Materials Chemistry and Physics 292 (2022) 126861

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Materials Chemistry and Physics

journal homepage: www.elsevier.com/locate/matchemphys

Facile synthesis of Er-MOF/Fe2O3 nanocomposite for oxygen

evolution reaction
Bushra Shabbir a, Mohd Zahid Ansari b, *, Sumaira Manzoor a, Abdul Ghafoor Abid a,
Mehar Un Nisa a, Ahmed M. Shawky c, Sami Znaidia d, e, Salma Aman f,
Muhammad Naeem Ashiq a, **, T.A. Taha g, h
a
Institute of Chemical Sciences, Bahauddin Zakariya University, Multan, 60800, Pakistan
b
School of Materials Science and Engineering, Yeungnam University, Gyeongsan, 712749, South Korea
c
Science and Technology Unit (STU), Umm Al-Qura University, Makkah, 21955, Saudi Arabia
d
College of Sciences and Arts in Mahayel Asir, Department of Physics, King Khalid University, Abha, Saudi Arabia
e
Laboratoire de Recherche (LR 18ES19), Synthese Asymetrique et Ingenierie Moleculaire de Materiaux Organiques pour l’Electroniques Organiques, Faculte des Sciences
de Monastir, Universite de Monastir, 5000, Tunisia
f
Institute of Physics, Khwaja Fareed University of Engineering and Information Technology, Abu Dhabi Road, Rahim Yar Khan, 64200, Pakistan
g
Physics Department, College of Science, Jouf University, P.O. Box 2014, Sakaka, Saudi Arabia
h
Physics and Engineering Mathematics Department, Faculty of Electronic Engineering, Menoufia University, Menouf, 32952, Egypt

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• Er-MOF and MOF/Fe2O3 was success­

fully synthesized by one pot hydrother­
mal method.
• The fabricated nanocomposite (MOF/
Fe2O3) have high BET surface area of
350.804 c m2/g.
• MOF/Fe2O3 presented lower onset po­
tential and overpotential for OER as
compared to Fe2O3 and MOF
electrocatalysts.
• MOF/Fe2O3 shows low Tafel slope 40
mV/dec gives the outstanding way for
electron transfer process.
• The composite shows outstanding sta­
bility for about 25 h confirmed via
chronoamperometry.

A R T I C L E I N F O A B S T R A C T

Keywords: Currently, energy disasters and environmental contamination are of worldwide concern, and to replace the
MOF dependency on fossil fuels, it is required to use a different alternate energy resource. to confirm a green and
Nanocomposite sustainable future. In the current effort, simple Er-MOF and its nanocomposite (Er-MOF/Fe2O3) were manu­
Alkaline media
factured through hydrothermal method which freshly produced on the conducting surface of NF (Nickle Foam)
OER
for OER (oxygen evolution reaction) in 1.0 M KOH electrolyte. The synthesized materials were determined
through various analytical methods to study the structure, porosity and morphology by using X-ray Diffraction
Analysis (XRD), Brunauer Emmet-Teller (BET) and Scanning Electron Microscopy (SEM), and studies,

* Corresponding author.
** Corresponding author.
E-mail addresses: zahid.smr@yu.ac.kr (M.Z. Ansari), naeembzu@bzu.edu.pk (M.N. Ashiq).

