Maliha 2022 Investigation of Copper Cobaltmofsn

1099114x, 2022, 12, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/er.
8406 by Naveed Mazhar - National University of Science and Technology , Wiley Online Library on [23/03/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
Received: 1 April 2022 Revised: 19 June 2022 Accepted: 1 July 2022
DOI: 10.1002/er.8406
RESEARCH ARTICLE
Investigation of copper/cobalt MOFs nanocomposite as an

electrode material in supercapacitors
Zeerak Maliha1 | Malika Rani1 | R. Neffati2,3 | Arshad Mahmood4 |

Muhammad Zahir Iqbal5 | Aqeel Shah6
1
Department of Physics, The Women
University, Multan, Pakistan Summary
2
Department of Physics, King Khalid MOFs (Metal-organic frameworks) emerging as newest materials with porous
University, Abha, Saudi Arabia structure and ease to synthesize results in new material growth with enhanced
3
Laboratoire de Physique de la Matière surface area. Nanocrystalline copper-metal organic framework (Cu-MOF),
Condensée, Département de Physique,
Faculté des Sciences de Tunis, Université
cobalt-metal organic framework (Co-MOF), and copper/cobalt metal organic
Tunis El Manar, Campus universitaire, framework (Cu/Co MOF) nanocomposite have been synthesized via superficial
Tunis, Tunisia cost-effective hydrothermal method by using trimesic acid in order to restrict
4
National Institute of Lasers and
nano-particle growth. X-ray powder diffraction of the synthesized material
Optronics College, Pakistan Institute of
Engineering and Applied Sciences, Nilore, indicates a reduction in the c-lattice parameter for Cu/Co nanocomposite to
Islamabad, Pakistan value 8.062 Å. Existence of oxygen, copper, chromium, and cobalt inside the
5
Nanotechnology Research Laboratory, Cu/Co MOF nanocomposite is indicative of successful nanocomposite synthe-
Faculty of Engineering Sciences, GIK
Institute of Engineering Sciences and
sis whereas surface morphology gives a fall in particle growth resulting value
Technology, Topi, Pakistan 3.53 nm. PL (Photoluminescence) spectra showing reduction in peaks whereas
6
Department of Metallurgical Raman spectra demonstrate the presence of both copper and cobalt peaks
Engineering, NED University of
inside the nanocomposite. Electrochemical studies were analyzed using IM
Engineering and Technology, Karachi
City, Pakistan KOH as an electrolyte resulting in enhanced specific capacitance of 228 Fg1
for Cu-MOF, 280 Fg1 for Co-MOF, and 935.8 Fg1 for Cu/Co MOF nanocom-
Correspondence
posite respectively. Galvanostatic charge discharge (GCD) analysis reveals
Malika Rani, Department of Physics, The
Women University, Multan 66000, power density value increment from 1092 Wkg1 to 2495.5 Wkg1 for Cu/Co
Pakistan. MOF nanocomposite with energy density value decreases to 45.2 WhKg1
Email: [email protected]
allowing rapid ions transport at electrode/electrolyte interface suggesting
Cu/Co MOF nanocomposite as a high performance electrode material with
maximum storage capacity in supercapacitors.
KEYWORDS
co-MOF, cu/co MOF nanocomposite, cu-MOF, supercapacitor electrode
1 | INTRODUCTION are nearly all cost-efficient renewable energy options.3,4

