiCNWs@NiCo2O4NAs were fabricated by growing Co-
MOF on carbon cloth decorated with silicon-carbon nanowires, annealed at 800°C in argon
atmosphere for 2h and then the Co ions were etched with a mixture of FeCl3/HCl. The resulting
CC/SiCNWs@NiCo2O4NAs displayed higher capacitance of 1604.7 F g−1 at 0.5A g-1 current
density in 1.0 M KOH due to the binder-free and open standing structure of nanosheets. The
active material reduced agglomeration and provided a complete area of electrode for effective
interaction of electrolytic ions with active component, thereby increasing capacitance of the
cell and interwoven structure. This gave the stability to withstand the charge-discharge cycles
[46].
Similarly, Hu et al. tried to design nanoflower core-shell structure of CuCo2O4@CoS-
Cu/Co-MOF by two steps electrodeposition of CuCo2O4 on MOF-coated Ni foam as
represented in Fig. 3 (a). The synergetic effect of MOF, Cu and CoS was an increased in active
sites and imparted the structure stability to withstand the cyclic rates, as shown in the SEM
images from Fig. 3 (b, c, d and e). The extraordinary specific capacitance of ~3150 Fg-1 was
displayed by as-fabricated electrode at 1 A g-1 current density with enhanced cyclic reliability
of 10,000 cycles, which was evident from the CV and GCD curve, proving that among all the
10

complex, the rectangular curve of CuCo2O4@CoS-Cu/Co-MOF presented higher capacitance
area implying highest capacitance. Cyclic performance of CuCo2O4@CoS-Cu/Co-MOF core-
shell structure at 30Ag-1 current density baring 10000 cycles with detention of 96.74% initial
capacitance indicated no deterioration of the active material during charge-discharge cycles.
When tested in designed ASC system using CuCo2O4@CoS-Cu/Co-MOF as anode and CNT
as cathode in 2 M KOH, it displayed 849.94 W kg-1 power density with 73.19 Wh kg-1 energy
density, proving to be an excellent material for energy storage sector[47].
Yin et al. reported Co3O4@NiCoLDHNSs/CC as electrode material with excellent
storage capacitance of 1708 Fg-1 at 1 A g-1 current density along with 89% retention of
capacitance after 4000 cycles at 10 Ag-1 density. Such an outstanding active material was
synthesized by growing MOF on the carbon cloth in solution, which served as a template for
growing Co3O4NSs by annealing it at 350°C for 2h in air. It was finally converted to
Co3O4@NiCoLDHNSs/CC by electro-deposition of NiCo LDHNSs on Co3O4NSs/CC as
represented in Fig. 2(f). The synthesized material exhibited core-shell morphology with
Co3O4NSs as core and NiCo LDH NSs as shell, structure that induced high surface area for
charge accumulation and several channels for ion diffusion/transport, thus increasing its
storage capability. The morphologies of the designed MOF at different stages were analyzed
by SEM, which illustrates the structural changes of Co-MOFNSs after annealing in Fig. 3 (g-
g’). Similarly, Fig. 3 (h-i’) shows the interconnected honeycomb thread structure of NiCo LDH
nanosheets which were uniformly grown on the Co3O4NSs/CC. The ASC was designed using
fabricated material and activated carbon with (PVA)-KOH as solid-state electrolyte, and
displayed 44.44 Wh kg−1 energy density at 800Wkg−1 power density [48]. From the above-
mentioned literature, it is understood that Co-MOF shows outstanding ability as a template
medium by providing its intrinsic properties to the derived materials. Table 1 gives brief
11

development in Co-based MOF synthesized using different technique for supercapacitor
application.
Table 1. Different Co-based MOF synthesized for supercapacitor application and its
performance analysis.
Type of cobalt Specific Current Energy

density density Cyclic
based/derived capacitance Electrolyte Ref.
stability
MOF (Fg-1) (Ag-1) (Whkg-1)
Co-MOF 120.2 1 40.6 10000 6 M KOH [49]
Co-BTB-I-450 342.1 0.5 - 2000 [50]
Co-MOF 446.8 1.2 - - 800 [51]
Co-MOF/PANI 504 1 - 5000 1M KOH [52]
CoP-350 560 1 21.4 6000 6 M KOH [53]
CuCo-DS5 563 1 27.8 3000 2 M KOH [54]
MOF-Co 713.9 0.5 5000 3 M KOH [55]
Co-MOF (DUT-58) 734 1 - 140,000 6 M KOH [40]
CoS2@CNTs 825 0.5 - 5000 2 MKOH [41]
CoP–CoNC/CC 975 1 39.2 5000 2 M KOH [56]
Co3O4nanosheet 1121 1 32.8 6000 6 M KOH [57]
cobalt oxide/C-700 1372 2.5 - 2000 - [58]
CC/SiCNWs@NiCo
1604.7 0.5 49.9 4,000 1 M KOH [59]
2O4NAs
Co3O4@NiCoLDH
1708 1 44.44 4,000 1 M KOH [60]
NSs
CuCo2O4@CoS-
3150 1 73.19 10,000 2 M KOH [61]
Cu/Co-MOF
221.7
Co–Mo–Se 1 44.7 8000 3 g KOH [62]
mF/cm-2
CoSe2/CNT 543.5 mF/cm-2 1 0.25 4000 - [63]
12

mW h cm−
2
2.2. Cu-MOF templates
Currently, copper-based MOF and derived materials are the type of metal oxide nanostructures
having non-toxicity, low cost, high oxidizing efficiency, high surface area, porosity, non-
corrosive, durability and the copper abundance in nature makes it suitable for super-capacitor
application[64]. Li and co-workers designed flower-like morphology of nitrogen doped porous
carbon materials derived from Cu-MOF by self-assembly method. To form flower like
structure and maintain the structural integrity of Cu-MOF, Cu@C composites were etched with
hydrochloric acid, bearing hole-forming effect of Cu particles. Nitrogen doping caused the
nitrogen and oxygen to improve surface properties of the composite and enhance the
pseudocapacitance by 149 Fg-1 at a very low current density of 0.5 Ag-1. Further crystallization
of graphitic carbon improves the electron transfer at huge discharge rate with cyclic stability
of 2000 cycles[65]. Duan and co-workers synthesized Cu-MOF with three different
morphologies namely squama, truncated bipyramid, and rhombic flake at 25, 60 and 0 °C by
co-precipitation, which was confirmed by FESEM in the Fig. 4 (a). These synthesized Cu-
MOFs were further pyrolyzed to from Cu@C, which was etched with hydrochloric acid and
activated with potassium hydroxide to yield porosity in the activated carbon, as seen the
FESEM in Fig. 4 (a-c). The derived activated porous carbon (APS) showed the intrinsic
properties of MOF by providing high surface area of 1880.4 m2 g−1 and 0.81 cm3 g−1 pore
volume. Among all the synthesized APS from MOF, the squama morphology (APC-5) showed
higher capacitance of 196 F g−1 with current density 0.5 A g−1, and one was suitable as
symmetrical super capacitor, with 11.8 Wh kg−1 and 350 W kg−1 energy and power density
respectively with 10000 cyclic rates at 1 A g−1 current density. The symmetrical ones lit five
LED lights when were connected to 6 symmetric super-capacitor cell [66].
13

Li et al. utilized the same process while using 2-dimensional Cu- MOF as a precursor for the
synthesis of Cu@C, which was further HCL-etched and KOH-activated for the fabrication of
Cu@C for APC and lately APC nano-sheets. Ultra-high ASA of 2491 m2 g-1 was exhibited by
the synthesized APC nano-sheets with 1.50 cm3g-1 pore volume. It provided large active sites
for the accumulation of charges on the electrode, thereby increasing ion transfer, which proved
its good EDLC quality. When tested as electrode, quasi-rectangular shape of CV and
rectangular curve from GCD curve proved its suitability as an EDLC material with 260.5 F g-
1 specific capacitance at 0.5 A g-1 current density. Energy and power density of 18.38 Wh Kg-
1 and 350 W Kg-1 respectively were displayed with 5000 cyclic stabilities. When testing the
practical efficiency of APC nano-sheets by glowing red LED light, it lighted for over 12
minutes [67].
The Cu2O/Cu nano-sheets were prepared by thermalizing Cu-MOF and depositing it on
the carbon sheets with 336.3 m2 g -1 surface area, which is higher than the pristine MOF. The
DET curve further confirmed that synthesized sheets had both micro and mesoporous structure,
which helped to enhance the electrochemical properties and increase the interaction of active
material with ions of electrolyte, thereby reducing the path length and increase diffusion
respectively. Specific capacitance of 665 F g-1 was observed at 0.5 A g-1 current density by Wu
and his team in 1 M KOH electrolyte solution, due to the combination of both EDLC and
pseudo-capacitance behavior given by both porosity and redox reaction. When nanosheets were
assembled as cathode electrode along with activated carbon as anode in PVA-KOH gel
electrolyte, the resulted asymmetric super-capacitor showed 466.5 W·kg-1 power density at
maximum ED of 38.6 Wh kg-1 [68].
To overcome the electric hindrance and increased cyclic stability, Chhetri and his co-
workers derived copper oxide at 600°C from Cu-MOF and entrapped it into carbon matrix, as
represented in Fig. 4 (d). The SEM analysis of the synthesized materials showed the porous
14