https://doi.org/10.1016/j.matchemphys.2022.126861
Received 13 May 2022; Received in revised form 29 September 2022; Accepted 3 October 2022
Available online 9 October 2022
0254-0584/© 2022 Elsevier B.V. All rights reserved.
B. Shabbir et al.
respectively. The water-splitting measurement of the fabricated composite material showed the outstanding
oxygen activity for oxygen evolution reaction and observed lower overpotential of 216 mV to achieve a current
density of 10 mA/cm2, a lower onset potential of 1.43 V through lower Tafel slope of 47 mV/dec. Hence, present
effort may present a novel opportunity. avenue for OER.
1. Introduction
Currently the main sources of energy for energy production are fossil
fuels, and these sources are rapidly reducing while their use is respon­
sible for environmental pollution as well. With the increase in the need
for global energy and dwindling fossil fuel supplies, in addition to the
aggravation of environmental issues, it is essential to find out a pro­
gressively more sustainable and cleaner source of energy [1–3]. There
are many renewable resources, for example biomass power, solar power,
tidal power and wind power, etc., but due to seasonal factors, energy
resources suffer from intermittent availability. As a result, an effective
storage system or energy conversion is necessary along with the analysis
of renewable energy resources for huge-scale applications. Hydrogen as
a fuel is a promising energy source with endless potential because it is a
carbon-free energy source [4–6]. Hydrogen must be created utilising
plentiful and environmentally acceptable materials and techniques to
end this reliance on fossil fuels [7,8].
In recent decades, technologies like electrolysis-based systems for
producing hydrogen from water have drawn much attention [5,9]. For
the production of H2 at a large scale, it is very significant to find cheap
and environmentally friendly method [8,10,11]. An eco-friendly way for
renewable energy is water splitting using various methods such as
photocatalytic and chemo-catalytical [8,12]. The fuels produced by the
water splitting, either directly in the form of oxygen and hydrogen,
provide a tremendous amount of energy density, and scalability is a
more conventional method than other energy sources [5,13–17].
Currently, several different OER electrocatalysts are being used to
increase the reactivity of electrode and stability in various electrolyte
conditions [18–24]. Lots of scientists are involved in metal-based ma­
terials for OER as metal-based electrocatalysts have good oxygen evo­
lution catalytic properties [25–32]. The maximum unusual OER
catalytic activity was shown by Ru, Ir, and Rh-based nanomaterials
catalysts [6,33–35] and these also have excellent conductivity, normal
chemical and thermodynamic stability [36–40]. However, the shortage
of resources, expensiveness, and less stability restrict the application of
these catalysts [40–47]. Considering these constraints, designing inex­
pensive substitutes with high efficiency and durability is difficult but
necessary to undertake [48–50].
Apart from oxide materials, MOFs have significant advantages in
applications as electrocatalysts, including high design flexibility,
tunable pore channels, huge surface-to-volume ratios, the ability to be
functionalized with multiple ligands and metal centers, and a wide range
of compositions that are highly interesting for water splitting [51–61].
Nowadays, MOF materials have been used in various applications,
including medication delivery, separation, fluorescence, electrode ma­
terials, catalysis, nanomaterial carriers, magnetism, and so forth
[62–64]. For high storage devices and efficient energy conversion, a
single material is not enough for complex functions with the increased
requirements because pure MOFs have limited conductivity and stability
in alkaline and acidic conditions, although their composites are stable
[65]. Thus, it is preferable to use MOF-based composites to synthesize
electroactive nanoparticles and other porous materials for excellent
electrocatalytic performance. However, MOF- based composites with
well-defined chemical compositions, synthetic procedures,
nano-structured morphologies, reaction mechanisms, and electro­
catalytic activities are directly required to give future development and
strong inspiration in engineering composites for water splitting. Finally,
we present a detailed analysis of the current major problems and pros­
pects for designing and commercializing MOF-based derivatives
2
Materials Chemistry and Physics 292 (2022) 126861
electrocatalysts for water splitting.
Rare elements are simple to combine with stable compounds and
share a common valence state of +3. The 4f orbitals of the RE3+ ions
gradually fill up and they have a range of different electronic energy
levels. The filled 5s and 5p orbits act as a shield, making the empty 4f
orbits insensitive to the chemical surroundings around them, resulting in
well-defined electronic energy levels [66]. So that rare earth
element-based materials exhibit distinctive features in a variety of do­
mains, including luminescence, magnetic materials, catalysis, and en­
ergy conversion [67] because of their unusual structure and verity in the
oxidation states. Therefore, we have selected the rare earth MOF.
From the above-motivated concerns, in this study, a novel Er-MOF/
Fe2O3 nanocomposite was fabricated using 4′ -biphenyl dicarboxylic acid
(H2PBDC) and Erbium nitrate Er (NO3)3.5H2O as a precursor via hy­
drothermal route. The synthesized electrocatalysts were characterized
by SEM, FTIR, and BET analysis to confirm the morphological, struc­
tural, and textural characteristics. The electrochemical behavior was
achieved in a 1.0 M alkaline solvent (KOH) environment employing
three working electrodes system. Among all the fabricated materials, Er-
MOF/Fe2O3 nanocomposite has better OER performance with a small
Tafel slope of 47 mV dec− 1 and lower overpotential (216 mV). The
synergetic action of the metals in MOF has been used to explain the
catalytic process for water splitting.
2. Experimental part
2.1. Chemicals and reagents
Erbium nitrate Er(NO3)3.5H2O, (99.99%, Sigma-Aldrich), N,N-
Dimethylformamide (DMF, 99.5%, Sigma-Aldrich), 4,4′ -biphenyl
dicarboxylic acid (H2PBDC, 95%, Sigma-Aldrich), ethyl alcohol (99.8%,
Analar), iron nitrate (Fe(NO3)3.9H2O (98%, Sigma Aldrich), Potassium
hydroxide (KOH, 85%, Sigma-Aldrich), Nickel foam (NF, Shanghai
Zhonghui, China) were all commercially bought. Without purifications,
all these were used as such.
2.2. Formation of Fe2O3
For the production of Fe2O3 nanoparticles, the sol-gel auto-com­
bustion technique was applied. Fe (NO3)3.9H2O (0.05 M) precursor so­
lution was chelated using a 0.2 M solution of citric acid as a chelating
agent in 100 ml deionized H2O as a solvent. Then the solution pH was
maintained up to 7–8 by adding 2 M ammonia solution; after that, the
mixture was continuously stirred on the magnetic hotplate and heated at
70 ◦ C by stirring till the gel was produced. The dehydrated gel was then
burnt at 200–250 ◦ C, and the red color powder was formed. Finally, the
resultant powder could be ignited at high temperature of 550 ◦ C for 5 h
to synthesize Fe2O3 nanoparticles.
2.3. Formation of Er-MOF/Fe2O3
Er-MOF was fabricated through the hydrothermal method using N,
N-dimethylformamide (DMF) as a solvent, 4,4′ -biphenyl dicarboxylic
acid (0.226 g) as a ligand, and Er (NO3)3.5H2O (0.200 g) as a metal
precursor. All were combined and swirled on the magnetic hotplate for
20 min, so then synthesized Fe2O3 nanoparticles (0.1 g) were poured to
the reaction precursor. So that, the resultant precursor was added into
the autoclave for 48 h at 160 ◦ C. The resulting precipitates were filtered,
rinsed with ethanol, and evaporated in oven at 60 ◦ C for 5 h. The
B. Shabbir et al. Materials Chemistry and Physics 292 (2022) 126861