Reliance of astral and also wind energy on climate and
The need for renewable energy resources is growing sunshine, on the other hand, is a major impediment to
owing to rising environmental pollution, energy costs, the continuous supply of energy.5,6 Supercapacitors, ordi-
and fossil fuels depletion.1,2 Wind and astral type energy nary capacitors, batteries, and fuel cells are among the
17404 © 2022 John Wiley & Sons Ltd. wileyonlinelibrary.com/journal/er Int J Energy Res. 2022;46:17404–17415.
1099114x, 2022, 12, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/er.8406 by Naveed Mazhar - National University of Science and Technology , Wiley Online Library on [23/03/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
MALIHA ET AL. 17405
most often utilized energy storage systems.7,8 Despite supercapacitors stretched also sparked widespread atten-
having an elevated energy frequency, batteries limited tion.39-41 Because MOFs are typically electrically insulat-
power type density blocked their practical usage when ing, Han’s group discovered fine pseudocapacitors
maximum power needs to be enforced.9,10 Electrochemi- manners and charge custody in Co-based MOFs as bar-
cal supercapacitors (SCs) are one of these energy storage rier for their practical traits, producing poor cadence per-
solutions that have piqued the interest of researchers all formance and ability fading above cycles.42,43
around the world.11-13 Supercapacitors (SCs) are the most Herein, we reported sono-chemical approach to make
advantageous devices for storing energy efficiently due to Cu-MOF, Co-MOF, and Cu/Co MOF nanocomposite as
their unique characteristics such as high clean-cut power, acting electrode materials for energy storage application.
clean-cut energy, great life cycle consent, prompt charge In a three-electrode assembly, electrochemical tests were
discharge type process, and their environmentally affable performed by EIS, CV, and GCD. Energy dispersive spec-
nature.14 SCs are classified as electric dual type coating troscopy (EDS), X-ray diffraction analysis (XRD), Scan-
or pseudocapacitors based on the charge storage tech- ning electron microscopy (SEM) were used to examine
nique.15-17 Carbonaceous type resources are employed as the structure, morphology, and content of as-prepared
electrode type materials in EDLCs.18-20 The redox faradic nano-electrode material whereas Photoluminescence
processes, on the other hand stuck in pseudocapaci- spectroscopy (PL) and Raman Spectroscopy were utilized
tors.21-23 The battery case (high detailed energy) and to have optical measurements.
supercapacitor (superb detailed power) can be coupled in
a mono asymmetric type of device called super-capattery
to gain superb benefit.24 Conducting type polymers (CPs) 2 | EXPERIMENTAL SETUP
have recently been identified as a promising electrode
resource for energy depot devices.25-27 2.1 | Materials
Metal oxides such as ruthenium, iron, and cobalt
oxide, on the other hand have been emerged as suitable Trimesic acid (C9H6O6), Copper nitrite (Cu (NO3)2,
electrode resource for energy depot device.28-30 Nonethe- Cobalt nitrite (Co (NO3)2, Distilled (DI) water, and Etha-
less, electrical strength, structural elasticity, carrier motil- nol (C2H5OH). All these chemicals are available in phys-
ity optimization, and bandgap are some of the essential ics department lab of The Women University Multan.
concerns that must be addressed.31-35 Wang et al uses
magnesium cobaltite micro flora (MgCo2O) as a battery
type electrode material. In a three-electrode assembly, 2.2 | Synthesis of copper and
the electrode demonstrated superb fixed capacity of cobalt MOFs
nearly 313 Cg1 at 1 Ag1. After 5000 cycles, the elec-
trode has a cyclic solidity of 74.5% as an electrode consent First of all, appropriate amount of trimesic acid is mixed
for supercapacitors and batteries.36 in DI water. After a while, appropriate amount of copper
Anjon et al., used Urchin-akin to NiO nanospheres nitrite and cobalt nitrite was added to it with continuous
manufactured through microwave aided hydrothermal stirring. When the solution becomes homogenous, con-
method. When employed since an anode in case of lith- vert this solution in Teflon autoclave and placed it in
ium ion array, the material has exact ability of oven for 24 hours at 200 C. Orange hard material was
1026.9 mAhg1, in case of a supercapacitor it used as an obtained which was with distilled water and ethanol to
electrode, it has exact capacitance of 736 Fg1. In high- attain neutral pH at 6. Place it in petri dish for drying in
performance SC devices, cobalt type phosphates are fre- oven at 70 C for 24 hours.
quently used for electrode resource.37 J. Zhao et al., also
conducted hydrothermal approach focusing on ammo-
nium nickel type phosphate and employed for supercapa- 2.3 | Synthesis of copper/cobalt MOF
citor traits achieving superb capacitance is 1072.1 Fg1 at nanocomposite
1.46 Ag1 at three cell configuration with 95% cyclic sta-
bility after 3000 Galvanostatic charge discharge (GCD) In a Teflon-lined steel autoclave, a solution containing
cycles.38 5 mmol trimesic acid, 0.25 g Cu(NO3)2, and Co(NO3)2
On the other hand, Metal-Organic framework was finely mixed with 60 mL DI water following the pro-
(MOFs) exhibits good electrode resource for supercapaci- cedure described before.44,45 The autoclave was then
tors with large site area and a customized pore range. placed in oven at 200 C for nearly 7 hours. Subsequent
The exploration of MOFs electrode type resource for cooling at ambient temperature results in orange hard
17406 MALIHA ET AL.
product. It was filtered three times using ethanol, DMF, 3 | RESULTS A ND DISCUSSION
and also DI water along with centrifugation at 6000 rpm
nearly for 8.5 minutes each time. The highly pure mate- 3.1 | X-Ray diffraction
rial was dried overnight at 80 C under vacuum.
Powder type Xrd technique provide information about
sample crystal structure and phase clarity. Cu-MOF and
2.4 | Electrode Fabrication Co-MOF exhibit XRD patterns with comparatively high
intensity peaks reflecting the compounds strong crystal-
For electrochemical analysis, three electrode assembly is linity as shown in Figure 1A, B. The peak values are com-
utilized with active material coated over nickel foam that parable to parent material. Cu-MOF has high intensity
acts as current collector as well. Prior to usage, nickel peaks at 2θ = 9.35 , 11.31 , 13.78 and 16.16 , while Co-
foam was washed with Ethanol and DI water to remove MOF has high intensity peaks at 2θ = 11.99 , 16.42 ,
the impurities. The produced electrode material is mixed 18.04 and 24.0 respectively. For Cu/Co MOF the shar-
together with carbon black and PVDF binder in an pest peaks in resulting template correspond to 2θ = 9.34
80:10:10 ratio until a homogenous slurry is generated and 11.97 as shown in Figure 1C in accordance with
with continuous stirring for 8 hours without interruption. JCPDS no is 003-1018 denoting metals allocation with
The slurry is then dried after being poured on a ligands. The greater the crystallite size, the more consis-
1 1 cm2 patch of nickel foam. The electrode material tent the results are. Tables 1 and 2 are showing crystal
active mass was around 4 mg. All electrochemical mea- data and miller indices values of Cu-MOF, Co-MOF and
surements were employed using IM KOH aqueous elec- Cu/Co MOF nanocomposite respectively.
trolyte at RT (room temperature).
3.2 | Photoluminescence spectroscopy
The photoluminescence spectrum was explored to study

the electron–hole recombination tool computing band
(C) gap at specific related energy state.46,47 The optical prop-
erties of nanoparticles are truly mirrored in nanocompo-
site formation as demonstrated in Figure 2. A power of
(B) 40 MW at room temperature with a wavelength of
325 nm using a He-Cd laser to achieve the optical spectra
of Cu-MOF, Co-MOF and their nanocomposite were dis-
cussed.48 By using the formula Eg = 1240/ℷ, the band
(A) gap of copper MOF is almost 3.28 eV. The optical band
gap of Cu/Co MOF nanocomposite is about 3.21 eV esti-
mated in the visible region is a strong predictor of nano-
particle allocation mostly due to sp2 hybridized carbon
atoms recombination electron-hole pairs.49 Near the
F I G U R E 1 X-ray spectra of (A) Cu-MOF, (B) Co-MOF and ground skip to the valence band (VB), the conducting
(C) Cu/Co MOF nanocomposite band (CB) and negative charges by virtue of a complicate
T A B L E 1 Cu-MOF, Co-MOF and