structure of CuxO-C/PANI and PANI as displayed in Fig. 4 (e, f). The synthesized CuxO/C was
decorated with PANI, which not only acted as interface between current collector and active
material to enhance electron transfer, but also upgraded the conductivity of the composite
material, which in turn resulted in a high storage capacitance of 1308F g-1 at 1 A g-1 current
density. This was shown by cyclic voltammetry and galvanostatic charge discharge curves at
100mV s-1 in Fig. 5 (a-f). Non-distorted CV curve and symmetric curve in GCD proved the
stability of such electrode material, with high energy and power density of 55.1 W h kg-1 and
8668.2 W kg-1 respectively, and 88.3 % confinement of initial capacitance after 10000 cycles,
when employed as positive electrode with ZIF-8NPC as negative electrode in asymmetric
super-capacitor cell [69].
Li et al. reported the use of flexible supercapacitor in practical application of textile by
fabricating electrode material through epitaxially growing Cu-MOF HKUST-1 on cotton cloth
taken from commercially available T-shirt using LEP pump technique. Calcination of MOF-
grown cloth at 800°C resulted in copper-based helical carbon tube with extraordinary areal
capacitance at low current density of 1812 mF-1 cm2 and 1 mA-1 cm2 respectively with 2000
cycles, which is attributed to greater Faradaic redox reactions favored by copper oxides and
reduced resistance channels by carbon tubes. The CV and non-linear curve of GCD represent
the pseudo-capacitance activity of the HKUST-1@TS-800 shown in Fig. 5 (g), while Fig. 4 (i)
and (j) display the comparison of capacitance and power densities of bare calcinated cotton
cloth and MOF-coated carbon cloth. Cotton imparted the lightweight and flexible nature to the
electrode, while the calcination of MOF and cloth added high surface area and better ion
diffusion for charge storage, making it an excellent electrode material for wearable devices [70].
Table 2 gives electrochemical comparative performance study for Cu-Based MOF.
15

Table 2. Performance comparison of Cu-based MOF for supercapacitor electrode.
Type copper- Specific Current Energy Cyclic Electrolyte Ref.

based/derived capacitance density density stability
MOF
(Fg-1) (Ag-1 (Whkg-1)
Cu-MOF 149 0.5 - 2000 6 MKOH [71]
Cu@C, PAC 196 05 11.8 10000 6 M KOH [72]
Cu@C, PAC 260.5 0.5 18.38 5000 6 M KOH [73]
Cu2O/Cu@C 665 0.5 38.6 5000 1 M KOH [74]
CuxO-C/PANI 1308 1 55.1 10000 3 M KOH [75]
HKUST-1@TS- 1812 1 - 2000 - [76]
800
(Areal
(Cu-MOF) capacitance)
2.3. Mn-MOF templates
Among metal and metal oxides (MO) of transition elements, manganese and manganese oxide-
based material have attracted more attention due to its low cost, availability, mechanical
stability, and high theoretical capacitance. However, manganese as individual material is
insufficient to withstand volume expansion of electrode due to charge-discharge cycles in
supercapacitors. To overcome this problem of MO disintegration, MOF-derived MO are used.
Mn-MOF-derived materials show excellent stability as electrode material, owning properties
to MOF and the complementary element [77].
Chen et al. synthesized 6-coordinated cubic structure of manganese oxide through
calcination of hydrothermally-synthesized Mn-MOF, using melamine, H2ipa and
Mn(CH3COO)2.4H2O for 3 days at 180°C. The further calcination at 500/600 °C for two hours
lead to the formation of 3D hollow cubic structures of Mn3O4/Mn2O3 cluster, which offered
pseudocapacitance of 150 Fg-1 at 1 Ag-1 current density in Na2SO4 electrolyte, due to the high
surface area of non-interpenetrated primitive cubic structure of manganese oxide and multiple
16

redox states of Mn[78]. Chen et al. documented electrode material with mixed valence MnOx
extracted from Mn-MOF and grown in-situ on the carbon sheet with ultrathin 2D matrix. The
insertion of carbon matrix imparted conductivity by improving transport of electrons and ions
from electrode to the collector and prevented volumetric change of MnOx with dissolution
during charge/discharge cycles. Mixed valent Mn nanoparticles induced electronic and ionic
defects, enhanced storage capacity for super capacitor by 220 Fg-1 at 1 Ag-1 current density and
reversible capacitance of 1217.7 mA hg-1 with 160 cycles at 200 mAg-1 current density as an
anode material for lithium ion batteries[79]. To overcome the electrical instability of metal
oxide, Zhao et al synthesized MnO2 nanostructure derived from Mn-MOF that was vertically
assembled on carbon nanosheets, which was further annealed at low temperature of 60 °C in
high alkaline solution. The oxidation caused by low temperature transformed the low valence
Mn ions to high valence Mn ions and prevented carbon oxidation during synthesis. The robust
integration between MnO2 and carbon sheets enhanced cyclic stability by 5000 cycles at 5 Ag-1,
whereas high surface area imparted excellent ion diffusion and charge storage area by yielding
capacitance of 339 Fg-1 with 0.1 Ag-1 current density [80].
Yuan et al. reported different structures of manganese oxide, depending on
crystallographic phases of MOF. The reaction of Cu-MOF and KMnO4 at different pH led to
nanostructures of manganese oxide with α, β, and δ phases. Among the three crystallographic
phases, α manganese oxide with layered morphology displayed better capacitance of 416 Fg-1
at low current density of 0.5 Ag-1 with 5000 cyclic stabilities. The well-defined surface area of
240 m2g-1 and layered structure of α phase provided free space for catalytic reaction, whereas
manganese oxide favored faradic reaction inducing fast charge transfer mechanism resulting in
high capacitance. The practical application of α-MnO2 was studied by using it as negative
electrode with AC as positive electrode in ACS system, which showed high power density of
425 Wkg-1at 23.2 Whkg-1 energy density [81].
17

Chen and his team constructed hallow-microspheres by utilizing hierarchal properties of Mn-
MOF as a template for synthesizing manganese oxide and carbon microparticles composites,
which resulted in Mn2O3-HMS complex with high capacitance at low current density of 1058
F g−1 and 1 Ag-1 respectively, which was relatively greater than the state-of-the-art composite.
The synergetic effect of oxides and carbon-induced oxygen vacancies increased redox active
species and reduced path length, thereby increasing capacitance. The hollow spherical structure
of Mn2O3 examined by SEM in Fig. 6 (a, b, c) pawed higher surface for ion interaction and
stabilized the material from undergoing degradation by retaining 90.2% of capacitance after
4000 cycles. The flexible solid-state hybrid supercapacitors was constructed with Mn2O3-HMS
cathode and activated carbon as anode with KOH-PVA electrolytic gel in between them, and
showed excellent flexibility up to 180°, with 487.86 mF cm− 2 areal capacitance at 1Ag-1 current
density along with 100% retention of capacitance after 1500 cycles [82]. Table 3 gives idea
about different Mn0based MOF developed for supercapacitor application.
For improved capacitance rate, Wang and his coworkers designed a new bimetallic
phosphide complex by phosphorizing nickel embedded Mn-MOF, which resulted indeed in an
enhanced capacitance of 1060 Fg-1 at 1 A g− 1 current density with 2000 cycles at rate of 75%
retention of capacitance. The incorporation of nickel nanoparticles and phosphate group
facilitated the fast charge transfer activity and storage capacity. The material delivered high
power and energy density of 799.6 kW kg-1 and 21.1Wh kg-1 respectively along with 59.3 Fg-1
capacitance when incorporated into and ASC designed with Ni0.4Mn1.6P and activated carbon.
It also maintained 65% the initial capacitance after 1400 cycles[83]. When comparing the
properties of the derived functional materials with Mn-MOF, it showed good storage capacity
and therefor it is widely used in lithium-ion batteries rather than in the super capacitor
application.
18

Table 3. The comparison of performances of Mn-based MOF for supercapacitor applications.
MOF-Mn Specific Current Energy

capacitance density density Cyclic
based/derived Electrolyte Ref.
stability
functional material (Fg-1) (Ag-1) (Whkg-1)
Mn-pPDA 109.3 1 34.2 5000 KOH [84]
MnOX 150 1 500 Na2SO4 [85]
MnOx-CSs-600 1.0 M
220 1 27.5 2000 [79]
Na2SO4
328.4 0.5 M [74]