resultant product was collected, grind, and then kept in the vacuum
desiccator. A similar procedure was used to form Er-OF except for the
addition of iron oxide nanoparticles and was used for comparison
purposes.

2.4. Characterization

The surface morphology of the MOF, iron oxide and their composite
were investigated through SEM (scanning electron microscopy) instru­
ment with Quanta 200-FEG. The volume, size, and surface area of the
pores of all the products were measured by BET (Brunauer-Emmett-
Teller using NOVA-2200e. For the structural confirmation and crystal­
linity, XRD was performed via an innovative Bruker-D-8 diffractometer.
The formation of MOF and its composite with Fe2O3 was confirmed by
the Fourier transform infrared (FTIR) spectroscopy by means of Fourier
Infrared Spectrometer FTIR (Bruker Tensor27) in the range 400–4000
cm− 1.

2.5. Ink preparation

The formation of a working electrode is the most critical step for

electrochemical performance experiments. Before performing, the
nickel foam (NF) was cut into small 1 × 1 cm pieces, and then these tiny
pieces were cleaned with distilled water, ethanol, 2.0 M HCl, and
acetone in all solvents subsequently. After being rinsed, the pieces were
dried in the drying oven at 333 K. Finally, the resultant dried NF pieces
were then placed in the autoclave in an oven at 373 K. The grown
products on nickel foam was washed with ethanol and evaporated at
ambient temperature. The active mass loading of Er-MOF/Fe2O3 on NF
is 0.005 g.

