Title: Heterometallic Feed Ratio-Dominated Oxygen Evolution Activity

in Self-Supported Metal-Organic Framework Nanosheet Arrays

Electrocatalyst

Authors: En-Cui Yang, Rui-Jie Li, Yu-Feng Qi, Qian Wang, Jia-Jun
Wang, Zheng-Yu Liu, Xiu-Guang Wang, and Xiao-Jun Zhao

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Zeitschrift für anorganische und allgemeine Chemie 10.1002/zaac.202000121

Heterometallic Feed Ratio-Dominated Oxygen Evolution Activity in Self-Supported Metal-Organic

Framework Nanosheet Arrays Electrocatalyst

Rui-Jie Li,[a] Yu-Feng Qi,[a] Qian Wang,[a] Jia-Jun Wang,[a] Zheng-Yu Liu,[a] Xiu-Guang Wang,[a] Xiao-Jun

Zhao,*[a] and En-Cui Yang*[a]

Accepted Manuscript
To Z. Anorg. Allg. Chem. (Article)

* Prof. Dr. E.-C. Yang

[a] College of Chemistry
Key Laboratory of Inorganic-Organic Hybrid Functional Material Chemistry, Ministry of Education
Tianjin Key Laboratory of Structure and Performance for Functional Molecules
Tianjin Normal University
Tianjin 300387, P. R. China
Email: [email protected]
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/zaac or from the author.

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Zeitschrift für anorganische und allgemeine Chemie 10.1002/zaac.202000121

Abstract. Developing earth-abundant, highly active and long-term durable electrocatalysts for oxygen

evolution reaction (OER) is highly desirable and great challenging for large-scale industrial application of

electrochemical water splitting. Herein, in-situ growth of uniform nanosheet arrays on nickel foam (NF) is

hydrothermally achieved by varying feed ratios of Fe(III) and Ni(II) salts. The feed ratio of the two active

metals has significantly dominated both the morphological and electronic structures of the resultant

Accepted Manuscript
electrocatalysts, leading to feed ratio-dependent volcano-type OER activity. The optimized

Fe0.89Ni0.11-BDC/NF exhibits the best OER performance, affording a low overpotential of 220 mV to drive

a current density of 50 mA·cm 2 with small Tafel slope of 44.8 mV·dec 1 and long-lasting stability over 20

hour. The synergistic effect from the Fe(III) and Ni(II) species on both the morphological and electronic

structure modulations have dramatically accelerated the reaction kinetics, responsible eventually for the

enhanced OER activity. This work provides valuable information for nanostructured MOFs as efficient

electrocatalysts.

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Introduction

Increasing concerns on both environmental pollution and energy crisis have offered significant necessity

and urgent demand for finding new alternative and clean energy sources.[1, 2] Hydrogen production from

electrocatalytic water splitting, one of important ways to produce green and sustainable hydrogen energy,

has received tremendous interest due to highly efficient energy storage and conversion.[3] However, the

Accepted Manuscript
sluggish kinetics and low efficiency make the oxygen evolution reaction (OER) on the anode of the

electrocatalytic cell become the bottleneck of the electrocatalytic water splitting.[4] Therefore, it is

essentially important and urgent to design earth-abundant, high-performance and long-term durable OER

electrocatalyst to replace highly active but expensive and scarce noble metal-based nanomaterials (IrO2,

RuO2 and so on) for large-scale developments of electrochemical water splitting.[5]

Self-supported metal-organic frameworks (MOFs) with inexpensive transition metals or metal clusters

and functionlized organic ligands in situ grown on the conductive substrates have emerging as promising

OER electrocatalysts due to their adjustable compositions, well-tailorable microstructures, and increased

conductivity.[6  11] Up to date, lots of layered monometallic Co-, Ni-, Fe- and bimetallic NiFe-, FeCo-,

NiCo-MOFs with aromatic dicarboxylate ligands (terephthalate, 2-aminoterephthalate,