Empirical formula Cu(NO3)2 CO(NO3)2 Cu/Co Nanocomposite
Cu/Co MOF crystal data and structural
Formula mass 293.74 391.88 123.55 refinement
Temperature in K 292 293 293
Space group C2/m P21/c P21/c
Crystal structure Monoclinic Monoclinic Monoclinic

a/A 12.840 5.3043 3.4253

b/ A 15.649 14.720 12.765

c/ A 6.828 11.065 8.062
3
Volume/A 1275.86 834.97 575.73
MALIHA ET AL. 17407
T A B L E 2 Miller indices of Cu-

2θ(Cu) θ hkl 2θ(Co) θ hkl 2θ(Cu/Co) θ hkl
MOF, Co-MOF and Cu/Co MOF
nanocomposite 11.81 5.905 110 10.34 5.17 110 10.34 6.825 110
13.5 6.75 111 13.65 6.825 111 13.65 8.04 111
18.08 9.04 111 18.76 9.38 111 18.76 9.38 111
19 9.5 210 21.29 10.645 210 21.29 10.645 210
27.4 13.7 211 21.41 10.705 211 21.41 10.705 211
48000
and Cu/Co MOF with various wavelengths at different
Co/Cu-MOF
40000 Cu-MOF points. The in-plane stretching action between sp2 carbon
atoms causes the G peak. The D band is a disordered
band that results from structural flaws, edge effects, and
pl intensity
32000
dangling sp2 carbon bonds that disrupt the symmetry of
24000 the molecules.
16000
8000
3.4 | Energy dispersive spectroscopy
EDS is used to examine the elemental compositions of

320 360 400 440 480 520 560 600 640 680 720
wavenumber (nm)
the suggested capacitive materials.60 It elucidates the
qualitative makeup of components in the Cu-MOF
F I G U R E 2 PL spectra of (A) C-MOF and (B) Cu/Co MOF including Cu, C and O, Co-MOF including Co, C and O
nanocomposite and Cu/Co MOF with Cu, Co, C and O respectively (see
Figures 4-6).61 Table 3 enlists the elements in terms of
atomic percent ratios. From EDS, it is clearly shown that
photoluminescence mechanism, resulting in a advocated Cu/Co MOF nanocomposite synthesized successfully
speed of charges carried by the irradiation effect of light without any impurity.
on Cu/Co nanocomposite.50-52 Negative and positive
charges in an aqueous media interacted to radicals create
on the outside of the Cu/Co nanocomposite when light 3.5 | Scanning electron microscopy
was predictable.53,54
The shape of the MOF sheets with copper nanoparticles
plainly aggregated and covers the entire MOF
3.3 | Raman spectroscopy nanosheets face clearly visible in Figure 7A, B.62 Irregu-
lar and spherically dispersed grains of cobalt MOF with
This approach simply joins the materials spectral traits to rod like structure of different sizes are visible in
its structural behavior. The Raman spectroscopy tech- Figure 7E, F. It can be seen that change in symphony
nique was used to probe the dynamic vibrational pho- ratios of Cu/Co results in homogeneously spread of cop-
nons of Cu-MOF, Co-MOF and their nanocomposite per and cobalt nanoparticles resulting more dispersed
astonishingly and more mechanically at the wavelength blocks on the surface.63 Grain size was calculated from
of 1400 nm with power of 150 mW.55,56 There were two SEM images using Image j. software by using the below
main reasons for the aerial capacitance of Cu/Co MOF formula:
nanocomposite in basic results. One was induced pseudo-
capacitance and the other was ion exchanging, which Grain Size ¼ Length of line=Number of grains
resulted in charge storage.57,58 In the Raman spectros-
copy of Cu/Co MOF nanocomposite, a characteristic The average grain size of Cu-MOF is almost 5.92 nm, Co-
peak at a specified position of 1.96 cm1 with a notable MOF is approximately 5.38 nm and the spherical nano-
intensity owing to the presence of functional groups particles present in Cu/Co MOF nanocomposite attain
involved as shown in Figure 3.59 There are two bands D- average grain size of 3.53 nm. Grain size distribution is
band and G-band in Raman spectra of Cu-MOF, Co-MOF clearly visible in Figure 8.
17408 MALIHA ET AL.
(A) (B) (C)

21000 Cu-MOF Co-MOF 21000 Cu/Co MOF
20000
18000 18000
16000
Intensity(a.u.)
Intensity(a.u.)
Intensity(a.u.)
15000 382(D-band) 392(D-band) 15000 382( D- band)
12000 586(G-band) 12000 584(G-band) 12000 584 (G -band)
9000 9000
8000
6000 6000
4000
3000 3000
0 500 1000 1500 300 600 900 1200 1500 1800 500 1000 1500
Raman shift (cm–1) Raman shift (cm–1) Raman shift (cm–1)
FIGURE 3 Raman spectra of (A) Cu-MOF (B) Co-MOF and (C) Cu/Co MOF nanocomposite
FIGURE 4 EDS of Cu-MOF
FIGURE 5 EDS of Co-MOF
FIGURE 6 EDS of Cu/Co MOF nanocomposite

MALIHA ET AL. 17409
T A B L E 3 Elemental composition
Elements Weight% Elements Weight% Elements Weight %
of Cu-MOF, Co-MOF and Cu/Co MOF
nanocomposite Cu k 4.46 Co k 43.64 Cu k 21.83
Ck 10.29 Ck 30.77 Co k 3.41
Ok 38.84 Ok 25.59 Ck 38.09
Ok 36.67
F I G U R E 7 SEM structure of (A, B) Cu-MOF with 10 and 50 nm resolution (C, D) Cu/Co MOF nanocomposite (E, F) Co-MOF with
10 and 50 nm resolution
(A) (B) 16 (C)10