Mn3O4@C/rGO 0.5 - 10000
Na2SO4
1M
MnO2/CNS 339 0.5 - 5000 [80]
Na2SO4
α & βMnO2 416 0.5 23.2 5000 1 M NaOH [81]
Mn2O3-HMS 1058 1 36.73 3500 6 M KOH [82]
Ni0.4Mn1.6P 1060 1 21.1 2000 - [83]
MnOx/NC/MnO2 30.1 0.5 16.8 5000 - [87]
MnO/C@rGO 1536.4mAh/g 100 - 500 -
2.4. MOF-5 functional derivatives
The MOF-5 is the zinc-based MOF which is also known as IRMOF-1 that have been
extensively applied as precursors for developing porous carbon material as it imparts good
porosity, high surface area and stability to the structure which generally gives rise to EDLC
behavior [89]. Kukulka at el. examined the capacitance of three different kinds of MOF, i.e., 1D,
2D and 3D hallow carbonous composites which was synthesized by in-situ physical and
chemical mixing methods. It was observed that electrochemical properties varied with different
morphologies, in which 2D morphologies of CMOF-5-GO gave better performance exhibiting
195.4 Fg-1 at 1 Ag-1 current density with cyclic constancy of 3500 cycles due to meso and
19

microporous structure of CMOF-5-GO composite in comparison to the CMOF-5-CNT in
which CNT’s reduced the pore size resulting in agglomeration that further reduced the surface
area for ion interaction. The incorporation of GO in MOF acted as the conductive network
between CMOFs favoring electrical conduction[90]. Banerjee et al. reported 3-dimensional
cuboidal shaped porous carbon derived from pyrolyzing MOF-5 in argon ambiance for 8h at
1000 °C. The derived porous carbon was used as cathode material along with Li4Ti5O12 as
anode for lithium-ion hybrid capacitors which displayed better execution of electrochemical
activity than the commercially available activated carbon with 65 W hkg-1 energy density.
The high surface area offered by the crumpled sheet-like structure of cuboidal carbon
enhances the ion diffusion and charge accumulation on the electrode giving rise to a
capacitance of 149 F/g in an organic medium when checked for single electrode and delivered
10000 cycles with integration of Li4Ti5O12 and carbonized MOF proving as a good material for
batteries[91]. Supercapacitor electrode interconnected with 3-dimensional porous carbon
structure was synthesized by treating MOF-5 with KOH through microwave assisted technique
which offered high specific capacitance of 212 Fg-1 at 0.05 Ag-1current density. Yu et al.
observed that the activation of MOF by KOH induced shorter diffusion length and high
mesoporous nature with interconnected structure provides a path for ion storage and conduction
of electrons with retentivity of 95.9% after 1000 cycles [92]. Cendrowski et al reported the
synthesis of zinc-based MOF using recycled terephthalic acid and DMF that resulted in more
cost-effective and eco-friendly materials. For the fabrication of electrode poly(vinylidene
fluoride), MOF-5 were fused in three different ratios of 75:25, 80:20, and 85:15, before
subjected to carbonization for the synthesis of carbonized MOF/PVDF electrode which
displayed capacitance of 180 Fg-1, 210 Fg-1, and 218 Fg-1 respectively. These varied values of
capacitance proved that the concentration of the precursor and binder elements influenced the
storage capacity of the material to greater extent.
20

The high wettability, dielectric constant, and strong electron-withdrawing groups introduced
by PVDF in highly crystalline MOF induced the high storage capacitance of 99.99 Fg-1 at 50
Ag-1 current density. The recycling of active material from the used electrodes, DMF &
terephthalic acid for electrode fabrication showed greater stability with cubic structure of
MOF-5 making them cost-effective and nontoxic for practical application [93]. Mesoporous
carbonous nanospheres were synthesized from transforming MOF encapsulated on activated
carbon by pyrolysis method to form MOF/carbon composite with spherical spheres having 677
m2g-1 surface area with 0.412 cm3g-1 pore as reported by Khan et al. On carbonization, it not
only increased yield of CNS but use of soft template approach provided good surface area for
capacitive storage and uniform meso-macro-porous improved ion diffusion by providing 300
Fg-1 capacitance at 1.5 Ag-1 current density with cyclic durability of 3000 cycles at 91.5%
retention[94].
Banerjee et al. doped nickel in MOF-5 and carbonized it at 650 °C that formed one
dimensional plate-like graphitic nanofiber morphology. The as-formed nanofiber of graphitic
carbon by MOF improved the conductivity as well as surface area with more active sites for
ion diffusion promoting double-layer capacitance whereas nitrogen particles from complex
induced by doping undergo Faradic reactions in potassium hydroxide electrolyte by yielding
348F/g specific capacitance with 5000 cyclic stability[95]. Li et al. synthesized electrodes for
supercapacitors by integrating nitrogen-doped graphene quantum dots onto porous carbon
derived by carbonizing MOF-5 at 700 °C in argon gas which yielded N-GQD/cMOF-5. The
integration of MOF in complex imparted high surface area with extreme porosity whereas
nitrogen-doped graphene quantum dots introduced pseudocapacitance by improving the
interaction between electrode and electrolyte giving rise to high storage capacitance of 780 Fg-
1. Incredible cyclic durability of 5000 cycles was observed at 0.5 A g−1 current density with
94.1% retention in the initial capacitance of 294.1 F g−1 when used as symmetric capacitor,
21

whereas in case of ASC built with activated carbon as negative electrode, 91% retentivity was
observed with high power and energy density of 400.6 W kg−1 and 14.4 W h kg−1,
respectively[96].
Yi at el. designed asymmetric supercapacitor with CNT@NiO composite as positive
and PCPs as negative electrode. Where polyhedron carbon was synthesized by carbonizing
MOF-5 and CNT@NiO was formed by chemical bath deposition method, on annealing gave a
core-shell structure. The enhanced electrochemical activity provided by core-shell structure of
the composite induced greater capacitance of 996 Fg-1 in KOH solution at 1.0 Ag-1 current
density. The presence of a nickel doped carbon network along with MOF imparted high
electrical and mechanical stability with 25.4 Whkg-1 energy density along with 10000
cycles[97]. The comparison of various results displayed that MOF-5 has several advantages
varying from easy synthetic approach, integrity and effectively carbonizes the material,
however it still lacks to meet the demand of storage devices when compared to other MOF’s.
Table 4 explains comparative performance evaluation of MOF-5.
Table 4. The evaluation of performances of MOF-5 based electrode material for super
capacitor application.
MOF-5
Specific Current Energy Cyclic
based/derived
capacitance density density stabili Electrolyte Ref
functional ty
(Fg-1) (Ag-1) (Whkg-1)
materials
1M
Zn-MOF 80 0.1 - - [98]
TEABF4/AN
[91]
1 M LiPF6 in
MOF-5 149 - 65 10000
the EC–DMC
[90]
CMOF-5-GO 195.4 1 - 3500 1M H2SO4
MOF-5 212 0.05 - 1000 6M KOH [92]
22

CMOF-5 218 1 - - 1M H2SO4 [93]
K@bio-MOF-1
230 1 - 10000 KOH [99]
Zinc
MOF-5 and 239

- - 10 000 1 M H2SO4 [100]
IRMOF-3
N-MC 295 0.5 - 400 6 M KOH [89]
MOF-5 300 1.5 - 3000 KOH [94]
10000
Zn-MOF 322 1 70 6 M KOH [101]
0
MOF-5 1 M Na2SO4,
348 0.5 - 5000 [95]
1 M KOH
Zn(tbip) 369 1 12.5 2000 6 M KOH [102]
N-GQD/cMOF-5
780 0.5 14.4 5000 1 M H2SO4 [96]
composite
CNT@NiO 996 1 - 10 000 1 M H2SO4 [97]
2.5. Nickel-based MOF
The Nickel-based MOF is one among the most commonly used MOF for supercapacitor
application as it has shown very good conductivity, absorption, and catalytic activity due to the
presence of Ni+2 cations within the framework as it helps in producing more redox reactions
[103]. Sheberla et al. reported capacitive material using conductive MOF which was developed
by using Ni3(HITP)2, the Π stacking of conjugated 2D layers in Ni3(HITP)2 helped to get a
large surface area and small pore size, showing double-layer capacitance of 117 Fg-1 areal
capacitance at 0.1 Ag-1 current density with high cyclic stability and also acted as the best
material for electrochemical double-layer capacitors[104]. Yang et al. tried to improve the charge
storage capacity by simple annealing the Ni-CAT Nano crystal by turning into rod-shaped
23

nanoporous carbon that retained the shape of MOF and improved storage capacity by 127 Fg-1
at 0.5 current density due to the enhanced electron conduction and ion transport path[105].
Similarly, Zhang et al. also tried to improve capacitance by transforming Ni-MOF into
Ni(OH)2 nanoflake-like structure by facile hydrolysis method in potassium hydroxide solution
and controlled its shape and size by varying its concentration and soaking time. The inter and
deintercalation of hydroxyl ions provided by the remarkable interlaced flake-like structure
through the active surface area improved the storage stabilities whereas tunnel-like structure
helped in migration of hydroxyl ions to the active sites, by reducing inner resistance which in
turn gave rise to high capacitance of 830.6 Cg-1 with high cyclic stability of 15000 cycles at
low current density of 0.5 Ag-1 [106]. Lam et al. combined nickel and carbon to form a composite
by transforming rod-shaped Ni-MOF to spherical nickel nanoparticles using a CO2 laser. It was
found that the redoxitivity of α-Ni(OH)2 nanoparticles increased owing to their small pore size
when compared to the β-particles proving smaller pore size and higher surface area enhances
the redox reactions and favor storage capacitance.
Hence, existence of α- and β-Ni(OH)2 phase imparted more redox-active sites which
improved storage capacitance of a material by increasing the pseudo-capacitance up to 925 Fg-1
at 0.5 Ag-1 current density with 5.5 nm particle size and cyclic stability of 5000 cycles[107]. Li
et al. synthesized core-core shell structure of nickel based MOF and cobalt-MOF-74 using
solvothermal method by growing Ni-MOF over Co-MOF in presence of Na2S which favored
the dissolution of MOF ions as shown in the Fig. 7 a, hydrolyzation speed of S2- ions and
Kirkendall effect arise due to small pore size that resulted in the double core in core-shell
structure which was evident from SEM, that presented the double-shell formation in Fig. 7 (b-
c). The coupling interface formed by electronic interaction between Ni3S4 and the Co9S8 favors
high storage capacity with a specific capacitance of 1257.4 Fg-1 at 4 Ag-1 current density along
with 1000 cyclic stability which provided a path for self-template fabrication of electrode[108].
24