2,6-naphthalenedicarboxylate, 2,5-dihydroxybenzenedicarboxylate, 1,4-naphthalenedicarboxylate and so

on) have been directly anchored on the three-dimensional conductive Ni foam (NF), porous -Al2O3, NiFe

alloy foam through ultrasonic method,[12] chemical deposition,[13] hydro/solvothermal approach,[14]

semisacrificial template growth,[15] and dissolution-crystallization mechanism.[16, 17]

It was found that

various factors including the feed ratio of the reactant components, preparation process, condition control,

and characterization method have been found to be significantly regulated the morphologies and

electronic structures of the resulting electrocatalysts. In particular, the cooperated effects from different

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Zeitschrift für anorganische und allgemeine Chemie 10.1002/zaac.202000121

components, such as mixed metallic species, structurally related organic ligand as well as the nanomaterials

and the substrate, can greatly improve the electrocatalytic performances by modulating the morphological

and electronic structures, which then further enhance the electrocatalytic activity and durability through the

optimized absorption energy towards the active species.[18  25] For example, a bimetallic MOF with mixed

terephthalate and 2-aminoterephthalate ligands directly immobilizated on the NF has exhibited enhanced

Accepted Manuscript
OER performance than the single ligand-derived counterpart resulting from the cooperated electronic

interaction between the two organic linkers with different electron-donating group.[18] The bimetallic

clusters {Fe2Ni(µ3-O)(COO)6(H2O)3} in the water-stable NH2-MIL-88B MOF directly grown on the NF

have exhibited positive coupling effects between Ni and Fe metal ions as well as between the MOF and NF,

achieving ultralow over-potentials of 240 mV at current density of 10 mA cm − 2 for the OER and a minor

chronopotentiometric decay of 7.8% at 500 mA cm −2 after 30 hour.[21] Herein, to systematically search the

most suitable electronic interaction from different low-cost metals during the OER process, NiFe-BDC

(BDC= 1,4-bezenedicarboxylate) nanosheet array with different feed ratios of Fe(III) and Ni(II) salts were

uniformly anchored on the NF through the facile solvothermal method, and utilized directly as OER

electrocatalysts for the structure-activity correlations establishment. The feed ratio of the active Fe(III)

and Ni(II) components has significantly modulated the morphological and electronic structures, leading to

feed ratio-dependent volcano-type oxygen evolution activity. The optimal Fe0.89Ni0.11-BDC/NF requires a

low overpotential of 220 mV to drive a large current density of 50 mA·cm  2, a Tafel slope of 44.8

mV·dec  1 and durable stability for at least 20 hour in 1.0 M KOH electrolyte. The good activity of

Fe0.89Ni0.11-BDC/NF is attributed significantly to the highly ordered nanosheet array and favorable

electronic structure, which is originated from the catalyst-substrate interaction and the favorable charge

transfer between Fe(III) and Ni(II) centers.

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Results and Discussion

Syntheses and PXRD Patterns

NF-supported bimetallic FexNi1  x-BDC nanomaterials were in situ hydrothermally synthesized at

125 °C by varying the feed ratios of cheap inorganic Fe(III) and Ni(II) salts. The NF in the present system

serves as both substrate and Ni source, which can also observed in the transition metal-based nanomaterials

Accepted Manuscript
systems with NF as substrate.[26, 27] Thus, the atomic content for Ni(II) in the resultant product is roughly

higher with the feed ratio (Table S1). The different colors of the deposits covered on the NF confirm the

successful preparation of the target samples, and the increased Ni(II) content has induced the dark brown

product to pale green in appearance (Figure S1). In the FT-IR spectra, the asymmetric and symmetric

stretching vibrations for the deprotonated carboxylate group are observed at 1581  4 and 1381  5 cm  1

(Figure S2), suggesting the presence of BDC ligand.

Powder X-ray diffraction (PXRD) patterns of these FexNi1x-BDC/NF are feed ratio-independent (Figure

1), suggesting their isomorphic crystalline phase. All these samples show characteristic peaks at 8.9°, 14.2˚,

_
15.9˚ and 17.9˚, corresponding respectively to (200), (001), (20 1 ) and (400) crystal facets of monoclinic

Ni-BDC MOF.[28] A strong peak at 44.5° is assigned to the metallic Ni (JCPDS no. 65-2865) from the NF

substrate.[29] Notably, the intensity of the main peaks decreases with the increased feed ratio of Ni(II) and

Fe(III) ion, suggesting possibly the changed crystallinity by the hybrid of binary metals with slightly

different ionic radius. Notably, compared with the reported nanoployhedra with the same chemical

compositions,[24] the FexNi1  x-BDC/NF samples own better crystallinity probably resulting from the

optimized reactant media.