6 (Co)
14 (Cu/Co)
Cu
8
5 12
4 10
6
Count
Count
Count
8
3
6 4
2
4
2
1
2
0 0 0
0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6
Area m2 Area m2 Area m2
FIGURE 8 Grain size histogram of (A) Cu-MOF (B) Co-MOF (C) Cu/Co MOF nanocomposite
17410 MALIHA ET AL.
3.6 | Electrochemical impedance 1.72 Ω,1.52 Ω and 1.3 Ω with kapp values 1.55 107
spectroscopy cm2s1, 1.75 107 cm2s1 and 2.01 107 cm2s1
respectively.67,68 Obvious from the Nyquist plot suitable,
The EIS method is used to explore process that occurs at for a semicircle high power related to charge shift resis-
the electrode boundary.64,65 EIS spectra obtained using tance Rct.69 Ions disperse always shown as a direct line in
three electrode assembly within frequency range 0.1 to the low frequency array representing hydroxyl ions diffu-
100 KHz where x-axis represents impedance real part sion within electrode material resulting in Warburg
whereas y-axis representing impedance imaginary part Impedance (W).70
respectively.66 Figure 9 shows Nyquist plot for Cu-MOF,
Co-MOF and Co/Cu MOF nanocomposite utilizing an
EIS fitted model to investigate the electron-transfer 3.7 | Cyclic voltammetry measurements
mechanism. The electron shift rate constant kapp has
been determined for the veteran electrode using CV is used to determine how well the current response of
kapp = RT/F2.Rct.C where Rct calculated values are a redox reaction deals to a prospective gradient set
between two values.71 It is superb powerful analysis tool
for analyzing chemical reactions involving an electron
350 Cu-MOF transfer.72 CV was performed using 1 M KOH electrolyte
Co-MOF with varying scan rate 3 mV/s-50 mV/s having potential
300 Cu/Co-MOF
window of 0 V to 0.6 V vs an Hg/HgO reference electrode
250
to understand produced resulting sample electrochemical
performance and shown in Figure 10A-C.73 Increasing
200 scan rate results in reduction peaks vary even reaching
-Z(Ohm)
low potential, attaining oxidation peaks towards positive

150
potential.74 Company of redox peaks including CV graph
100 of observing electrode for 1 M KOH aqueous solution as
an electrolyte tells control of redox reaction in charge
50
storage system. Specific capacitance was determined from
0 cyclicR voltametric data using equation75 Qs =
vf
1=vm vi I VdV Where Qs is representing fixed capaci-
-50
0 20 40 60 80 100 120 tance, m denotes electrode mass in gram, V = scan rate
' and integral part of area under curve.76 Table 4 is show-
Z (Ohm)
ing specific capacitance values showing an increasing
F I G U R E 9 EIS spectra of Cu-MOF, Co-MOF and Cu/Co MOF trend in scan-rate with a fall in specific capacitance as
nanocomposite in a three-electrode arrangement with a frequency ions of electrolyte ions were not able to penetrate interior
range of 0.1-100 KHz of electrode anymore.77 It is important for the
(A) 150 (B) (C) 80

3 mV/s 3m V/s 3m V/s
5 mV/s 0.15 5 m V/s 6m V/s
10 m V/s
10 mV/s 10m V/s
20 mV/s
20m V/s 60 20m V/s
30m V/s
100 30 mV/s 40m V/s 30m V/s
40 mV/s 60m V/s 40m V/s
50 mV/s
0.10 60m V/s
40
50
0.05 20
Current (mA)
Current (mA)
Current (mA)
0 0.00 0
-20
-50 -0.05
-40
-0.10
-100
-60
-0.15
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
FIGURE 10 CV profile of (A) Cu-MOF, (B) Co-MOF and (C) Cu/Co MOF in IM KOH electrolyte
MALIHA ET AL. 17411
TABLE 4 Specific capacitance measurements of Cu-MOF, Co-MOF, and Cu/Co MOF in IM KOH electrolyte
Scan Cu-MOF specific Co-MOF specific Cu/Co MOF specific

rate (mVs1) capacitance (F/g) capacitance (F/g) capacitance (F/g)
3 228.52 280.190 935.8
5 220.54 264.6 752.9
10 210.514 232.6 700
20 180.414 183.07 697.8
30 154.271 145.32 615
40 129.632 116.4 546.8
50 108.798 111.38 406.8
(A) (B) (C)

0.5 A/g 0.5 A/g 0.6A/g
0.6 0.6 0.6 0.8A/g
0.8 A/g 0.8A/g
1 A/g 1 A/g
1A/g
0.6 A/g 2 A/g
0.5 0.6A/g 0.5 4 A/g
3 A/g 0.5
5 A/g 3A/g 8 A/g
8 A/g 5A/g 11 A/g
0.4 11 A/g 8A/g
0.4 0.4
Voltage (V)
Voltage (V)
Voltage (v)
0.3 0.3 0.3
0.2 0.2 0.2
0.1 0.1 0.1
0.0 0.0 0.0
0 200 400 600 800 1000 1200 1400 0 200 400 600 800 0 50 100 150 200 250 300
Time (s) Time (s) Time (s)
(D) 24
(E) (F) 110
28
22 26 100
24
20
Energy Density WhKg-1
90
22
18 80
20
16 18
70
16
14
60
14
12
12 50
10 10
40
250 300 350 400 450 500 550 300 400 500 600 700 1200 1400 1600 1800 2000 2200 2400 2600
-1
Power Density Wkg-1 Power Density Wkg Power Density Wkg-1
FIGURE 11 (A-C) GCD curves and (D-F) Ragone plot of Cu-MOF, Co-MOF, and Cu/Co MOF nanocomposite in IM KOH electrolyte.
maintenance of curves of tilted CV at maximum scan-rate 3.8 | Galvanostatic charge discharge

as well. Copper and cobalt nanoparticles incorporation analysis
within Cu/Co MOF affects ionic as well as electronic con-
ductivity resulting maximum electrode surface utilization Galvano static charge-discharge analysis curve depicts a
with an improvement in reaction kinetics. It is evident non-linear behavior during charging and discharging that
that with an increase in scan rate, peak current is also is in good agreement with CV curves oxidation-reduction
increasing a clear evidence of good capacitive behavior peaks by indicating material redox-active nature as
with best charge storage phenomena. Also internal resis- shown in Figure 11A-C. With an increase in current den-
tance increases with increasing scan rate leads to sity, discharging time goes on decreasing. At lowest cur-
increased peak separation among anodic and cathodic rent density value, electrode possess maximum time for
peaks respectively.78 hydroxyl ion insertion within electrode material resulting
17412 MALIHA ET AL.
maximum capacitance with increased discharging time.79 A C KN O WL ED G EME N T S