2.6. Electrochemical characterization

The electrocatalytic characterization, such as cyclic voltammetry

(CV) and electrochemical impedance spectroscopy (EIS), was done by
equipped Autolab PGSTAT-204 (Metrohm). All parameters were con­
ducted with three electrode systems, including a Pt wire as a counter
electrode, Ag/AgCl which was used as reference electrode, and working
electrodes (synthesized materials coated on NF) that were fixed in place
with a pyrex glass cell. All electrochemical experiments were carried out
at ambient temperature (298 K). Argon gas was used to gas the solution
for 20 min before use. The cyclic voltammetry experiments were per­
formed with both positive and negative potentials, scanning at a range of
5 mV s− 1; the LSV only used positive potential. Using the following
equation, the RHE potential was obtained from reference electrode (Ag/
AgCl) potential [68]:
ERHE = E Ag/AgCl + 0.059 × pH + E0Ag/AgCl (1a)
The electrocatalyst’s kinetics rely exclusively on its ability to cata­
lyze the chemical response. To compute a Tafel slope by drawing a graph
between logj vs. overpotential (η) from the polarization curve to eval­
uate the kinetics and performance of the prepared materials and were
calculated via equation (2).
Fig. 1. XRD patterns of Fe2O3, Er-MOF and Er-MOF/Fe2O3.
scan rates, such as 5, 10, 15, 20, and 25 mV/s. In this case, the variation
in j was calculated using the difference between the positive and nega­
tive current densities. The values of j were drawn in contrast to the
necessary scan rates to make the Cdl value appear as a straight line. Then
the resultant slope was divided by 2 to get the double-layer capacitance.
Further, for ECSA calculation, relation (2) was used. The electro­
chemical activity of prospective working materials requires a broad
electrochemical surface area with multiple exposed active sites.
EIS (Electrochemical impedance spectroscopy) is another useful
method to understand the water splitting reaction mechanisms, charge
transfer processes in materials, and electrode surface characteristics.
The electrical conductivity of a substance may be measured using this
approach, which is widely accepted.
3. Results and discussion
3.1. Textual, structural and morphological discussion

η = a + (2.303RT/αnF) × logj (2a) Using BET measurements, the active sites of the manufactured
products were studied via adsorption isotherm for N2 as given in Fig. S1.
In the above equation, j is density of current, ‘a’ is the transfer of
The resultant BET surface area of Fe2O3, Er-MOF, and Er-MOF/Fe2O3
charge coefficient, ‘F’ is the Faraday constant, η shows the overpotential,
were 39 m2/g, 143.4 m2/g, and 352 m2/g, respectively. Among all, the
and The quantity "n" refers to how many electrons are active within the
nanocomposite material has a much higher surface area than individual
catalytic reaction.
materials. The introduction of the Fe2O3 in the fabricated Er-MOF can
Electrochemical surface area (ECSA) is another significant consid­
cause morphological changes, and even cause opening of some pores
eration, and it may be calculated using equation (3) to increase the
which can coordinate to the active sites of strong adsorption interaction,
eletrocatalytic performance of all synthesized products:
present in some Er-MOFs. Therefore, the presence of these active sites
ECSA = Cdl/Cs (3a) can involve in the improvement of the surface area of the nano­
composite. Accordingly, these results suggest that a material’s huge
Various CV plots in the non-faradic region were taken at multiple