Morphological Characterizations

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The morphology of these FexNi1x-BDC/NF samples was identified by scan electron spectroscopy (SEM)

to unravel the influence of the co-coordination of Fe(III) and Ni(II) ions with 1,4-bezenedicarboxylate. As

shown in Figure 2, uniform nanosheet arrays are tightly and firmly anchored on the surface of the NF. The

thickness of the nanosheets becomes thinner and thinner with the increasing feed ratio of Ni(II) and Fe(III).

The TEM characterizations of Fe0.89Ni0.11-BDC was investigated as a representative sample. As shown in

Accepted Manuscript
Figure 3a, the nanosheets of the Fe0.89Ni0.11-BDC are solid and have smooth surface. The high-resolution

TEM (HR-TEM) image shows a d-space lattice of 0.99 nm, corresponding to (2 0 0) facet of Ni-BDC

(Figure 3b). Selected area electron diffraction (SAED) result of Fe0.89Ni0.11-BDC shows highly ordered

diffraction spots (Figure 3b inset), indicating the relatively high crystallization. STEM-EDS elemental

mappings show the uniform distribution of Fe, Ni, C and O elements (Figure 3c), in which the higher

atomic percentage of both O and C indicates the presence of BDC ligand (Table S1). Moreover, the metal

contents in the Fe0.89Ni0.11-BDC/NF sample determined by XPS, STEM-EDS, and SEM-EDS are roughly

consistent (Ni:Fe= 7.81: 6.34, 6.06:3.54, and 2.97:2.12), and their slight difference is resulting from the

different selected surface areas of the nanosheet array. All these observations clearly indicate the successful

preparation of NF-supported heterometallic MOF nanosheet arrays via solvothermal treatment. Previously

reported nanomaterials with the same chemical compositions have owned various morphology including

nanopolydra,[24] nanoclusters,[15] sheet-like two-dimensional structure[22] nanosheet arrays by controlling the

fabrication conditions,[10, 14, 28] which are highly important for the electrocatalytic performances.

Electronic Structure

Chemical environments and oxidation states of each element in Fe0.89Ni0.11-BDC/NF were explored by

X-ray photoelectron spectroscopy (XPS), together with Ni-BDC/NF and Fe-BDC/NF for comparison. The

full spectrum demonstrates the co-existence of Ni, Fe, C and O elements (Figure S3). The C 1s spectrum

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involves three binding energies (BEs) at 285.1 eV, 286.6 eV and 289.1 eV (Figure S2). The latter two BEs

should be assigned to the arylcarbon from the phenyl ring (C=C) and the carboxylate carbon of OC=O.[14]

High-resolution O 1s region contains three peaks at 531.5 eV, 532.7 eV and 534.0 eV (Figure S2),

corresponding respectively to Fe  O and Ni  O, O  C=O bonds and absorbed water molecule.[14, 22]
As

shown in Figure 4a, the high-resolution Fe 2p region includes two main peaks at 713.4 eV and 726.7 eV for

Accepted Manuscript
the Fe 2p3/2 and Fe 2p1/2, showing the existence of Fe(III) species. Moreover, as compared with

Fe-BDC/NF, the Fe 2p region of Fe0.89Ni0.11-BDC/NF red shifts about 0.5 eV, indicating an increased

electron density around Fe(III) centers by co-coordination.[14] The Ni 2p spectrum is deconvoluted into

three pairs of peaks (Figure 4b). The binding energies at 877.0 eV (2p1/2) and 858.9 eV (2p3/2) are attributed

to the NiO bond resulting from the coordination of Ni(II) ion with 1,4-bezenedicarboxylate ligand. Two

peaks at 879.0 eV (2p1/2) and 860.3 eV (2p3/2) were designated as NiOH bond between the Ni(II) ion and

the hydroxyl group. The binding energies at approximately 864.6 eV (2p3/2) and 882.9 eV (2p1/2) are

corresponding to the Ni 2p satellite peaks.[30] Compared with Ni-BDC/NF, the Ni 2p orbit in