Among the two parameters including energy density and We are thankful to National Institute of Lasers and
power density there is visible inverse relationship Optronics College, PIEAS Islamabad for characterization.
between them calculated by using relations E = ΔV We are also thankful to Nanotechnology Research Labo-
Q/3.6 2 and P = E 3600/Δt respectively.80 Power ratory, Faculty of Engineering Sciences, GIK Institute of
density (Figure 11D-F) ranging from 253.33 to Engineering Sciences and Technology for electrochemical
533.2 Wkg1 for Cu-MOF, 259.9 to 653.7 Wkg1 for Co- results. The Authors extend their appreciation to dean-
MOF and 1092 to 2495.5 Wkg1 for Cu-Co MOF nano- ship of Scientific Research at King Khalid University for
composite whereas energy density from 22.22 to financial support through reesarch groups program
10.56 WhKg1 for Cu-MOF, from 27.24 to 10.82 WhKg1 under garant number (RGP.2/74/43)
for Co-MOF and 103.97 to 45.2 WhKg1 for Cu/Co nano-
composite suggesting nanocomposite based electrode CONFLICT OF INTEREST
material good electro active one for supercapacitor Authors declared no conflict of interest.
applications.
DA TA AVAI LA BI LI TY S T ATE ME NT
Data can be available on reasonable request
4 | C ON C L U S I ON S
A straightforward “One-for-All” technique is employed ORCID

