i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 4 0 8 4 9 e4 0 8 5 9

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Electrodeposited amorphous nickeleiron

phosphide and sulfide derived films for
electrocatalytic oxygen evolution

Chao Wang a,*, Yili Wu a, Zixiang Zhou a, Jinlian Wang a, Shaotong Pei b,
Shuling Liu a,**
a
Department of Chemistry and Chemical Engineering, Shaanxi Collaborative Innovation Center of Industrial
Auxiliary Chemistry & Technology, Key Laboratory of Auxiliary Chemistry and Technology for Chemical Industry,
Ministry of Education, The Youth Innovation Team of Shaanxi Universities, Shaanxi University of Science and
Technology, Xi'an, Shaanxi, 710021, China
b
Hebei Key Laboratory of Distributed Energy Storage and Micro-Grid, North China Electric Power University,
Baoding, Hebei, 071003, China

highlights graphical abstract

One-step electrodeposition of Ni
eFe sulfide and phosphide films
on Ni foam.

The NieFeeS shows the highest
OER activity, with 0.23 V over-
potential at 0.05 A cm2.

The electron interaction tunes the
hydroxyl adsorption energy and
accelerates OER.

Nickel phosphide exhibits higher
intrinsic OER activities than nickel
sulfide.

article info abstract

Article history: The preparation of inexpensive and efficient electrocatalysts for oxygen evolution reaction
Received 2 July 2022 (OER) is crucial in the widespread application of water electrolyzers. A simple one-step
Received in revised form aqueous electrodeposition method is utilized to prepare amorphous nickel-iron sulfide
14 September 2022 (NieFeeS) and phosphide (NieFeeP) films on Ni foam. The deposited films are highly
Accepted 20 September 2022 porous, and can convert to active electrocatalysts for OER. In 1 M KOH, the NieFeeS shows
Available online 12 October 2022 the highest OER activity, and requires only 230 mV overpotential to reach 0.05 A cm2 OER
current densities. The FeeNieS also sustains the 30 h 0.05 A cm2 galvanostatic OER test.
Keywords: Ex-situ characterizations show that sulfur in the FeeNieS is oxidized and leached into the
Electrodeposition solution during OER, and that (oxy)hydroxide layer is formed at the surface. The adsorption
Oxygen evolution reaction energy of the hydroxyl group, an OER intermediate, is tuned by the electron interaction

* Corresponding author.
** Corresponding author.
E-mail addresses: [email protected] (C. Wang), [email protected] (S. Liu).
https://doi.org/10.1016/j.ijhydene.2022.09.200
0360-3199/© 2022 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
40850 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 4 0 8 4 9 e4 0 8 5 9

Phosphide between the Ni and Fe, and the NieFeeS exhibits the optimum hydroxyl group adsorption
Sulfide energy and the most facile OER kinetics. Also, higher intrinsic OER activity is observed for
Nickel the electrodeposited amorphous nickel phosphide-derived film than the amorphous nickel
Iron sulfide-derived film.
© 2022 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