Shi et al. fabricated composite material for practical application of supercapacitor by growing
Ni-MOF on carbon oxide sheets using hexadentate ligand that enabled self-doping of oxygen,
phosphorus, and nickel in the Ni/rGO matrix-forming Ni/C/rGO composite.
The pyrolysis of MOF grown in Ni-foam enabled high porosity to the composite which
induced high surface area with large functional sites. Further the synergetic effect of rGO and
MOF complex along with hetero dopants curtailed ion diffusion path and amplified charge
transfer kinetics within the electrode material giving rise to the high specific capacitance of
1258.7 Fg-1 with 50000 cycles at 8 Ag-1 current density. Homogenous dissemination of Ni-C
complex on rGO sheets, reduced the decomposition of active material during charge-discharge
cycles thereby imparting structural rigidity to the electrode. When asymmetric supercapacitor
was built using Ni/C/rGO-4 and AC as positive & negative electrodes respectively, high energy
and power density of 79.7 Wh kg-1 and 1275 W kg-1 was observed in KOH electrolyte
solution[109]. Yang and his team documented the composite of Ni-MOF and carbon nanotubes
doped with nitrogen that improved the conductivity and imparted greater redox current density
along with high storage capacity of capacitance 1489.9 Fg-1 at 1 Ag-1 current density. The
doping of nitrogen in the carbon matrix improved the moment of electrolytic ions and the
reaction kinetics of the elements in the complex by inducing the 3D structure to the complex
and cyclic stability of 3000 cycles[110].
Yang et al. further reported binder-free fabrication of ZnNiP array by growing zinc
doped Ni-MOF on nickel foam, which on phosphorylation yielded ZnNi-MOF-0.5 as
represented in Fig. 7 (e) displaying the schematic preparation of active material. However,
synthetic effect of zinc, phosphate, and nickel ions induced numerous redox-active sites, high
conductivity, and charge transport helped it to attain great electrochemical properties
implementing its use in both hybrid-super-capacitors and zinc batteries. High energy and power
density of 67.4 Wh kg−1 and 15.9 kW kg−1 were displayed with the high cyclic performance of
25

10,000 cycles after 88% retention. When tested as a hybrid capacitor and as a zinc battery, it
displayed 529.58 Wh kg−1 energy density at nearly 1.9 V discharge voltage with 91.6 %
retention after 300 cycles. Thus, the process reported systematic binder-free synthesis for
electrode material[111]. Ultrahigh capacitance material using p-π conjugated-MOF with nitrogen
doping was reported by Huang and his team. Graphitization of p-π conjugated-Ni-MOF
resulted in nitrogen-containing carbon-rich multi-structures with inherent properties of MOF.
Table 5 shows different Ni-based MOF used for supercapacitor electrode and its obtained
performance.
The conjugation of ligands and MOF, enhanced conductivity and stability of the
carbonized material attributed to high capacitance of 2727.5 F·g−1 at 1.0 A·g−1.current density
with 20,000 cycles which was evident from C-V and GCD test at a scan rate of 10 mV s-1.
When asymmetric capacitor designed with MOF-B-600 and activated carbon as electrodes
displayed great power and energy density of 400 W·kg−1 and 63.62 Wh·kg−1 respectively with
the efficiency of 90.7% [112]. The efficiency of nickel-based MOF as a precursor for
synthesizing highly functional materials has been discussed above, by which it is evident that
Ni-MOF plays a significant role in inducing the conductivity and charge transport efficiency,
thereby improving the capacitance of the derived material.
Table 5. Supercapacitor electrode based on Ni-based MOF and its comparative performance.
Type of Nickel Specific Current Energy

capacitance density density Cyclic
based/derived Electrolyte Ref
stability
MOF (Fg-1) (Ag-1) (Whkg-1)
MOF Ni3
117 0.1 - 10000 [104]
-
(HITP)2
6.0 M
CN rods 127 0.5 - 2000 [105]
KOH
26

2D Ni-MOF
Ni@NC core-shell 448 0.5 33 4000 - [113]
rings
NiO/rGO 435.25 1 76.96 25,000 6 M KOH [114]
NiO/C@CNF 742.2 1 58.43 5000 3 M KOH [115]
Ni-MOF 830.6 0.5 37.8 1500 6 M KOH [106]
MOF-74(Ni) 925 0.5 5000 6 M KOH [116]
Ni-MOF-74@Co-
1257.4 4 1000 2 M KOH [117]
MOF-74
Ni-MOF/GO-n 5 1258.7 8 79.7 50000 6 M KOH [118]
Ni-MOF/CNTs
1489.9 1 - ̴3000 1 M KOH [110]
ZnNiP 1416.3 C g−1 5 mA cm−2 67.4 10000 6 M KOH [111]
Ni- 3626.4
2 45.6 10000 - [119]
MOF/PANI/NF (areal cap)
MOF-B-600 2727.5 1 63.62 20000 3M KOH [112]
2.6. Rare MOF templates
Other than the above-mentioned MOF’s, researchers have tried to fabricated electrode material
with different types of MOF by using various metal nodes such as cerium, cadmium, iron,
zirconium, aluminum, and many more. Apart from the materials derived from the commonly
used precursors, these MOF’s also showed good electrocatalytic activity in enhancing the
capacitance of material[120]. Pan et al. developed a new method to fabricate porous carbon
electrodes by using bare bio-MOF-1 and potassium inserted bio-MOF as a precursor for
synthesizing porous carbons. The nitrogen-rich linker molecules decorated nitrogen on the
porous carbon without doping nitrogen in it, which helped in capturing CO2 and increases the
surface conductivity. The incorporation of potassium in MOF imparted micro-porous structure
(KBM-T- 700) giving rise to a capacitance of 230 Fg-1 with 97% of retention after 10000 cycles
27

whereas bare MOF-1 (BM-T 700) showed mesoporous structure with the comparatively low
capacitance of 192 Fg-1 at 1 Ag-1 CD.
Apart from electrochemical storage of charge, it also showed higher selective
absorbance of carbon dioxide over dinitrogen at 298 K and 1 bar, showing its utility in multiple
ways [121]. Zhang and his coworkers thermally derived porous carbons namely NPC800 and
NPC900 at 800 and 900 °C respectively from cadmium-based MOF’s which were synthesized
by using two types of organic linkers to derive L-I and D-1 order of the framework which
stored charge up to 257.2 Fg-1 at 0.25 Ag-1 current density. When compared to PNC900
structure, PNC800 showed higher charge retention and storage capacity even at extreme
charge/discharge rates because of the low resistance provided by non-distorted uniform
mesoporous structure of PNC800, along with a shorter diffusion path resulting in a high power
density of 300 W kg-1, whereas PNC900 displayed low capacitance because for damaged
morphology due to high degree of carbonization of MOF[122].
To increase the capacitance of the material, Chen and his coworkers fabricated a
ZnCo2O4 nanostructure-based electrode using JUC-155 by solvent-thermal process, where
JUC-155 was transformed to highly porous ZnCo2O4 nanoparticles with a ASA of 55 cm2g-1
by heating it at 400 °C in open air for two hours. The synthesized material showed EDLC
behavior with slightly pseudocapacitive nature due to large surface area offered by
nanostructures and redox reactions caused by mixed metal ions, led capacitance of 451 Fg-1 at
a scan rate of 5 mVs-1 in 6.0 M KOH electrolyte along with counter and reference electrode as
platinum and Ag/AgCl respectively. It was seen that only 2.1% loss of capacitance was
witnessed after 1500 cycles at 2 Ag-1 current density, and thus indicating its potential in being
good electrode material for super capacitors[123].
28

In order to enhance the capacitance, Yu and his group fabricated electrodes of hollow
metal oxide nanowire derived from MOF-74 with a 1:1 ratio of cobalt and nickel oxide
synthesized by a solvent-free method. The synergetic effect of two different metal oxide phases
induced excellent redox activity, conductivity, and storage capacity of 732.0 Cg-1 at Ag-1
current density. To test the power and energy density, synthesized material was used as a
negative electrode whereas commercially available AC was used as the positive electrode in
ASC setup which gave rise to a high power and energy density of 425.3 Wkg-1and 46.9 Whkg-1
in 6 M KOH. The exceptional charge transfer and diffusion of ions was acquainted by
mesoporous structure of NiO/NiCo2O4 (1:1) nanowires with pore size of 5 nm and profuse
redox reaction through surface functionalities. Lattice defects of NiO and NiCo2O4 improve
overall electrochemical reaction.
Further, the hollow structure of material helped in the expansion of electrode without
affecting its structural integrity by 3000 cycles during charge-discharge cycle[124]. Mahmood
et al. designed asymmetric supercapacitor from MOX-Al and MOX-Fe that were derived from
MIL-100. The as-synthesized xerogels were subjected to carbonization to form porous carbon-
nanoparticles which contained uniformly distributed Fe3O4 in carbon matrix. An abundance of
oxides and multiple conversion of iron to Fe2+ and Fe3+ in the sample increased the rate of redox
reaction which in turn increased the capacitance by 600 Fg-1 at 1 Ag-1 current density. To test
the efficiency of synthesized hybrid nanostructures, Fe3O4/Fe/C nanoparticles were considered
as cathode whereas NPC derived from MOX-Al was taken as an anode in 6M KOH electrolytic
solution, displayed high power density of 388.8 WKg-1 at 17.496 WhKg-1 energy density due
to effective redox reaction of Fe+ and Al- ions[125]. Wang also synthesized metal oxide
incorporated porous carbon by carbonizing mixed metal oxide MOF’s at 3 different
temperatures of 600, 700, and 800 °C forming three different samples. Among the obtained
samples, M/MO@C-700 showed the highest ASA and large pseudo-capacitance due to the
29