to manufacture electrode material for SCs from a single Malika Rani https://orcid.org/0000-0002-9117-3403
bimetal-organic framework accompanied annealing for
limited time at 200 C featuring hierarchically porous RE FER EN CES
structures. Peaks observed in XRD spectra confirms the 1. Azar C, Lindgren K, Andersson BA. Global energy scenarios
meeting stringent CO2 constraints—cost-effective fuel choices
phases of copper and cobalt within Cu/Co MOF nano-
in the transportation sector. Energy Policy. 2003;31(10):961-976.
composite. Surface morphology clearly depicts mixed par-
2. Jacobsson S, Johnson A. The diffusion of renewable energy
ticle formation along with dispersion over MOF sheets technology: an analytical framework and key issues for
resulting in rod-like structures. Also Cu-MOF has an research. Energy Policy. 2000;28(9):625-640.
average grain size of 5.92 nm, Co-MOF has an average 3. EV MG, Deane JP, Leahy PG. How much wind energy will be
grain size of 5.38 nm, and spherical nanoparticles in curtailed on the 2020 Irish power system? Renew Energy. 2013;
Co/Cu MOF nanocomposite have an average grain size 55:544-553.
of 3.53 nm. PL spectra shows reduction in bandgap from 4. Iqbal MZ, Alam S, Faisal MM, Khan S. Recent advancement in
the performance of solar cells by incorporating transition metal
3.28 eV of Cu-MOF to 3.21 eV in Co/Cu MOF nanocom-
dichalcogenides as counter electrode and photoabsorber. Int J
posite showing enhanced conductivity whereas from Energy Res. 2019;43(8):3058-3079.
Raman spectra D and G bands existence at comparable 5. Khare V, Nema S, Baredar P. Solar–wind hybrid renewable
values is evident. The electrochemical performance was energy system: a review. Renew Sustain Energy Rev. 2016;58:23-33.
evaluated using CV, GCD, and EIS measurements. The 6. Evans A, Strezov V, Evans TJ. Assessment of sustainability
electron transfer rate constant kapp for the veteran elec- indicators for renewable energy technologies. Renew Sustain
trode was estimated using kapp = RT/F2.Rct.C resulting Energy Rev. 2009;13(5):1082-1088.
values1.55 107 cm2s1, 1.75 107 cm2s1, and 7. Jain D, Hashmi SA, Kaur A. Surfactant assisted polyaniline
nanofibres—reduced graphene oxide (SPG) composite as elec-
2.01 107 cm2s1 for Cu-MOF, Co-MOF, and Cu/Co
trode material for supercapacitors with high rate performance.
MOF nanocomposite respectively. Synthesized Cu/Co Electrochim Acta. 2016;222:570-579.
MOF nanocomposite shows excellent performance with 8. Kötz R, Carlen MJEA. Principles and applications of electrochem-
maximum power density of 2495.5 Wkg1 suggesting that ical capacitors. Electrochim Acta. 2000;45(15–16):2483-2498.
nanocomposite based working electrode as a good electro 9. Senthilkumar ST, Kalai Selvan R. Fabrication and performance
active material for supercapacitor applications. studies of a cable-type flexible asymmetric supercapacitor. Phys
Chem Phys. 2014;16(29):15692-15698.
10. Mi H, Zhang X, An S, Ye X, Yang S. Microwave-assisted syn-
A U T H O R C ON T R I B U T I O NS
thesis and electrochemical capacitance of polyaniline/multi-
Zeerak Maliha wrote the manuscript. Zeerak Maliha and
wall carbon nanotubes composite. Electrochem Commun. 2007;
Malika Rani designed the research scheme. Synthesis 9(12):2859-2862.
was carried by Zeerak Maliha. Arshad Mahmood per- 11. Gonzalez A, Goikolea E, Barrena JA, Mysyk R. Review on
formed the characterization techniques. Muhammad supercapacitors: technologies and materials. Renew Sustain
Zahir Iqbal performed the electrochemical experimenta- Energy Rev. 2016;58:1189-1206.
tion. Malika Rani supervised the whole project.
MALIHA ET AL. 17413
12. Zhi M, Xiang C, Li J, Li M, Wu N. Nanostructured carbon– performance supercapacitor application. Micropor Mesopor
metal oxide composite electrodes for supercapacitors: a review. Mat. 2017;244:101-108.
Nanoscale. 2013;5(1):72-88. 32. Kazemi SH, Hosseinzadeh B, Kazemi H, Kiani MA, Hajati S.
13. Wang G, Zhang L, Zhang J. A review of electrode materials for Facile synthesis of mixed metal–organic frameworks: electrode
electrochemical supercapacitors. Chem Soc Rev. 2012;41(2): materials for supercapacitors with excellent areal capacitance
797-828. and operational stability. ACS Appl Mater Interfaces. 2018;
14. Salanne M, Rotenberg B, Naoi K, et al. Efficient storage mecha- 10(27):23063-23073.
nisms for building better supercapacitors. Nat Energy. 2016; 33. Padmanathan N, Shao H, Razeeb KM. Multifunctional nickel
1(6):1-10. phosphate nano/microflakes 3D electrode for electrochemical
15. Miller JR, Simon P. Electrochemical capacitors for energy man- energy storage, nonenzymatic glucose, and sweat pH sensors.
agement. Science. 2008;321(5889):651-652. ACS Appl Mater Interfaces. 2018;10(10):8599-8610.
16. Trasatti S, Kurzweil P. Electrochemical supercapacitors as ver- 34. Wang Y, Li S, Sun J, Zhang Y, Chen H, Xu C. Simple solvother-
satile energy stores. Platinum Metals Rev. 1994;38(2):46-56. mal synthesis of magnesium cobaltite microflowers as a battery
17. Simon P, Gogotsi Y, Dunn B. Where do batteries end and grade material with high electrochemical performances. Ceram
supercapacitors begin? Science. 2014;343(6176):1210-1211. Int. 2019;45(12):14642-14651.
18. Simon P, Gogotsi Y, Dunn B. Where do batteries end and 35. Mondal AK, Su D, Wang Y, Chen S, Liu Q, Wang G. Micro-
supercapacitors begin? Science. 2014;343(6176):1210-1211. wave hydrothermal synthesis of urchin-like NiO nanospheres
19. Chen Z, Ye S, Evans SD, et al. Confined assembly of hollow as electrode materials for lithium-ion batteries and supercapa-
carbon spheres in carbonaceous nanotube: a spheres-in-tube citors with enhanced electrochemical performances. J Alloys
carbon nanostructure with hierarchical porosity for high- Compd. 2014;582:522-527.
performance supercapacitor. Small. 2018;14(19):1704015. 36. Rockinson-Szapkiw AJ, Courduff J, Carter K, Bennett D. Elec-
20. Chen Z, Ye S, Evans SD, et al. Confined assembly of hollow tronic versus traditional print textbooks: a comparison study
carbon spheres in carbonaceous nanotube: a spheres-in-tube on the influence of university students' learning. Comput Educ.
carbon nanostructure with hierarchical porosity for high- 2013;63:259-266.
performance supercapacitor. Small. 2018;14(19):1704015. 37. Zhao J, Pang H, Deng J, et al. Mesoporous uniform ammonium
21. Augustyn V, Simon P, Dunn B. Pseudocapacitive oxide mate- nickel phosphate hydrate nanostructures as high performance
rials for high-rate electrochemical energy storage. Energ Envi- electrode materials for supercapacitors. CrstEngComm. 2013;
ron Sci. 2014;7(5):1597-1614. 15(30):5950-5955.
22. Iqbal MZ, Alam S, Afzal AM, et al. Binary composites of stron- 38. Mancino G, Console R, Greco M, Iacovino C, Trivigno ML,
tium oxide/polyaniline for high performance supercapattery Falciano A. Assessing vegetation decline due to pollution from
devices. Solid State Ion. 2020;347:115276. solid waste management by a multitemporal remote sensing
23. Iro ZS, Subramani C, Dash SS. A brief review on electrode approach. Remote Sens. 2022;14(2):428.
materials for supercapacitor. Int J Electrochem Sci. 2016;11(12): 39. Huang L, Sun Z, Shen Q, et al. Rational design of nanocarriers
10628-10643. for mitochondria-targeted drug delivery. Chin Chem Lett. 2022;
24. Alam S, Iqbal MZ. Nickel-manganese phosphate: an efficient 33:4146-4156.
battery-grade electrode for supercapattery devices. Ceram Int. 40. Yan J, Liu T, Liu X, Yan Y, Huang Y. Metal-organic
2021;47(8):11220-11230. framework-based materials for flexible supercapacitor applica-
25. Alzaid M, Iqbal MZ, Alam S, Almoisheer N, Afzal AM, Aftab S. tion. Coord Chem Rev. 2022;452:214300.
Binary composites of nickel-manganese phosphates for super- 41. Nagarajarao SH, Nandagudi A, Viswanatha R, et al. Recent
capattery devices. J Energy Storage. 2021;33:102020. developments in supercapacitor electrodes: a mini review.
26. Fu H, du Z-j, Zou W, Li H-q, Zhang C. Carbon nanotube rein- Chem Eng. 2022;6(1):5.