Fe0.89Ni0.11-BDC/NF shift towards a higher binding energy, indicating that the electron density of Ni(II)

decreases. A further charge analysis based on the Bader method quantitatively indicates that the charge of

the FexNi1x-BDC sample decreases from 8.78 |e| for Ni-BDC to 6.55 |e| for Fe0.875Ni0.125-BDC.[31] With the

further increased Fe amount, the charge increases slightly (Figure S4). Thus, the partial substitution of

active Ni(II) by Fe(III) species has significantly adjusted the electronic structure of the resultant

nanomaterials, which is highly important for the manipulations of the electrocatalytic activity.[32]

OER Performance

The OER performances of FexNi1x-BDC/NF electrodes were tested by a standard three-electrode cell in

1.0 M KOH electrolyte at room temperature. Linear sweep voltammetry (LSV) curves were recorded at a

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scan rate of 5.0 mV s  1 with 90% automatic ohmic compensation. As shown in Figure 5a, the anodized

peak that located at about 1.35 V should be assigned to the oxidation of Ni0 to Ni2+ from the NF substrate,

and the one at higher potential is from the transformation of Ni2+ to Ni3+. These oxidation processes mean

the formation of high valence metal species, which can behave as substantially active sites during the OER

process. Herein, to avoid the interference of the oxidation peaks, the overpotential to drive a current density

Accepted Manuscript
50 mA·cm2 (50) is chosen to compare the electrocatalytic activity. The 50 value is 220 mV, 250 mV, 260

mV, 340 mV, and 400 mV for Fe0.89Ni0.11-BDC/NF, Fe0.7Ni0.3-BDC/NF, Fe0.5Ni0.5-BDC/NF,

Fe0.3Ni0.7-BDC/NF and Fe0.11Ni0.89-BDC/NF, respectively. These data indicate that the OER activities of

these bimetallic MOFs are highly feed ratio-dependent (Figure 5b). Apparently, Fe0.89Ni0.11-BDC/NF has

endowed the best OER performance among the five bimetallic electrocatalysts. By contrast, monometallic

Ni-BDC/NF (  50 = 440 mV) shows much inferior OER performance than that of Fe-BDC/NF (  50 = 330

mV), suggesting that the better activity of Fe-BDC/NF than Ni-BDC/NF. Thus, the Fe0.89Ni0.11-BDC/NF

electrocatalyst with two electrocatalytic metals have exhibited cooperate effect on the enhancement of the

OER activity. The electrocatalytic activity of the optimized Fe0.89Ni0.11-BDC/NF are comparable with

diverse NiFe-based MOF nanomaterials with different substrates (NF and NiFe alloy foam), organic

ligands (1,4-bezenedicarboxylate, 2-aminoterephthalate, and 2,5-dihydroxybenzenedicarboxyate) and

morphological structures (crystalline grain, nanoployhedrons, nanocluster, rod-like nano-crystals, and

nanosheet with different thickness, Table S2). Also, the optimized Fe0.89Ni0.11-BDC/NF is much better than

the self-supported NiCo- NiCu-, FeCo-, and FeCoNi-derived MOF electrocatalysts (Table S2).[32]

Tafel slopes of these electrocatalysts were further calculated to deep understand the kinetics of the OER

process. The optimized Fe0.89Ni0.11-BDC/NF has a Tafel slope of 44.8 mV·dec1, dramatically decreased by

65.4 mV·dec  1 and 126.29 mV·dec  1 than those of Fe-BDC/NF and Ni-BDC/NF (Figure 5c). The greatly

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decreased Tafel slope highlights the significant roles of the mixed metals on the kinetics of the OER

process, suggesting that the OER activity over Fe0.89Ni0.11-BDC/NF is kinetically favored. Other four

FexNi1x-BDC/NF samples have owned different Tafel slopes (47.7 mV·dec1 ~ 167.4 mV·dec1, Figure 5c),

implying that the ratio of the two metal components have important roles for the kinetics of the OER.