higher content of Mn, Co and C in the matrix along with OH- ion and uniform porous structure,
when compared to MOF-600 and 800, which helped in increasing capacitance by 800 Fg-1 at 1
Ag-1 current density by improving the redox reactions[126].
Zhou et al. tried to test the practical applicability by designing a wearable high-handed
asymmetric supercapacitor by growing α-Fe2O3@C on CNT fibers derived from (MIL-88-Fe)
iron-based MOF. The development of S-α-Fe2O3@C on carbon nanotubes imparted properties
such as large surface area, lightweight, conductivity, and exhibited considerable specific
capacitance of 1232.4 mFcm-2 at a current density of 2 mAcm-2, due to synergetic effect of
oxygen, iron, and carbon content in α-Fe2O3@C and MOF. When FASC device was fabricated
by using S-α-Fe2O3@C/OCNTF as anode and Na-MnO2 NSs/CNTF as cathode, displayed
high power density of 2199.9 µWcm-2 at an aerial energy density of 135.3 µWhcm-2 and
maintained the same power density of 91.7 µWhcm-2 even at 21998.8 µWcm-2 with 4000 cyclic
rates and 94.1% retention which was evident from the C-V curves[127]. R. Ramachandran,
instead of using MOF as a precursor he used cerium-based MOF as a functional material along
with GO and CNT to form a composite separately for supercapacitor application. Due to
synergetic effect of MOF and GO, superior capacitance of 2221.2 F/g was observed in 3 M
aqueous KOH + 0.2 M K3Fe(CN)6 electrolyte solution at 1 Ag-1 current density. Table 6
demonstrate the different MOF used for supercapacitor application and its performance
analysis. The incorporation of GO increases the interaction between electrolyte and electrode
thereby inducing pseudocapacitance due to redox reaction carried by oxygen species[128].
Therefore, MOF does not only act as a template or building cells for electrode material but
when combined with other elements, it gives a resultant material a new direction of properties,
functionalities, and multidimensional application. Owing to such an extraordinary feature, the
MOF-derived material can open its practical application in various fields.
30

Table 6. Comparison of performance of different types of MOF based electrode material for
supercapacitor application.
Different type of
Specific Current Energy
MOF and derived Cyclic
capacitance density density Electrolyte Ref.
materials stability
(Fg-1) (Ag-1) (Whkg-1)
(TCNQ)-MOF
223.117 1 3000 6 M KOH [96]
(Sr-MOF)
6.0 M
K@bio-MOF-1 230 1 - 10000 [88]
KOH
6.0 M
Cd-MOF 257.2 0.25 - 3000 [122]
KOH
6.0 M
ZnCo2O4 451 1 - 1500 [123]
KOH
MOF xerogels (MOX-

600 1 17.496 5000 6 M KOH [125]
Fe, MOX-Al)
MOF-74/Co/Ni
732.0 1 46.9 3000 - [124]
CoMn-MOF-74 800 1 - 1000 6 M KOH [126]
1232.4
1M
MIL-88-Fe (areal 2 4000 [127]
Na2SO4
capacitance)
3 M KOH+
Ce-MOFs composite 2221.2 1 111.05 5000 0.2 M [95]
K3Fe(CN)6
0.1 M
SiCNWs@NiCo2O4NAs 1604.7 F 0.5 49.9 5000 [29]
KOH
3. ZIF templates for electrode materials
Zeolitic imidazolate framework is considered the finest subclass of the metal-organic
framework, which is a synthetically modified version of alumino-silicate zeolites with zinc as
a metal ion and imidazole as a linker having a strong coordination bond between them that
31

makes them more chemically and thermally stable[130]. Due to the ultra-high surface area,
flexible pore size, crystallinity, diversity in structures and morphologies make it a more suitable
candidate for numerous applications varying from gas absorption, storage, filtrations, pollutant
degradation, batteries, and supercapacitors to drug delivery in medication. When it comes to
supercapacitors ZIF’s are most widely used as precursors because of its ultra-high surface area
for ion diffusion storage capacity and robust chemical and mechanical stability[131].
Liu et al. synthesized hierarchical carbon electrode by integrating carbon derived from
ZIF-8 onto graphene sheet that imparted flexibility with high micro/mesoporous surface of
2837 m2g-1 for the moment of large and small ions through it by favoring high charge transfer
in organic gel electrolyte providing specific capacitance of 201 Fg-1 with improved durability
of 10000 cycles[132]. Similarly, Zhang et al. performed carbonizing ZIF-7 and treated with other
carbonous agents such as glucose resulting MOF derived porous carbon, that lead to good
conductivity and stability, attributed to the presence of carbon content and inherent
microporous structure, that favored fast ion transfer during charge-discharge cycles there by
increasing conductance by storing charge of 228Fg-1 at 0.1Ag-1 current density with 5000
cycles[133]. Salunkhe et al. reported synthesis of nanoporous carbon and Co3O4 nanoparticles
by annealing ZIF-67 in the nitrogen atmosphere which retained the polyhedron structure of
ZIF. It has been observed that the porous carbon like structure gave good chemical stability to
the material whereas Co3O4 being a pseudocapacitive material imparted fast ion diffusion and
charge transfer by inducing capacitance of (Co3O4) 508 Fg-1 and (porous carbon) 251 Fg-1 at 5
Ag-1 current density with 2000 cyclic stability[134].
Zhang et al. designed asymmetric capacitor by fabricating two different types of
composites, one with zinc oxide quantum dots and other with nitrogen doping in carbon/CNT
matrix using ZIF-8 as a precursor, among which nitrogen-doped complex showed better
capacitance than ZnO quantum dots with 250 Fg-1 at 0.5 Ag-1 current density because of higher
32

charge transfer and conductivity in nitrogen doped complex than zinc oxide quantum dots.
When tested practically, by assembling as asymmetric supercapacitor of QDs/carbon/CNTs &
N-doped carbon/CNTs as positive and negative electrodes which displayed a good energy and
power density of 23.6 Wh kg-1 and 16.9kW kg-1[135]. A simple carbonization of polydopamine
treated/coated ZIF-8 polyhedrons was synthesized by Zhang et al. which yielded ZIF-8@PDA-
C composite. Grater nitrogen content in the composite added higher electrochemical activity
thereby inducing pseudocapacitance with a specific capacitance of 253 Fg-1 at 0.2 Ag-1 current
density and ordered hollow structure of carbonous complex imparted grated cyclic stability of
10000 cycles with 93% retention of capacitance [136].
Liu et al. reported composite by depositing ZIF-67 on carbon cloth which was further
treated with polypyrrole to give high conductive, flexible, and durable composite with ultra-
high cyclic stability of 40000 cycles. The EDLC and pseudocapacitance offered Ppy and ZIF
imparted storage capacitance of 284.3 Fg-1[137]. The growing demand for supercapacitors with
high capacitance and durability made researchers dig more into different types of morphologies
such as layered, hollow cages, flowerlike, core-shell, Hollow mesh, quantum dots, sheetlike
structures, etc. so that they can improve the cyclic durability along with the capacitance. Hout
et al. fabricated Co9S8@N−C@MoS2 composite with core-shell structure by sulfurizing,
calcining, and vulcanizing ZIF-67. High surface area and synergistic effect of two transition
metals with core-shell structure impart high chemical stability and enhanced area for volume
expansion of electrode during charge-discharge cycles, yielding high stability of 20000 cycles
at 10Ag-1 which is examined by the GCD curve. Interaction of molybdenum and cobalt induced
redox conductivity for storing charge up to 410Fg-1 at 0.1 Ag-1 current density[138].
The practical application was tested of flexible electrode by Zhu at el, fabricated
carbonous composite fusing ZIF-8 and graphene oxide, where oxygen species from GO
captures ZIF & ZIF helps to bind Ni2+ and Co2+ and provide stable structure to withstand
33

charge-discharge expansion of 10,000 cycles at 1 Ag-1 current density with relatively high
capacitance of 843.0 Cg-1 with 97.96% rate. When the fabricated electrode setup was tested
with three LED lights it glowed for 50 minutes proving its applicability[139]. Yu et al. fabricated
layer by layer ZIF-LDH/GO complex using ZIF-68 as precursor and graphene oxide as anchor
which not only provided site for nucleation of nanocrystals but also prevented staking of
layered nanosheets which facilitated high ion/charge transfer by creating inter connected
networks inside ZIF-LDH hybrid, thereby improving the capacitance up to 904.3 Fg-1with
cyclic stability of 5000 cycles at 1Ag-1current density favored by nanoporous structure of
composite[140].
Guo et al. practically fabricated asymmetric electrodes for supercapacitor by growing
ZIF-67 on nickel foam which was further subjected to types of sulfurization at different
temperatures to form NiCo2S4 and CoS2 with hollow mesoporous morphology which
empowered active site and led continuous ion diffusion by providing specific capacitance of
939 Fg-1 at 1 Ag-1 current density. Direct contact of hybrid structures with nickel ensures good
electrical conductivity by favoring electron transfer within the electrode and imparts
mechanical stability with 7.2% loss of capacitance after 5000cycles[141]. Dai et al. designed
CC@CoO@S-Co3O4 composite material for flexible supercapacitor by depositing hollow
sulfur-doped Co3O4 formed by transforming ZIF-67 on commercially available carbon cloth.
High pseudocapacitance of 1013 Fg-1 at 1 Ag-1 current density was attributed to synergistic
effect of hetero-doping which induced high electron transport with improved cyclic durability
of 5000 cycles. The use of carbon cloth along with Co3O4 nanoparticles imparted conductivity,
light-weightiness and flexibility to the material proving it to be reliable material for flexible
electrodes for storage devices[142].
Wei et al. reported the charge storage ability of Co3O4 nanoparticles with a 2D ultrathin
nano meshes like structure by annealing ZIF-67 offered a large surface area yielding number
34