3
B. Shabbir et al.
Fig. 2. (a) Fourier Transform Infrared spectroscopy of all synthesized products (b) SEM image of Fe2O3 (c) SEM image of Er-MOF (d) SEM image of Er-MOF/Fe2O3
with their relative histogram.
surface area predicts the multiple active spots on its surface that makes it
more conducive to the OER.
The purity and phase structure of the materials were examined using
XRD. The crystallinity and phase of Fe2O3, Er-MOF, and their composite
were determined. All of the X-Ray Diffraction (XRD) graphs of synthe­
sized materials are given in Fig. 1. The strong peaks in the XRD pattern
of Fe2O3 present at 2θ = 24.5◦ , 32.61◦ , 35◦ , 38.7◦ , 48.9◦ , 53.7◦ , 56.7◦ ,
62.1◦ , 63.9◦ , and 69.4◦ correspond to the crystal planes of (012), (104),
(110), (112), (113), (024), (116), (122), (214), (300), and (208),
respectively which confirm the fabrication of Fe2O3 (Maghemite) ac­
cording to reference pattern JCPDS 00-001-1053. The crystal system of
Fe2O3 is rhombohedral, Space group is R-3c and space group number is
167. The XRD pattern of Er-MOF, synthesized via hydrothermal tech­
niques, is depicted in Fig. 1. The sharp peaks in pattern indicate that the
material is in crystalline form while the broadness in peaks suggest that
the size of the particle is in the nanometer range. On the other hand, Er-
MOF/Fe2O3 (Fig. 1) has the peaks for both the materials i.e. Er-MOF
(indicated by *) and Fe2O3 (indicated by #), indicating that the nano­
composite (Er-MOF/Fe2O3) was successfully synthesized. Using the
well-known Scherrer equation, the materials’ crystallite sizes were
determined and found to be 35, 42 and 45 nm for composite, Er-MOF
and iron oxide, respectively. The composite’s lower crystallite size
compared to other materials indicate that it has larger favourable sur­
face area for electrocatalytic application. The XRD of the modified
composite sample shows another hump at 2 theta range near 45◦ this
means that the composite has an extra peak of carbon which comes from
MOF.
The structure of the products was confirmed using FTIR in addition
to XRD. Fig. 2a shows FTIR spectra for Er-MOF, Fe2O3, and Er-MOF/
Fe2O3 nanocomposite. The stretching vibrations of C– – O and C–OH,
respectively, are represented by the distinctive peaks at 1650 cm− 1 and
1393 cm− 1 in the FTIR spectra of Er-MOF [69]. The Er–O band is
responsible for the band at 540 cm− 1, while OH group vibration repre­
sented by the peak at 3145 cm− 1. The FTIR spectrum of Fe2O3 showed
peaks below 1000 cm− 1 especially at 672 cm− 1, due to Fe–O vibration
[70]. The Fe–O band vibrations are responsible for the significant ab­
sorption peaks below 700 cm− 1 due to the hematite product. Hydroxyl
groups and water molecules’ bending and stretching vibrations are
allocated to the broad band at 3331 cm− 1 and 1625 cm− 1 [71]. The
4
Materials Chemistry and Physics 292 (2022) 126861
results demonstrate that the synthesized materials were produced in an
aqueous solvent containing surface-absorbable water in a small amount
and also on the same surface, structural hydroxyl groups. Additionally,
CH3 is responsible for a peak at 1437 cm− 1 [72]. Nonetheless, after
calcination, all organic species were eliminated. Then, at 672 cm− 1, we
discovered a band attributable to the Fe–O in hematites. The stretching
vibrations of C– – O and C–OH, respectively, are determined by the
distinctive peaks at 1650 cm− 1 and 1393 cm− 1 in FTIR spectrum of
Er-MOF/Fe2O3 compound. The Er–O band is responsible for the peak at
540 cm− 1 and the Fe–O band vibrations are attributable for the band at
670 cm− 1,the significance of the peaks at 540 cm− 1 and 760 cm− 1
confirms the synthesis of Er-MOF/Fe2O3 [73].
For several practical applications, morphology plays an important
role, and SEM has been used for investigating the surface morphology of
Fe2O3, Er-MOF, and Er-MOF/Fe2O3. Fig. 2b represents the SEM image of
Fe2O3, which shows that the morphology of all the nanoparticles is
round in shape, with an average particle size of 0.384 μm, while Fig. 2c
depicts the SEM image of Er-MOF representing the morphology in the
form of blades with relatively smooth surfaces having an average par­
ticle size of 0.241 μm. On the other, Fig. 2d depicts the SEM image Er-
MOF/Fe2O3 nanocomposite; the morphology of Er-MOF/Fe2O3 shows
that the spherical shape nanoparticles of Fe2O3 are densely and uni­
formly distributed on the cuboid block of Er-MOF, and their surface is
relatively rough confirming both phases in the composite with average
particle size is 0.218 μm. More activity will be present in the produced
materials the smaller the average particle size.
3.2. Electrochemical measurements
Using a standard three electrode system the electrocatalytic char­
acterization of the products was evaluated, respectively by using Ag/Cl
as a reference electrode, synthesized product for working electrode and
Pt wire as counter electrode using a computer-controlled AUTOLAB
(PGSTAT-204). ECSA, EIS, and CV were utilize to calculate the mate­
rials’ innate catalytic activities toward OER. All electrochemical ex­
periments were taken at ambient temperature (298 K) in 1. 0 M KOH
electrolyte. BET analysis has shown that nanocomposite has increased
OER activity because of its huge surface area and significantly active
spots. Hence, for the measurement of OER performance, cyclic
B. Shabbir et al.
Fig. 3. (a) Cyclic Voltammogram (b) Enlarge CV curves (c) LSV for all the synthesized materials, (d) Overpotential (e) Tafel Slope for all the synthesized products.
voltammetry was used to analyze the characteristics of the RuO2, Fe2O3,
Er-MOF, and Er-MOF/Fe2O3 at the 5 mV s− 1 as illustrated in Fig. 3a.
Form the CV, the recorded onset potential values were found to be
1.55,1.56, 1.45, 1.51 and 1.43 V vs. RHE for bare NF, Er-MOF, Fe2O3,
and their nanocomposite. Er-MOF/Fe2O3 composite has lesser onset
potential, indicating the highest current response due to a strong syn­
ergistic effect. The other important parameter is the overpotential for
the initiation of sluggish OER, which was measured from enlarged CV
curves illustrated in Fig. 3b and the determined values for the nano­
composite, Er-MOF, Fe2O3, RuO2 and bare NF were 216, 314, 323, 372
and 388 mV, respectively (Fig. 3c). The overpotential at 100 mA cm− 2
for Er-MOF/FeO3, Er-MOF and Fe2O3 is 416 mV,536 mV and 506 mV
which were also calculated via CV curves. Fig. 3d represent the linear
sweep voltammetry curve (LSV), representing the intrinsic current
density of all the fabricated materials. Among all, the nanocomposite has
highest current density of 275 mA cm− 2 in contrast to the bare NF, RuO2,
Fe2O3, and Er-MOF having 64, 47, and 62 mA cm− 2, respectively, con­
firming the high conductivity of the fabricated nanocomposite. Er-
MOFs-based composite, among others, offers advanced matrices with
implanted active metal sites and larger surface area generally. Gener­
ally, Er-MOF and Fe2O3 have the lowest electrocatalytic activity,
requiring a high overpotential of 316 mV and 323 mV and an onset
potential of 1.51V 1.45V at 10 mA cm− 2, respectively. Moreover, when
Fe2O3 is loaded on Er-MOF, the Er-MOF/Fe2O3 exhibits highest catalytic
measurement, with small overpotential of 216 mV and an onset poten­
tial of 1.43 V owing to its huge surface area with multiple active sites,
uniform size of particles and complete associations between active sites
and reactants.
Typically, the four stages of the cationic and anionic transmission
process are involved in the overall mechanism of OER., which are
5
Materials Chemistry and Physics 292 (2022) 126861
depicted below, along with the formation of OH- intermediates
M + OH− → M − OH + e− (1b)
M-OH- + OH− → M − O + H+ + e− (2b)
−
M − O + OH → M-OOH + e −
(3b)
− −
M OOH + OH → M + O2(g) + H + e + −
(4)
The catalytic site of the obtained materials, which is represented by
M − O here, is the Er (III). Hydroxide ions are deposited on the catalytic
site in the first stage as a result of the oxidation of hydroxide anions (1e-
), forming M − OH (Er–OH). The production of Er–O then follows the
removal of linked protons and electrons from Er–OH. The transition
metal hydroperoxide is created by a nucleophilic approach (hydroxyl
anion) on the O–Er (Er–OOH). Another proton and transmission of
electron involve in the removal of oxygen and the creation of additional
free active centers. The two Er–O species are combined to create metal
(Er) and oxygen (O2) in the following phase. The majority of the
hypothesised mechanisms are based after the method presented above,
with differences caused by the quantity of protons or electrons
exchanged at each point. Proton and electron transfers were typically
described as being dissociated. The information presented above
confirmed the outstanding electrocatalyst-electrolyte interface contact
that occurred during OER.
The Tafel slope is a vital measurement to discuss the electro-kinetics
illustrating the dependency of overpotential (η) and current density (j).
The observed Tafel slope for bare NF, RuO2, Fe2O3, MOF, and MOF/
Fe2O3 was found to be 99, 86, 78, 51, and 47 mV/dec, as illustrated in
Fig. 3c, which demonstrate the excellent transfer of charge in the alka­
line medium. The Tafel slope for Er-MOF/Fe2O3 (47 mV dec− 1) is the
B. Shabbir et al. Materials Chemistry and Physics 292 (2022) 126861