To gain more insights into the factors governing the high OER performance, the double layer

Accepted Manuscript
capacitance (Cdl) and the electrochemical impedance spectroscopy (EIS) of the seven FexNi1  x-BDC/NF

materials were also measured and compared. As shown in Figure 5d, the calculated Cdl of

Fe0.89Ni0.11-BDC/NF is 4.42 mF·cm  2, only slightly bigger by 0.19 mF·cm  2~1.57 mF·cm  2 than those of

the Fe-BDC/NF (3.88 mF·cm  2), Fe0.7Ni0.3-BDC/NF (4.23 mF·cm  2), Fe0.5Ni0.5-BDC/NF (3.89 mF·cm  2),

Fe0.3Ni0.7-BDC/NF (3.79 mF·cm 2), Fe0.11Ni0.89-BDC/NF (3.66 mF·cm 2) and Ni-BDC/NF (2.85 mF·cm 2),

respectively. These Cdl parameter is proportional to the electrochemical surface areas (ECSA) of the

electrocatalyst. Apparently, the largest Cdl value means that Fe0.89Ni0.11-MOF/NF had a larger active surface

area and more exposed active sites. For EIS test, the Fe0.89Ni0.11-MOF/NF presents the smallest semicircle

in the Nyquist diagrams of these samples (Figure 5e), indicating the lowest charge-transfer resistance at the

interface between the electrocatalysts and electrolyte for comparing the charge transfer resistance. The

enhanced electrocatalytic performance of Fe0.89Ni0.11-BDC/NF can be ascribed to the uniform nonosheet

array and optimized electronic structures, which significantly quicken the reaction kinetics.[29]

The electrocatalytic stability of the optimum Fe0.89Ni0.11-BDC/NF was further assessed by

chronoamperometry and cyclic voltammetry techniques. As illustrated in Figure 5f, the current density of

Fe0.89Ni0.11-BDC/NF at a constant potential of 1.5 V (versus RHE) has displayed negligible decrease over

20 h stability evaluation. The polarization curve after 3000 cycles of CV scans is overlapped well with the

pristine one. Moreover, the sample maintains both the nanosheet array morphology and the pristine phase

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structure after the stability test (Figure S5 and S6). These findings suggest that the active

Fe0.89Ni0.11-BDC/NF electrocatalyst has good long-term durability.

Conclusions

A series of heterometallic NiFe-BDC electrodes were in situ immobilized on the nickel foam through

facile solvothermal method, and used directly as OER electrocatalysts for the structure-activity correlations

Accepted Manuscript
establishment. The feed ratio of the active Fe(III) and Ni(II) components has significantly modulated the

morphological and electronic structures, leading to feed ratio-dependent volcano-type oxygen evolution

activity. The optimized Fe0.89Ni0.11-BDC/NF nanosheet arrays have exhibited the best OER performance in

1.0 M KOH electrolyte with a lower overpotential of 220 mV to drive a current density of 50 mA·cm 2, a

dramatically small Tafel slope of 44.8 mV·dec  1 and durable stability over 20 hour. The excellent OER

performance of the nanosheet array is due significantly to the synergistic effect from two active metals on

both the morphological and electronic structure, which quickens essentially the reaction kinetics.

Experimental Section

Chemicals and Materials: Nickel foam (NF), ferric chloride hexahydrate (FeCl3·6H2O, 99%), nickel

nitrate hexahydrate (Ni(NO3)2·6H2O, 99%), 1,4-bezenedicarboxylic acid (H2BDC, ≥99%), N, N-dimethyl

formamide (DMF) and ethanol (C2H5OH) were purchased from Tianjin Chemical Reagent Factory. All the

initial chemical reagents were of analytical grade and used without further purification. Deionized water

(DIW) purified by a Millipore system was used during the whole experiments.