physical/chemical vapor deposition methods [22]. Also, elec-

Introduction trodeposited films feature strong interaction to the substrate,
and the “blocking effect” caused by the polymer binder (to
Hydrogen production by electrolysis of water is regarded as bind the nanoparticle electrocatalysts to the conductive sub-
one of the most promising technologies, in which electricity strate) is avoided [23]. In addition, the morphology, composi-
generated from renewable energy sources can be utilized [1]. tion, and thickness of the deposited film can easily be tuned by
Water electrolysis consists of two half-reactions, the cathodic changing the electrolyte and the electrodeposition method.
hydrogen evolution reaction and the anodic oxygen evolution Nickel-based phosphides and sulfides have been electro-
reaction (OER) [2,3]. The OER (4 OH / H2O þ O2 þ 4 e) re- deposited on TiO2 nanotubes [24], Ni foam [13,25,26], Cu foil
quires consecutive transfer of four electrons, and is kinetically [23,27], Ti sheets [28] and carbon based substrates [29], and the
sluggish. Therefore, active electrocatalysts are required to resulting electrodes are evaluated towards hydrogen evolu-
reduce the overpotential and to accelerate the OER [4,5]. tion reaction and/or OER. The adopted electrodeposition
Nickel-based phosphides and sulfides have recently been methods in most cases are potentiostatic or galvanostatic.
discovered as active pre-catalysts for OER, owing to their high During the electrodeposition, the nucleation and growth rates
conductivity and abundant electrochemically active sites [6,7]. strongly depend on the applied potential. Therefore, unlike
Spontaneous conversion of the surface phosphides and sul- potentiostatic or galvanostatic deposition, the potentiody-
fides to oxides and (oxy)hydroxides is widely observed under namic deposition, e. g. cyclic voltammetry in a wide potential
OER conditions [8], and compared to as-synthesized oxides or range, offers the possibility to prepare sulfide or phosphide
(oxy)hydroxides, this conversion generates oxides and (oxy) film with unique structures, as the rate of nucleation and
hydroxides with higher amount of electrochemically active growth is changed significantly during the deposition. Also, a
sites. Also, the existing steric and electronic interactions be- comparative study on the nickel-based phosphides and sul-
tween the surface oxide or (oxy)hydroxide layer with the core fides that are synthesized using similar electrodeposition
phosphide or sulfide can enhance the OER activity. These method could aid the understanding of the structure-activity
advantages lead to significant efforts on optimizing the OER relationship. Therefore, we electrodeposited nickel-iron
activity of the phosphide and sulfide-based materials. phosphide and sulfide films on Ni foam from aqueous solu-
Incorporation of heteroatoms to the nickel phosphides and tions using cyclic voltammetry at room temperature. These
sulfides is an effective approach to dramatically enhance the films can form active and stable electrocatalysts during OER in
OER activity [6,7,9]. Metallic (e.g. Fe [10], Co [11], Mo [12]) and alkaline solutions.
non-metallic elements (e.g. O [13], N [14]) incorporated nickel
phosphides and sulfides have been synthesized and exhibit
good OER activity. For example, Yuan et al. synthesized Experimental
FeeNi3S2 on FeNi alloy foil, which required 282 mV over-
potential to reach 10 mA cm2 in 1 M KOH [15]. Wang et al. The nickel-iron phosphide and sulfide films were prepared by
obtained Fe0.5CoeP catalyst by phosphidizing MOF precursors, electrodeposition using the three-electrode system with
which can drive 10 mA cm2 at the overpotential of 260 mV in potentiostats (CHI660E and ParSTAT MC). The reference and
1 M KOH [16]. Marquez-Montes et al. reported electrodeposited counter electrodes are a saturated calomel electrode (SCE)
NieSePeO films on Ni foam, with the overpotential of 259 mV and a graphite rod, respectively. Bare Ni foam was soaked in
at 10 mA cm2 in 1 M KOH [13]. The binding energies of the 1.0 M HCl for 10 min under sonication, then washed with
OER intermediates are modulated through the electron ethanol and water. The cleaned Ni foam (1  1 cm2 immersed
interaction between the incorporated heteroatoms with Ni, in the electrolyte) was utilized as the working electrode. The
therefore the OER kinetics is accelerated. Also, the hetero- electrolytes for electrodeposition are listed in Table 1. The
atoms may act as the active site or accelerate the kinetics electrodeposition was conducted using cyclic voltammetry
through bifunction mechanism [17,18]. Besides, morpholog- (CV, 0.3 to (1) VSCE at 5 mV s 1 for 8 cycles). The concen-
ical control on the nickel phosphides and sulfides is an tration of the Ni2þ and Fe3þ in the electrolyte for deposition is
effective route in enhancing the number of electrochemically optimized to give the highest OER activity for the NieFeeS
active sites and in facilitating mass transport [19]. (Fig. S5). After electrodeposition, the working electrodes were
Controlled synthesis of nickel-based phosphides and sul- washed with water and dried in air. The mass of the depos-
fides under mild conditions is highly desirable. Electrodepo- ited film is around 2.5 mg cm2. Carbon fiber paper is also
sition offers a facile route under ambient temperature in used as the substrate to electrodeposit the nickel-iron phos-
synthesizing nickel-based phosphides and sulfides, in com- phide and sulfide films, and the deposited films were used for
parison to the calcination [2,20], solvothermal [21], or electrocatalytic methanol oxidation reaction (MOR), and for
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Phosphides are formed according to Eqs. (3) and (4) [25].