forced polypyrrole nanowire network as a high-performance 42. Sarac B, Karazehir T, Gilsing H-D, Eckert J, Sarac AS. Effect of
supercapacitor electrode. J Mater Chem A. 2013;1(47):14943- supporting electrolyte on capacitance and morphology of elec-
14950. trodeposited poly (3, 4-propylenedioxythiophene) derivatives
27. Wang X, Kim H-M, Xiao Y, Sun Y-K. Nanostructured metal bearing reactive functional groups. Mol Syst Des Eng. 2022;7(5):
phosphide-based materials for electrochemical energy storage. 460-479.
J Mater Chem A. 2016;4(39):14915-14931. 43. Kim P-J, You Y-W, Park H, et al. Separation of SF6 from
28. Iqbal MZ, Khan J. Optimization of cobalt-manganese binary SF6/N2 mixture using metal–organic framework MIL-100
sulfide for high performance supercapattery devices. Electro- (Fe) granule. Chem Eng J. 2015;262:683-690.
chim Acta. 2021;368:137529. 44. Zhang F, Shi J, Jin Y, Fu Y, Zhong Y, Zhu W. Facile synthesis
29. Sun M, Liu H, Qu J, Li J. Earth-rich transition metal phosphide of MIL-100 (Fe) under HF-free conditions and its application
for energy conversion and storage. Adv Energy Mat. 2016;6(13): in the acetalization of aldehydes with diols. Chem Eng J. 2015;
1600087. 259:183-190.
30. Bendi R, Kumar V, Bhavanasi V, Parida K, Lee PS. Metal 45. Sarycheva A, Gogotsi Y. Raman spectroscopy analysis of the
organic framework-derived metal phosphates as electrode mate- structure and surface chemistry of Ti3C2T x MXene. Chem
rials for supercapacitors. Adv Energy Mat. 2016;6(3):1501833. Mater. 2020;32(8):3480-3488.
31. Sahoo S, Mondal R, Late DJ, Rout CS. Electrodeposited nickel 46. Hu M, Li Z, Hu T, Zhu S, Zhang C, Wang X. High-capacitance
cobalt manganese based mixed sulfide nanosheets for high mechanism for Ti3C2 T x MXene by in situ electrochemical
17414 MALIHA ET AL.
Raman spectroscopy investigation. ACS Nano. 2016;10(12): binder-free active electrode materials for high-performance
11344-11350. supercapacitors. Electrochim Acta. 2019;296:59-68.
47. Saeed M, Rani M, Batool K, et al. Effect of Li concentration on 64. Iqbal MZ, Alam F, Alam S, Khan J, Ali A, Alzaid M. Synergetic
the structural and optical properties of Co1-xLixCr2O4 chro- electrochemical performance of strontium phosphate/polyanili-
mate nanoparticles prepared by sol-gel method. 2021. ne/graphene for high performance supercapattery devices. Dia-
48. Rania M, Tariq K, Younus A, et al. Sol-gel synthesis of nanos- mond Relat Mater. 2022;124:108918.
caled spinels using 1, 2-ethanediol as a gelation agent. 65. Yaqoob T, Rani M, Mahmood A, et al. MXene/Ag2CrO4 nano-
J Optoelectr Biomed Mat. 2021;13(3):89-94. composite as supercapacitors electrode. Materials. 2021;14(20):
49. Kannan K, Sliem MH, Abdullah AM, Sadasivuni KK, 6008.
Kumar B. Fabrication of ZnO-Fe-MXene based nanocompo- 66. Akhtar N, Rani M, Mahmood A, et al. Synthesis and character-
sites for efficient CO2 reduction. Catalysts. 2020;10(5):549. ization of MXene/BiCr2O4 nanocomposite with excellent elec-
50. Li J, Dong X’a, Sun Y, et al. Tailoring the rate-determining step trochemical properties. J Mater Res Technol. 2021;15:2007-2015.
in photocatalysis via localized excess electrons for efficient and 67. Shafique R, Rani M, Mahmood A, et al. Copper
safe air cleaning. Appl Catal Environ. 2018;239:187-195. chromite/graphene oxide nanocomposite for capacitive energy
51. Silva GS, Gracia L, Fabbro MT, et al. Theoretical and experi- storage and electrochemical applications. Int J Environ Sci
mental insight on Ag2CrO4 microcrystals: synthesis, character- Technol. 2021;1-10.
ization, and photoluminescence properties. Inorg Chem. 2016; 68. Shafique R, Mahmood A, Batool K, et al. Graphene
55(17):8961-8970. oxide/nickel chromite nanocomposite: optimized synthesis,
52. Batool K, Rani M, Younus A, et al. Nanosized magnesium structural and optical properties. ECS Journal of Solid State Sci-
doped copper chromites spinel particles synthesis and charac- ence and Technology. 2021;10(10):101005.
terization. ECS J Solid State Sci Technol. 2020;9(12):126005. 69. Lee CC, Omar FS, Numan A, Duraisamy N, Ramesh K,
53. Pan A, Ma X, Huang S, et al. CsPbBr3 perovskite nanocrystal Ramesh S. An enhanced performance of hybrid supercapacitor
grown on MXene nanosheets for enhanced photoelectric detec- based on polyaniline-manganese phosphate binary composite.
tion and photocatalytic CO2 reduction. J Phys Chem Lett. 2019; J Solid State Electrochem. 2017;21(11):3205-3213.
10(21):6590-6597. 70. Liu M, Shang N, Zhang X, Gao S, Wang C, Wang Z. Microwave
54. Khan TM, Mehmood MF, Mahmood A, et al. Synthesis of ther- synthesis of sodium nickel-cobalt phosphates as high-
mally evaporated ZnSe thin film at room temperature. Thin performance electrode materials for supercapacitors. J Alloys
Solid Films. 2011;519(18):5971-5977. Compd. 2019;791:929-935.
55. Saeed M, Rani M, Batool K, et al. Synthesis and fabrication of 71. Iqbal MZ, Amjad N, Khan MW. Metal-organic-framework as
Co1 xNixCr2O4 chromate nanoparticles and the effect of Ni novel electrode materials for hybrid battery-supercapacitor
concentration on their bandgap, structure, and optical proper- applications. Chem Electro Chem. 2022. doi: 10.1002/celc.
ties. J Comp Sci. 2021;5(9):247. 202200036.
56. Tariq A, Ali SI, Akinwande D, Rizwan S. Efficient visible-light 72. Ding R, Qi L, Jia M, Wang H. Facile and large-scale chemical
photocatalysis of 2D-MXene nanohybrids with Gd3+and synthesis of highly porous secondary submicron/micron-sized
Sn4+codoped bismuth ferrite. ACS Omega. 2018;3(10):13828- NiCo2O4 materials for high-performance aqueous hybrid AC-
13836. NiCo2O4 electrochemical capacitors. Electrochim Acta. 2013;
57. Irfan S, Rizwan S, Shen Y, et al. The gadolinium (Gd3+) and 107:494-502.
tin (Sn4+) co-doped BiFeO3 nanoparticles as new solar light 73. Iqbal MZ, Siddique S, Shaheen M, Alam S, Alzaid M. Role of
active photocatalyst. Sci Rep. 2017;7(1):1-12. ag and cu as an interfacial layer on the electrochemical perfor-
58. Zhao Y, Li C, Shen L. Recent advances on organic-inorganic mance of Ni/ag/Co3(PO4)2 and Ni/cu/Co3(PO4)2 electrodes for
hybrid perovskite photodetectors with fast response. InfoMat. hybrid energy storage devices. Ceram Int. 2022;48(11):15686-
2019;1(2):164-182. 15694.
59. Batool K, Shafique R, Akhtar N, et al. Synthesis and characteri- 74. Afzal AM, Iqbal MZ, Iqbal MW, et al. High performance and
zation of zinc-doped copper Chromites by sol gel method. gate-controlled GeSe/HfS2 negative differential resistance
J Nanoscope. 2021;2(1):15-28. device. RSC Adv. 2022;12(3):1278-1286.
60. Rani M, Batool K, Younus A, et al. Synthesis and characterisa- 75. Shafique R, Rani M, Mahmood A, et al. Investigations of 2D
tion of nanosized spinel particles of nickel-doped iron chro- Ti3C2 (MXene)-CoCr2O4 nanocomposite as an efficient elec-
mite. Philos Mag Lett. 2021;101(12):464-473. trode material for electrochemical supercapacitors. Int J Energy
61. Peng C, Yang X, Li Y, Yu H, Wang H, Peng F. Hybrids of two- Res. 2022;46(5):6689-6701.
dimensional Ti3C2and TiO2Exposing {001} facets toward 76. Akhtar N, Rani M, Mahmood A, et al. Synthesis and character-
enhanced photocatalytic activity. ACS Appl Mater Interfaces. ization of graphene oxide-based nanocomposite NaCr2O4/GO
2016;8(9):6051-6060. for electrochemical applications. J Mater Res Technol. 2021;15:
62. Iqbal MZ, Khan A, Numan A, Haider SS, Iqbal J. Ultrasonica- 6287-6294.
tion-assisted synthesis of novel strontium based mixed phase 77. Azar C, Lindgren K, Andersson BA. Global energy scenarios
structures for supercapattery devices. Ultrason Sonochem. 2019; meeting stringent CO2 constraints—cost-effective fuel choices
59:104736. in the transportation sector. Energy Policy. 2003;31(10):961-976.
63. Elkholy AE, El-TaibHeakal F, Allam NK. A facile electrosynth- 78. Chen Y, Wang N, Hu W, Komarneni S. In situ construction of
esis approach of amorphous Mn-co-Fe ternary hydroxides as porous Ni/co-MOF@ carbon cloth electrode with honeycomb-
MALIHA ET AL. 17415
like structure for high-performance energy storage. J Porous