Treatment of NF: A piece of NF (3.0 cm × 4.0 cm × 0.1 cm) was respectively sonicated in 2 M HCl,

ethanol and DIW for 30 min to remove the surface oxides and organic contaminants. The cleaned NF was

then vacuum dried at 60 °C overnight.

10

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Syntheses of FexNi1-x-BDC/NF: Fe0.89Ni0.11-BDC/NF was hydrothermally prepared according to the

following procedures. A mixture containing FeCl3·6H2O (0.89 mmol, 0.1427 g), Ni(NO3)2·6H2O (0.11

mmol, 0.0349 g) and H2BDC (1.0 mmol, 0.166 g) was dissolved in a mixture of DMF-ethanol-H2O (35.0

mL, vDMF: vethanol: vwater= 12:1:1) with constant stirring for 15 min. The resultant clear solution was

transferred into a 50.0 mL Teflon-lined stainless steel autoclave, together with the well pre-treated NF. The

Accepted Manuscript
autoclave was kept at 125 °C for 12 h and cooled down to room temperature naturally. The NF covered

with dark brown depositor (Fe0.89Ni0.11-BDC/NF) was taken out, washed with DIW and ethanol for several

times, and finally dried at 60 °C for 3 h. The mass loading of Fe0.89Ni0.11-BDC/NF is 2.6 mg·cm  2. Other

hybrid FexNi1x-BDC/NF samples were respectively prepared according to the same procedures by varying

the feed ratios of FeCl3·6H2O and Ni(NO3)2·6H2O, in which the total molar number of the two metal salts

was 1.0 mmol. The feed ratios were nFe :nNi = 1:0 for Fe-BDC/NF, nFe :nNi = 0.7:0.3 for Fe0.7Ni0.3-BDC/NF,

nFe :nNi = 0.5:0.5 for Fe0.5Ni0.5-BDC/NF, nFe :nNi = 0.3:0.7 for Fe0.3Ni0.7-MOF/NF, nFe :nNi = 0.11:0.89 for

Fe0.11Ni0.89-BDC/NF, as well as nFe :nNi = 0:1 for Ni-BDC/NF. The mass loadings for these samples are 1.2

mg·cm2 (Fe-BDC/NF), 4.3 mg·cm2 (Fe0.7Ni0.3-BDC/NF), 3.5 mg·cm2 (Fe0.5Ni0.5-BDC/NF), 2.7mg·cm2

(Fe0.3Ni0.7-MOF/NF) 1.8 mg·cm2 (Fe0.11Ni0.89-BDC/NF), and 3.8 mg·cm2 (Ni-BDC/NF), respectively.

Materials Characterizations: Fourier transform (FT) IR spectra (KBr pellets) were taken on an

Avatar-370 (Nicolet) spectrometer in the range 4000  400 cm−1. X-ray diffraction (XRD) patterns were

carried out on a Bruker D8 advance diffractometer (Bruker, Germany) at 40 kV and 40 mA for a Cu Kα

radiation (λ = 1.5406 Å). The morphology of the samples were observed by a field emission scanning

electron microscopy (FE-SEM, Nova Nano 230, FEI) with an accelerating voltage of 10 kV. Transmission

electron microscopy (TEM), high-resolution transmission microscopy (HR-TEM), selected area electron

diffraction (SAED), high-angle annular dark-field scanning transmission electron microscopy

11

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(HAADF-STEM) and TEM energy-dispersive X-ray spectra (TEM-EDX) test were performed on FEI

Talos F200X and G2 F20 transmission electron microscopy with an accelerating voltage of 200 kV. X-ray

photoelectron spectra (XPS) were obtained using AXIS ULTRADLD X-ray photoelectron spectrometer

(Kratos) with a mono-Al Kα radiation.