of active sites for ion diffusion and hydroxyl ion interaction induced high charge transfer.
Oxygen vacancies in Co3O4 and Co2+ ion-rich surfaces of 2D nanomesh enhanced faradic
reactions by providing high pseudocapacitance of 1216.4Fg-1 at 1 Ag-1 current density.
Nanoporous mesh-like structure prevented volume enlargement of electrode material during
charge/discharge process by providing structural integrity with 2000 cycles[143]. Vilian et al.
synthesized high capacitance electrode material by incorporating reduced graphene oxide into
a hexagonal sheet-like the structure of tricobalt tetraoxide derived from ZIF-67 by a
hydrothermal process which offered high surface area for ion diffusion and conductance
offered by Co3O4 enhanced charge storage capacity by providing high capacitance of 1300
Fg-1 at 4 Ag-1 current density with 5000 cyclic repeatability[144].
Xiao et al. synthesized nano hollow cage-like structure using ZIF-67 as a template for
coating with LDH and then subsequent etching using Na3PO4 to form ZIF-67@Co−NiLDH.
Open ends of hollow structure imparted surface functionalities whereas high conductive
properties of bimetallic phosphate impart high charge transfer and electron conduction thereby
inducing, improved storage capacitance of 1616 Fg-1 at 1 Ag-1 current density and synergetic
effect of ZIF and LDH stabilizes the structure by providing 10000 cyclic stability with 80.32%
retention[145]. Jayakumar et al. reported a hollow structural cage of NixCo3−xO4 nanoclusters
with superior capacitance of 2870.8 Fg−1 at 1 Ag-1 current density.
The mixed oxide composites derived from ZIF-67 and hydrogels of graphene enhanced
the conductance, porosity, rigidity, and charge transport ability of the material which resulted
in such high capacitance and cyclic stability of 5000 cycles which was evident by the cyclic
voltammetry and galvanostatic charge-discharge curves scanned at several scan rates along
with current density as shown in the Fig. 8 (a, b). Scanning electron microscopy graphs in Fig.
7(c, d) shows the spherical hollow morphology of the mixed metal which is covered with the
porous graphene sheet. Further when ASC was built by assembling GNi:Co 1:1 and 3D
35

graphene hydrogel as negative and positive electrode, displayed 750 W kg−1 power density
along with 50.2 Wh kg−1 energy density on potential window of 1.5 V[146]. Owning to such
tremendous properties, the ZIF has played an important role as sacrificial template for
transformation of metals into oxides, replacing host metal by other metal ions and graphitizing
core material which induced high electrochemical activity and surface area to the material.
Table 7 explains the comparative performance study of MOF-5 based electrodes.
Table 7. ZIF template-based MOF electrode and its comparative performance supercapacitor
applications.
Types of ZIF and

derived materials Specific Current Energy
capacitance density density Cyclic Electroly
Ref
stability te
(Fg-1) (Ag-1) (Whkg-1)
EMIMB [132]
F4/PVDF
ZIF-8@GO 201 0.5 86 10000
-HFP gel
polymer
ZIF-7/glucose 228 0.1 6M

composite-derived - 5000 [133]
10 KOH
Carbon-L-950
1M
ZIF-8 251 7.5 10.86 2000 [134]
H2SO4
ZIF-8/CNTs 1M
250 1 23.6 - [135]
Template Na2SO4
6M
ZIF-8@PDA-C 253 0.2 - 10000 [136]
KOH
6M
ZIF-67 284.3 1 - 40000 [137]
KOH
ZIF-67-
3.0 M
Co9S8@N−C@Mo 410.0 0.5 - 20000 [147]
KOH
S2
ZIF-8
GO/Zn−Co−Ni 843.0 - 64.91 10000 - [139]
LDHs
36

ZIF-67/GO and
-
ZIF-8/GO 904.3 1 50.5 5000 [140]
(ZIF-LDH/GO)
[141]
ZIF-67 939 1 55.8 - -

.
CC@CoO@ZIF-
1013 1 71 5000 - [142]
67
ZIF-67
1216.4 1 46.5 2000 2M KOH [143]
ZIF-67/
1,300 4 2,048 5000 KOH [144]
RGO‒Co3O4
ZIF-67- 6M
1616 1 33.29 10000 [145]
LDH−CNP-110 KOH
Ni:Co from ZIF- 2M

2870.8 1 50.2 5000 [146]
67 KOH
3M
Zn-Co-ZIF 358.1mAhg-1 10 66.9 1000 [148]
KOH
ZIF-
67/Co3S4/MWCN 976.5 2 - 500 - [149]
ZIF-8 3.18 F cm-2 6 mA cm-2 - 4000 2M KOH [150]
4. Bimetallic MOF derivatives
Bimetallic MOF’s are another type of metal-organic frameworks that contains two inorganic
elemental nodes connected by organic linkers. The two metallic nodes were integrated into the
framework and proposed to overcome the drawbacks of MOF such as conductivity, stability,
and its efficiency in various applications (supercapacitor, catalytic activity, gas absorption)[151].
Based on the structure, bimetallic MOF are categorized into solid solutions and core-shell
frames. In solid solution, metals are evenly distributed throughout the framework, they can be
directly synthesized and post modified for further uses[152].
The core-shell structure has two parts i.e., inner core and the outer shell where the
composition of both core and shell are entirely different from each other, consolidated in one
crystal. Core-shell structure can be developed from seed-induced growth on the other material
37

whereas exchange of metal ions takes place by post-synthetic method[153]. Lately bimetallic
MOFs are preferred over monometallic framework due to their intrinsic property of superior
redox activity and numerous valance states which help in achieving high electrochemical
activity. Thus the synergetic effect of two metal ions in the framework helps to improve the
charge transfer rates, adsorptive rates, active sites and redox reactions thereby enhancing
specific capacitance[154]. With such outstanding properties, BMOF are extensively used as
building blocks for synthesizing various functional materials with inherent properties of
bimetallic MOF[155]. Hexagonal composite of nickel oxide mesoporous carbon nano-discs was
synthesized by Zeng et al using heterobimetallic MOF’s which imparted crystalline structure
to nanorods after pyrolysis of Ni-Zn BTC at 910 °C yielding NiO/MNC complex.
The integration of Ni-Zntrimesic acid and interaction of Ni+2 and Zn+2 induced redox
reactions whereas graphitization of hexagonal Ni-ZnBTC imparted conductivity and active
sites for interaction of ions leading to high cyclic stability of 8000 cycles with a specific
capacitance of 261 Fg-1[156]. Yan et al fabricated MnS/MoS2/C nanoflakes by calcining and
sulfurizing Mn/Mo-MOF, which acted as a building block for nanoflakes formation with high
surface area crystallinity, porosity, and stability. The synergetic effect of carbon matrix and
MOF along with high ion absorption and charge transfer was imparted by open edges of the
molybdenum and sulfur atoms on the plane of MoS2which increased capacitance to 1162 Fg-1
with 0.5 Ag-1 current density with 75.7% retention of initial capacitance (880 Fg−1) at 10 Ag-1
current density and showed photocurrent response on irradiation of visible light. When
asymmetric supercapacitor was designed using MnS/MoS2/C nanorods & AC, as a positive and
negative electrodes, high capacitance of 75 Fg-1 was obtained along with 10000 cycles after
81% capacitance retention[157].
Chen et al. reported flower-like nanosheets assembly synthesized sulfurizing bimetallic
Ni/Co-MOF-5 obtained by etching Ni-MOF in Co(NO3)2 solution which yielded higher
38

capacitance of 1377.5 Fg−1 at 1 Ag−1 current density with a retention rate of 93.7% even after
3000 cycles whereas pristine bimetallic MOF displayed specific capacitance of 1220.2 Fg-1 at
1 Ag-1 current density. The improved capacitance of derived flower-like nanosheet of Ni-Co–
S was ascribed due to the synergetic effect of nickel, Cobalt, and sulfur in a complex which
induced more active sites for redox reactions that empowered charge storage and ion diffusion.
When used as an electrode along with activated carbon in the ASC system, it displayed a high
power and energy density of 1066.42 W kg−1and 36.9 Wh kg−1, respectively[158].
Ouyang reported porous nanosheets of NiCo2S4 derived from CoNi-MOF embedded on
nickel foam after annealing as prepared NF/CoNi-MOFs for 2hrs at 350 0C in the open air
which was then autoclaved for 24hrs at 90°C with 0.2 M Na2S⋅9H2O resulting in nanosheets
of porous NiCo2S4. The redox reaction caused by the metallic ions in the NF/CoNi-MOFs
complex induce high rate of faradic reactions yielding high capacitance of 1354.4 C g−1 with a
current density of 1 Ag−1 in 6M potassium hydroxide electrolytic solution. Strong interaction
between NiCo2S4 and nickel foam maintained the structural integrity of active material by
withstanding 10000 cycles when tested with three system electrodes. Nanosheets displayed a
high power density of 375 W kg−1 at 49.1 Wh kg−1 energy density when assembled as ASC
with activated carbon [159].
Xiong utilized two types of bimetallic MOF to synthesize multiple complexes of
NiCoMOF/NF, FeMOF/NiMOF/NF, CoMOF/NiMOF/NF, and NiFeMOF/NF by growing Ni,
Co, and Fe-based bimetallic elements on nickel foam, which on pyrolysis yielded sulfides.
When used as electrode material, NiCoS/NF-1 showed greater capacitance of 2815.4 Fg− 1 at 1
mA cm− 2 current density due to the synergetic effect of the nickel and cobalt, that offered high
charge transfer mobility, conductivity, and redox activity along with oxygen-evolving
property. It is prominent for catalyzing electrode and FeMOF/NiMOF/NF nanosheets in
39