Table:1
Comparison of OER activity of several MOFs and MOF-derived Composites electrocatalysts with present work.
Serial No. Material Substrate Overpotential Tafel Slope References
− 1
1 Fe-MOF Nickel foam 240 mV 34 mV dec [74]
2 Er-MOF Glassy carbon electrode 734 mV 133.4 dec− 1 [74]
3 Er-MOF/MoS2 Glassy carbon electrode 234 mV 55.9 mV dec− 1 [75]
4 CDs@MOF Nickel foam 272 mV 51 mV dec− 1 [76]
5 NiNH2BDC MOF/5 wt% reduced graphitic carbon hybrids Nickel foam 388 mV 57.3 mV/dec− 1 [77]
6 ZIF-67@Co3(PO4)2 (1:1.5) Nickel foam 73 mV 70 mV/dec− 1 [78]
7 LDH-ZIF-12 composite Nickel foam 337 mV 89 mV dec− 1 [79]
8 ZIF/MIL Nickel foam 267 mV 57 mV dec− 1 [80]
9 SiW9Co3[h]@ZIF-67 Nickel foam 150 mV 93.9 mV dec− 1 [81]
10 (GO 8 wt%) Cu-MOF composite glassy carbon electrode 209 mV 84 mV dec− 1 [1]
11 Fe2O3/Ni-MOF-74 Nickel foam 264 mV 48 mV dec− 1 [82]
12 Er-MOF/Fe2O3 Nickel foam 216 mV 40 mV dec¡1 This work