Electrochemical Measurements: Electrochemical measurements were carried out on an electrochemical

Accepted Manuscript
working station (CHI 660E, Shanghai) in a standard three-electrode system. As-prepared catalyst was

employed as working electrode, a graphite rod (CHI Inc. China) and Ag/AgCl (KCl saturated) were

respectively used as counter electrode and reference electrode in 1.0 M KOH solution (pH = 13.8). Before

electrochemical characterizations, cyclic voltammogram (CV) measurements were carried out for at least

20 cycles at a scan rate of 100 mV·s  1 to activate and stabilize the working electrode. The OER catalytic

activity was investigated using linear sweep voltammetry (LSV) at a scan rate of 5.0 mV s1 in N2-saturated

1.0 M KOH solution with 90% iR-compensation. The Tafel slope was calculated from the Tafel equation: ƞ

= blog j+a, where η is the overpotential (mV), j is the current density (mA∙cm-2), a is the constant and b is

the Tafel slope. The double layer capacitance was measured by cyclic voltammetry (CV) in the

non-faradaic region of the voltammogram (0.91－1.10 V, 0.96 V) at different scan rates of 40, 60, 80, 100,

120, 140, 160 and 180 mV·s1. Electrochemical impedance spectroscopy (EIS) was measured at 1.56 V (vs.

RHE) over the frequency range from 100 kHz to 0.1 Hz with an AC perturbation of 5.0 mV. The durability

test of the electrocatalyst was carried out using the potentiostatic electrolysis at a fixed potential of 1.5 V

without iR-correction. All the potentials reported herein were calibrated with respect to the reversible

hydrogen electrode (RHE) using the following Nernst equation ERHE= EAg/AgCl + 0.197 + 0.059 × pH unless

stated otherwise. The overpotential () was calculated using the formula,  (V) = E (RHE)  1.23 V.

Acknowledgments

12

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Financial supports were from the NSFC (Grants 21671149, 21571140 and 21531005), the 973 Program

(2014CB845601) and the Program for Innovative Research Team in University of Tianjin (TD13 5074),

which were gratefully thanked.

Conflicts of interest

The authors declare no conflict of interest.

Accepted Manuscript
Keywords: oxygen evolution reaction  metal-organic frameworks  electrocatalyst nanosheet

arrayelectrocatalytic activity
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Figure captions

Figure 1. PXRD patterns of FexNi1x-BDC/NF, Fe-BDC/NF, Ni-BDC/NF, and NF.

Figure 2. SEM images for FexNi1x-BDC/NF with x = 1 (a), x = 0.89 (b), x = 0.7 (c), x = 0.5 (d), x = 0.3 (e)
x = 0.11 (f), and x = 0 (g).

Figure 3. (a) TEM image, (b) HR-TEM image and SAED pattern, (c) HAADF-STEM image and
corresponding EDS elemental mappings for Fe, Ni, O and C elements in Fe0.89Ni0.11-BDC/NF.

Figure 4. High-resolution XPS spectra for Fe 2p (a) and Ni 2p (b) of Fe0.89Ni0.11-BDC/NF.

Figure 5. Electrocatalytic OER performance and stability over FexNi1  x-BDC/NF in 1.0 M KOH solution:

Accepted Manuscript
(a) LSV curves, (b) overpotentials at 50 mA·cm  2 for FexNi1x-BDC/NF, (c) Tafel plots, (d) Plots
of current density versus scan rate, (e) EIS Nyquist plots, and (f) LSV curves for
Fe0.89Ni0.11-BDC/NF before and after 20 h durability test (Inset: i-t curve for Fe0.89Ni0.11-BDC/NF
at an overpotential of 1.5 V).

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Accepted Manuscript
Figure 1.

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Accepted Manuscript
Figure 2.

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Accepted Manuscript
Figure 3.

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Accepted Manuscript
(a) (b)

Figure 4.

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Accepted Manuscript
Figure 5.

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Graphic Abstract

Heterometallic Feed Ratio-Dominated Oxygen Evolution Activity in Self-Supported Metal-Organic

Framework Nanosheet Arrays Electrocatalyst

Rui-Jie Li, Yu-Feng Qi, Qian Wang, Jia-Jun Wang, Zheng-Yu Liu, Xiu-Guang Wang, Xiao-Jun Zhao, and

En-Cui Yang

Accepted Manuscript
Feed ratio of Fe(III) and Ni (II) salts has significantly dominated the morphological and electronic

structures of the nanosheet arrays grown in-situ on the nickel foam, leading to feed ratio-dependent

volcano-type oxygen evolution activity.

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