particular to undergo ORE reactions for 24 h with 88% retention of current density under
ultralow potentials of 293 mV at 50 mA cm− 2 and 359 mV at 100 mA cm− 2[160].
Shinde et al. synthesized marigold flower-like structures of NiCoP complex by growing
bimetallic MOF (Ni–Co-MOF) on nickel foam with amino terephthalic acid as a linker, which
served as a rich source for doping nitrogen in carbon matrix, as shown in Fig. 9(a). The
morphology of synthesized nanoparticles was analyzed under SEM and revealed NiCoP
structure baring multiple petals on it that exactly resembled a marigold flower displayed in Fig.
9(b-d). The marigold nanostructured offered high surface area for storing charges during
charge-discharge, thereby reduced path length, enhanced conductivity, and stability of the
material. When used as positive electrode with AC as the negative one in a ASC cell, it
exhibited superior power and energy density of 1666 W kg–1 and 47 Wh kg–1 along with 10000
cycles[161].
Similarly, Zhao and his team reported Cu(NiCo)2S4/Ni3S4 flower-like structure of
NiCo, as shown in Fig. 9(e-h) which displays SEM images of copper and cobalt-based hollow
of CoCuNi-OH and Cu(NiCo)2S4/Ni3S4 under different magnitudes. They were synthesized by
hydrothermally fusing the developed CoCu-MOF with Ni(NO3)2, followed by Na2S to yield
Cu(NiCo)2S4/Ni3S4 hallow structure for extremely high surface area. The insertion of Cu, Co,
and Ni offered greater ion transport, conductivity, and accumulation rate of charges on
electrode, thereby providing high capacitance of 1320 Fg-1 at a current density of 1 Ag-1. HSC
was further built by Cu(NiCo)2S4/Ni3S4 and AC as an electrode and displayed a high power
density of 785.5 Wkg-1, which extends up to 7859.2 Wkg-1 with the energy density of 40.8
Whkg-1 and 27.1 Wkg-1 along with cyclic stability of 5000 cycles 15 Ag-1. Two fabricated HSC
were used to light 5 red and yellow lights to test their applicability, owning such high power
density it also drove fan motor at high speed showing its potential as a supercapacitor[162]. The
above experiments prove that bimetallic MOFs can improve charge density, electrochemical
40

tenability, conductivity, functionality, and stability in the derived materials when compared to
pristine MOF’s. Table 8 explains various bimetallic MOF based supercapacitor and its
electrochemical performance.
Table 8. Comparison of performances of Bimetallic MOF-5 based electrode material for

supercapacitor application.
Bimetallic MOF Specific Current Energy

and their capacitance density density Cyclic Electrol
Ref
derived stability yte
materials (Fg-1) (Ag-1) (Whkg-1)
6
NiO/MCN 261 0.25 - 8000 [156]
MKOH
2M
MnS/MoS2/C 1162 0.5 - 5000 [157]
KOH
3.0 M
Ni/Co-MOF 1377.5 1 30.9 3000 [158]
KOH
6M
NiCo2S4 1354.4 C g-1 1 49.1 10000 [159]
KOH
1M
NiCoS/NF-1 2815.4 1 mA cm− 2 - - [160]
KOH
1M
NiCoP 690.6 mA h g–1 1 47 10000 [161]
KOH
Cu(NiCo)2S4/Ni3S 6
1320 1 40.8 5000 [162]
4 MKOH
2M
2D Zn-Co-MOFs 267 mAh-1 1 - 6000 [163]
KOH
3 M
NiCoSe-4//AC 211 mAh g-1 1 61.24 5000 [164]
KOH
C@NiCo- 2M
1825 1 - 8000 [165]
hydoxide/NF KOH
41

5. MOF materials-based electrode state of the art challenges and way forward
In the past few years, significant progress has been made in the synthesis of MOFs and
application in various electronic field. The electronic properties of MOFs can easily be tuned
by chemically altering the linker, metal ion or guest species adsorbed in the pore space while
in case of purely inorganic or organic conductors such as MoS2 or graphene find difficult
chemical functionalization. As some elegant first demonstrations have been reported, for
instance for layered metal–organic graphene analogues, we expect intense efforts in this
area[166].
Though MOF exhibited superior performance still some state-of-the-art challenges limits
its practical application and need to be solved in future research[167]. First, in energy storage
application such as supercapacitor, active mass loading plays key role in device performance
and in order to produce practical devices, the mass loading of the electroactive materials on a
current collector needs to exceed 10 mg cm−2. However, from previous research work reflects
that MOF-based electrodes have a mass loading of only a few tens to hundreds of micrograms,
and the electroactive materials are not uniformly distributed which limits the performance
MOF based supercapacitor devices. Second challenge is the supercapacitor device
electrochemical performance which is far less as compared to same electrode performance in
three electrode system due to the mismatching electrochemical performance between the
positive and negative electrodes. In this regard, appropriate mass balancing and finding good
electrode match or MOF-based nanostructures derived from one single precursor are more
advantageous, since the two electrodes share similar properties, are some options. Moreover,
the assembly of the devices should be intensively studied and optimized. Third is the only few
self-supported MOF options are available for binder-free electrode, which means that the
application potential of other MOFs has not yet been explored. Therefore, great works from
42

MOF crystal design to electrode preparation and device assembly are needed to obtain the
desirable electrochemical performance.
6. Roadmap: MOF materials for supercapacitor electrode
The current review paper offered a glimpse into the evolution of metal-organic framework that
mauled a new direction for electrochemical storage devices by meeting the demands of large
active sites, tunable pore size, numerous robust structures with various chemical composition,
and high mechanical stability. These gained properties helped in achieving maximum
accumulation of charge in EDLC and increasing the rate of redox reaction in
pseudocapacitance, leading to improved capacitance, cyclic life, and power density of the
supercapacitor when compared to other conventional materials. Although MOFs are excellent
energy materials, they still lack electric conductivity, processability, and catalytic activity in
high acidic conditions, therefore extra efforts are necessary to achieve practical application in
storage devices. The Fig. 10 demonstrate the development of MOF based material and future
perspectives. The future outlooks are as the following:
 Large production of MOFs has been one of the major matter of concerns, simplified
laboratory synthesis through the traditional solvothermal method. When the same method is
bought to industrial scale, the costs of chemicals, equipment and operation increase
drastically, given that it requires high pressure and temperature. Techniques like spray
drying, electrochemical, continuous flow, microwave, and mechanochemical synthesis have
emerged, which use mild conditions for smaller crystalline MOF on the laboratory scale.
Furthermore, the low yield of MOF is also a concern, partly addressed by introducing the
aerogel and hydrogel techniques to produce a relatively high yield of MOF at room
temperature.
 The insulation property of MOFs also limits their application in energy storage devices.
Many strategies are developed to impart the conductivity in the MOFs along with ordered
43

tenability and flexibility, such as the incorporation of the conductive guest molecule into the
framework, carbonization of MOF, synthesizing 2-D MOF with π conjugation or regulating
π–π stacking in 3-D framework and by using redox-active or high conjugated organic linkers
in the matrix. Despite the improved conductivity, they still lack robustness in high acidic or
basic medium (harsh conditions of high temperature and pressure). It opens an area of
research for new strategies and techniques to optimize the conductivity of MOFs without
hindering their intrinsic property and exploring new configurations.
 The functional materials used in building the electrode gradually degrades with the number
of cycles, thereby deterring its capacitance and energy density. Hence it becomes vital for
the support material used along MOFs to be intrinsic with the framework, so that the
electrode could endure long cyclic rates. Therefore, the electrochemical activity of the
MOFs and complimentary material used in building electrode should be studied thoroughly
to identify the factors suppressing its activity. To monitor the chemical evolution of
electrodes within the electrolyte and better understand the underlying mechanism, structural
characterization by in situ or in operando should be carried along with simulation and
theoretical calculation.
Regardless of challenges and achievements, MOFs have shown excellent results as sacrificial
layer or precursor, as listed in the review. Thus, with tenacious research and technological
innovation, we can witness the revolution of metal-organic framework derived materials in the
renewable energy and electrochemical storage sector in near future.
Acknowledgement
The authors gratefully acknowledge the financial support from the International Association of
Advanced Materials.
44

Competing interests
The Authors declares that there is no conflict of interest.
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Figures
Fig. 1. Various MOF and its derivatives used for supercapacitor application.
50