Fig. 4. a) Combined EIS plot, (b–d) EIS Nyquist plot with their relevant circuit for Fe2O3, Er-MOF, and their composite.

lowest in comparison to Er-MOF (51 mV dec− 1), bare NF (99 mV dec− 1)
and Fe2O3 (78 mV dec− 1). The synergistic interaction between the Fe2O3
and Er-MOF interfacial area may be involved for the higher catalytic
performance. The composite product has a smaller Tafel slope indicating
a faster reaction charge. Table 1 represents the comparison of over­
potential and Tafel slope of Er-MOF/Fe2O3 with other reported results,
which demonstrated that the outcomes from the current investigation
are significantly improved.
Another principal method to clarify the OER is the EIS, in the low-
frequency domain, EIS generates a straight line, whereas, in the high-
frequency domain, it produces a semicircle-shaped curve and is used
to seek out the resistivity of products and electrolyte as shown in Fig. 4
(a–d), with their circuit fitting (inset). Among all, the Er-MOF/Fe2O3
signifies the smaller semicircle in comparison to Er-MOF and Fe2O3
representing the capacity to transmit charge at high frequencies and
increased electronic conductivity, as shown in Fig. 4a. The low charge

Fig. 5. a) CV cycles, b) chronoamperometry of the nanocomposite.