Mat. 2019;26(3):921-929. How to cite this article: Maliha Z, Rani M,
79. Iqbal MZ, Khan J, Alam S, et al. Enhanced electrochemical Neffati R, Mahmood A, Iqbal MZ, Shah A.
performance of battery-grade cobalt phosphate via magnetron
Investigation of copper/cobalt MOFs
sputtered copper interfacial layer for potential supercapattery
nanocomposite as an electrode material in
applications. Int J Energy Res. 2021;45(13):18658-18669.
80. Iqbal MZ, Alam S, Afzal AM, et al. Binary composites of stron- supercapacitors. Int J Energy Res. 2022;46(12):
tium oxide/polyaniline for high performance supercapattery 17404‐17415. doi:10.1002/er.8406
devices. Solid State Ion. 2020;347:115276.

Maliha 2022 Investigation of Copper Cobaltmofsn

Uploaded by

Copyright:

Maliha 2022 Investigation of Copper Cobaltmofsn

Uploaded by

Document Information

Original Description:

Original Title

Copyright

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Maliha 2022 Investigation of Copper Cobaltmofsn

Uploaded by

Copyright:

1099114x, 2022, 12, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/er.

Investigation of copper/cobalt MOFs nanocomposite as an

Zeerak Maliha1 | Malika Rani1 | R. Neffati2,3 | Arshad Mahmood4 |

1 | INTRODUCTION are nearly all cost-efficient renewable energy options.3,4

3.2 | Photoluminescence spectroscopy

The photoluminescence spectrum was explored to study

T A B L E 1 Cu-MOF, Co-MOF and

T A B L E 2 Miller indices of Cu-

EDS is used to examine the elemental compositions of

(A) (B) (C)

12000 586(G-band) 12000 584(G-band) 12000 584 (G -band)

Raman shift (cm–1) Raman shift (cm–1) Raman shift (cm–1)

FIGURE 4 EDS of Cu-MOF

FIGURE 5 EDS of Co-MOF

FIGURE 6 EDS of Cu/Co MOF nanocomposite

(A) (B) 16 (C)10

low potential, attaining oxidation peaks towards positive

(A) 150 (B) (C) 80

Scan Cu-MOF specific Co-MOF specific Cu/Co MOF specific

(A) (B) (C)

0.3 0.3 0.3

0.2 0.2 0.2

0.1 0.1 0.1

0.0 0.0 0.0

Energy Density WhKg-1

maintenance of curves of tilted CV at maximum scan-rate 3.8 | Galvanostatic charge discharge

maximum capacitance with increased discharging time.79 A C KN O WL ED G EME N T S

A straightforward “One-for-All” technique is employed ORCID

like structure for high-performance energy storage. J Porous

You might also like