Fig. 2. (a-b) CV and GCD curve showing capacitance of Co9S8/NS-C; (c) cyclic stability of
the material, Reproduced with permission from ref [27]. Copyright 2017 The Royal Society of
Chemistry.
51

a
b c d e
b’ C’ d’ e’
g h i
j k l
52

Fig. 3. (a) Schematic view of synthesis method for CuCo2O4@CoS-Cu/Co-MOF composites,
(b-b’) SEM images of Cu/Co-MOF substrate at the low and high magnification, (c-c’) SEM
pictures of CuCo2O4-Cu/Co-MOF with high and low focus (d-d’) picture of CuCo2O4@CoS-
Cu/Co-MOF core–shell nano flowers at different magnifications, (e-e’) SEM pictures of
CuCo2O4@CoS/NF at different magnifications. Replicated with approval from reference [28].
Copyright 2021 Elsevier., (f) Graphical representation of Co3O4@NiCoLDHNSs/CC synthesis
process, (g-g’) SEM pictures of Co-MOFNSs/CC; (h-h’) Co3O4NSs/CC; (i-I’)
Co3O4@NiCoLDHNSs/CC. Reproduced with permission from ref [27]. Copyright 2020
Elsevier.
53

a b c
a' b’ c’
a’' b’’ c’’
Fig. 4. FESEM of (a) regular rhombic flake morphology of Cu-MOF-0,(a’-a’) structures of

Cu@C and APC after calcination and treatment Cu-MOF-0, (b) squama morphology of Cu-
MOF-25, (b’-b’’) structure of Cu@C after calcination and APC treatment of Cu-MOF-25, (c)
truncated bi pyramid morphology of Cu-MOF-60, (c’-c’’) structure of Cu@C and APC after
calcination treatment of Cu-MOF-60. Replicated with approval from reference [40]. Copyright
2019 American Chemical Society. (d) Graphical presentation of preparation of CuxO-C/PANI
from Cu-MOF and their morphologies. (e)FE-SEM images of PANI. (f) TEM image of
porosity in CuxO-C/PANI. Reproduced with permission from ref [43]. Copyright 2021
Elsevier
54

a b
c d
e f
55

g h
i k
l m
Fig. 5. Represent the CV and GCD curves (a, b and e, f) showing the rate of capacitance of
CuO, CuO-C&CuO-C/PANI at several scan rates. Reconstructed with consent from ref [43].
Copyright 2018 Elsevier. (g-i) represent the measure of capacitance at 100 mV s-1 for HKUST-
1@TS-800. (k-l) represent the cyclic performance. Recreated with approval ref [44]. Copyright
2018 The Royal Society of Chemistry
56

a b c
d e
Fig. 6. (a-c) SEM images of spherical Mn2O3 hollow microspheres; (d)Shows the flexibility of
FHSC with different bending degrees; (e) demonstration of efficiency by glowing LED bulbs.
Replicated with consent from ref [50]. Copyright 2021 Elsevier
57

a
b c d
Fig. 7. (a) Graphical presentation of the synthesis method of Ni3S4@Co9S8 DSTs. (I): formation
of Ni-MOF-74@Co-MOF-74 core−shell crystals. (II) and (III) sulfurization of core−shell to
yield Ni3S4@Co9S8 DSTs; (b-d) shows the SEM images of Ni-MOF-74@Co- MOF-74,
Ni3S4@Co9S8 DSTs and Co9S8 SSTs. Recreated with consent from ref [75]. Copyright 2018
The Royal Society of Chemistry; (g) demonstration strategy to synthesize ZnNiP nanosheet
arrays and its morphology. Replicated with assent from ref [78], Copyright 2021 Elsevier
58

a b
c d
Fig. 8. (a&b) Represent the CV and GCD of GNi:Co 1:1 wheras; (c&d) shows the morphology
of wave like graphene layer in GNi:Co 1:1 incorporated with the Ni:Co 1:1 nanoparticles taken
by SEM. Recreated with assent from reference [113]. Copyright 2017 Wiley-VCH Verlag
GmbH & Co. KGaA.
59

a
b c d
e f g h
Fig. 9. (a) Graphical representation of the synthesis process for NiCoP/NC marigold flower;
(b-c) SEM images of NiCoP/NC nanostructures. Replicated with consent from reference [127].
Copyright 2020 Royal Society of Chemistry Copyright; (e,f) SEM-TEM analysis of CoCuNi-
OH (g,h) Cu(NiCo)2S4/Ni3S4 floral structures;. Reconstructed with acceptance from reference
[128]. Copyright 2020 Elsevier.
60

Figure 10
Work synthesis
method like
hydrogel,
Work on aerogel which
MOF derived will give mass
magnetic conductivity
MOF derived scale MOF
Carbon sponge improvement
LDH – Ni-Co
LDH, NCNTs, (MCS)
NiS2/ZnS, 2025
Carbon nitrides
2019 2027
2022
MOF derived 2015
Carbon 2017
Synthesis of 2011 2013 Work on

MOF-4 - Yaghi stability of
MOF derived
Hydrothermal superporous carbon functional
2006 MOF derived materials
Synthesis of 2008 aerogels and g-C3N4
MOF -Yaghi phosphides
(Ni2P)
Zn coordination 1997 1999
polymer
fabricated by
DuPont 1995
1990
1965 Scafold-like 3D
framework proposed
by Hoskins and Robson
Fig. 10. Roadmap and future perspectives for MOF based supercapacitor electrode
61

Highlights
 Advancement metal-organic frameworks derived electrode materials overviewed.
 Performance of different types of nano/hybrid structure derived from MOF discussed.
 Major challenges in use of MOF as supercapacitor electrode material examined.
 The challenges for using MOF in supercapacitor electrode elaborated in detail.
 Roadmap for progress and future progress revealed.
62

Graphical Abstract
63

The Progress and Roadmap of Metal-Organic Frameworks For High-Performance Supercapacitors

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The Progress and Roadmap of Metal-Organic Frameworks For High-Performance Supercapacitors

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The progress and roadmap of metal-organic frameworks

for high-performance supercapacitors

University, Phagwara 144411, India.

Phagwara 144411, India.

*Corresponding authors. E-mail: ajitsharma2003@gmail.com (AS) deepak.sharma99967@gmail.com (DK),

Electronic copy available at: https://ssrn.com/abstract=4098683

List of Abbreviations. MOF-Metal organic framework, ZIF-Zeolitic imidazolate

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charge/discharge cycles of batteries as well as low energy density of conventional capacitors

into three different classes, namely, electrochemical double-layer capacitors (EDLCs),

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cyclic stability than pseudocapacitors as degradation of active material is reduced due to

capacitance in pseudocapacitance material namely, intrinsic and extrinsic

pseudocapacitive conductance characteristic whereas extrinsic pseudocapacitance is shown by

nano-sized particles[9]. Dynamically, pseudocapacitive materials can be recognized from the

by a surface-related interaction rather than dissemination-controlled responses administering

are generally referred to as asymmetric supercapacitors as one electrode is made of carbon

Electronic copy available at: https://ssrn.com/abstract=4098683

class of porous material namely metal-organic framework or hybrid organic-inorganic

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electrons and electrolytic ions in supercapacitors, thereby overwhelming the drawbacks of

2. Metal-organic frameworks building blocks

structural diversity. These frameworks include uniformly organized 3-dimensional geometry

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carbonaceous materials are synthesized through thermal heating of coordinated frameworks in

Furthermore, derived materials can be modified accordingly by chemical doping of

dimensional to three-dimensional material. Moreover, MOFs also act as an efficient template

functional materials for super capacitor application.

2.1. Co-MOF templates

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intrinsic properties of MOF[39].

Co9S8/NS-C-1.5 matrix as an cathode and AC as an anode, it displayed specific capacitance of

6818.18 W kg-1 [40].

to the well aligned Co in lattice plane[41].

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(CC) through precipitation and subsequent pyrolysis in nitrogen atmosphere, yielding

CoNC/CC rooted with cobalt nanoparticles[42]. To enhance the electrochemical activity

furthermore, phosphate group was incorporated by using sodium hypophosphite monohydrate,

into cobalt phosphide resulting CoP–CoNC/CC complex. Electrochemical property was

kg−1 respectively analogous to the capacitance of 144 F g−1[43].

when dissolved in alkaline solution and 3,5,6-tetramethyl-1,4-disophthalate as linker element

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Hosseinzadeh and his coworkers synthesized cobalt-based graphitic carbon by simple

CC/SiCNWs@NiCo2O4NAs displayed higher capacitance of 1604.7 F g−1 at 0.5A g-1 current

Similarly, Hu et al. tried to design nanoflower core-shell structure of CuCo2O4@CoS-

Cu/Co-MOF by two steps electrodeposition of CuCo2O4 on MOF-coated Ni foam as

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area implying highest capacitance. Cyclic performance of CuCo2O4@CoS-Cu/Co-MOF core-

capacitance indicated no deterioration of the active material during charge-discharge cycles.

density, proving to be an excellent material for energy storage sector[47].

Yin et al. reported Co3O4@NiCoLDHNSs/CC as electrode material with excellent

growing Co3O4NSs by annealing it at 350°C for 2h in air. It was finally converted to

Co3O4@NiCoLDHNSs/CC by electro-deposition of NiCo LDHNSs on Co3O4NSs/CC as

mentioned literature, it is understood that Co-MOF shows outstanding ability as a template

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Type of cobalt Specific Current Energy

Co-MOF 120.2 1 40.6 10000 6 M KOH [49]

Co-BTB-I-450 342.1 0.5 - 2000 [50]