6
B. Shabbir et al.
Fig. 6. (a) SEM analysis after stability (b) XRD studies before and after stability of composite material (c) LSV before and after stability of composite materials.
transmition resistance is related to the smaller semicircle. The values of
polarization resistance (Rp) for Fe2O3, Er-MOF, and Er-MOF/Fe2O3 were
38 Ω, 2.14 Ω, and 395 mΩ, as illustrated in picture 4 (b-d); the smaller
the value of Rp represents the excellent conductivity of Er-MOF/Fe2O3
due to larger surface area, high crystallinity and good morphology.
Hence, it suggests that in composite, the effect of Fe2O3 incorporation
into the Er-MOF enhances the material’s conductivity and affects its
catalytic activity.
The significant way to assess the electrocatalytic potential of all
synthesized materials that may be taken into account using the equation
is the electrochemical surface area (ECSA): Cdl = ECSA. It is specified
that there is a need to have a significant value of ECSA with a consid­
erable amount of visible active sites for the capable activity of working
materials. As seen in figure S2 (a-c), numerous CV plots were taken for
this purpose at different sweep rates, including 5, 10, 15, 20, 25, and 30
mV/s in the non-faradic region. To get the straight line for indicating the
double-layer capacitance (Cdl) value was achieved when the value of Δj
was plotted versus scan rates. The Cdl values of Er-MOF/Fe2O3, Er-MOF,
and Fe2O3 were 0.016, 0.015, and 0.007 mF, as shown in figure S2 (d-f).
The computed ECSA of Er-MOF/Fe2O3, Er-MOF, and Fe2O3 were 0.4,
0.262, and 0.175 cm2 indicating greater surface area with the excellent
transfer of electrons. Among all, Er-MOF/Fe2O3 has the greater value of
ECSA, demonstrating the presence and availability of active sites, which
are important for the transport of electrons during electrolytic water
splitting.
An electrocatalyst must be stable enough for commercial application,
even if it has a high degree of activity. The synthesized nanocomposite
boosted catalytic activity and remained stable during 2000 CV cycles
testing in 1.0 M alkaline solvent at 50 mV s− 1. According to, cyclic
voltammograms indicated a minor variation between the 1st and 2000th
cycles, as illustrated in Fig. 5a. Electrolysis stability was also carried out
via chronoamperometry in a 1.0 M alkaline solvent (KOH) solution for
25 h at 0.8 V vs. Ag/AgCl electrode, as illustrated in Fig. 5b. Time-
versus-current density graphs revealed virtually constant activity
throughout electrolysis, with a modest reduction over time. Fig. 5 in­
dicates that as-synthesized material performs better and lasts longer
when Fe2O3 and Er-MOFs work together in harmony.
7
Materials Chemistry and Physics 292 (2022) 126861
The XRD, LSV and SEM micrographs from the Er-MOF/Fe2O3 after
long-term durability are shown in Fig. 6. The morphology of the com­
posite material remain same after the stability test except some voids are
produced (Fig. 6a). The obtained data revealed that the material’s peaks
intensity in the XRD pattern (Fig. 6b) has been changed very little, but
the peak position remain same confirming the material’s structure was
not changed. The XRD and SEM suggested that the product is very much
stable. Figure 6c shows the LSV curves for the Er-MOF/Fe2O3 before
and after stabilization. The image makes it evident that there is just a
small difference among the LSV curve before and after the constancy
test, demonstrating how much more stable the material.
4. Conclusion
In the present work, Er-MOF/Fe2O3 nanocomposite was synthesized
via the hydrothermal method, deposited on a conducting surface (NF),
and finally employed for OER activity. All the products are determined
via XRD, SEM, BET, and the structural, morphological, and textural
features are confirmed by FTIR. The fabricated Er-MOF/Fe2O3 nano­
composite has enhanced active sites due to greater surface area (350.80
m2/g) and high porosity, responding to outstanding activity for oxygen
evolution reaction such as lower onset potential of (1.43 V) with a small
overpotential of 216 mV to attain a current density 10 mA/cm2, repre­
sents its good catalytic activity. Er-MOF/Fe2O3 nanocomposite also
provides a lower tafel slope of 47 mV/dec and is good way for conve­
nient electrons transfer. Hence, all the attained outcomes supported our
designed material for good OER activity and fulfill the energy re­
quirements in the upcoming future.
CRediT authorship contribution statement
Bushra Shabbir: Conceptualization, Writing – original draft. Mohd
Zahid Ansari: Investigation, Writing – review & editing. Sumaira
Manzoor: Conceptualization, Writing – original draft. Abdul Ghafoor
Abid: Formal analysis, Writing – review & editing. Ahmed M. Shawky:
Investigation, Writing – review & editing, Soumaya Gouadria. Sami
Znaidia: Formal analysis, Writing – review & editing. Salma Aman:
B. Shabbir et al.
Writing – review & editing. Muhammad Naeem Ashiq: Supervision. T.
A. Taha: Writing – review & editing.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability
No data was used for the research described in the article.
Acknowledgments
The author (Sami Znaidia) extends his appreciation to the Deanship
of Scientific Research at King Khalid University for funding this work
through Large Groups Project under grant number (RGP.2/166/43). The
authors would like to thank the Deanship of Scientific Research at Umm
Al-Qura University for supporting this work by Grant Code:
(22UQU4331174DSR25).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.matchemphys.2022.126861.
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