Table 1 e Solutions used for electrodeposition.
The P can diffuse into the elemental metal atoms to generate
Electrode Ni(NO3)2 Fe(NO3)3 Na2S2O3 NaH2PO2 phosphides [32].
NieFeeS 0.025 M 0.025 M 0.1 M e
NieS 0.05 M e 0.1 M e Mnþ þ n e / M (3)
FeeS e 0.05 M 0.1 M e
NieFeeP 0.025 M 0.025 M e 0.25 M
H2PO2 þ 2 Hþ þ e / P þ 2 H2O (4)
NieP 0.05 M e e 0.25 M
FeeP e 0.05 M e 0.25 M
The nickel and iron are similar in atomic radius and elec-
tronegativity, and bimetallic phosphides and sulfides are
formed by electrodeposition [30,33].
ICP-AES to acquire the ratio of elements on the deposited
The surface morphologies of the NieFeeS (Fig. 1a and b)
films (Table S1).
and NieFeeP (Fig. 1c and d) are characterized by scanning
Electrocatalytic OER activities were measured in 1 M KOH
electron microscopy (SEM). The NieFeeS constitutes of
(pH ¼ 13.9) with SCE as the reference, and a cleaned graphite
nanoplates with 130 nm in side length and 25 nm in thickness.
rod as the counter. The potential is reported against reversible
The nanoplates are interconnected to form a three-
hydrogen electrode unless otherwise stated. The linear sweep
dimensional porous structure. The as-deposited NieFeeP
voltammograms (LSV) and galvanostatic results are iR-cor-
consists of nanoplates with side length at 100 nm, and 20 nm
rected with solution resistance acquired by electrochemical
in thickness. The nanoplates are assembled into flower-like
impedance spectroscopy (EIS). Chemicals and in-
shape, with abundant pores.
strumentations are provided in the supporting information.
Fig. 2a and b display the transmission electron micrograph
(TEM) and the high-resolution TEM (HRTEM), respectively, of
the NieFeeS powder exfoliated from the deposited electrode.
Results and discussion
The NieFeeS is composed of aggregated nanosheets. Lattice
fringes are observed in Fig. 2b, which indicates that the
The nickel-iron sulfide and phosphide films were prepared by
NieFeeS constitutes crystalline regions. However, the crys-
electrodeposition on Ni foam (Scheme 1), with Ni2þ and Fe3þ
talline regions are small, and NieFeeS exhibits long-range
as metal sources, and with S2O32 and HPO2 as sulfur and
disordered structures. The interlayer lattice spacing is
phosphorus sources, respectively. Under reductive potentials,
measured to be 0.182 nm, which corresponds to the (113)
sulfides are formed according to Eqs. (1) and (2), where M
plane of the Ni3S2 phase (JCPDS card no. 44e1418) [34]. The
represents Ni or Fe [30,31].
XRD pattern (Fig. S1) of the NieFeeS shows only diffraction
peaks of the Ni foam substrate, which suggests that the
Mnþ þ x S2O32 þ n e / M(S2O3)x2x (1)
crystalline sulfides are small and lack long-range order,
consistent with the HRTEM results. The high-angle annular
M(S2O3)x2x þ 2x Hþ / MSx þ x H2SO3 (2)
dark filed (HAADF) image and elemental mapping of the

Scheme 1 e Illustration of electrodeposition of nickel-iron sulfide and phosphide films on nickel foam.
40852 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 4 0 8 4 9 e4 0 8 5 9

Fig. 1 e (a, b) SEM images of the NieFeeS; (c, d) SEM images of the NieFeeP.

NieFeeS in Fig. 2cef show that Ni, Fe, and S are homoge- 861.2 eV and 879.3 eV. These binding energies correspond to
neously distributed. the Ni2þ species [35]. In comparison, the NieS also exhibits
Fig. 3 show the XPS spectra of the electrodeposited films. peaks that can be assigned to Ni2þ, but the Ni 2p3/2 peak shifts
The deconvoluted high-resolution Ni 2p spectra of NieFeeS to lower binding energies. This suggests decreased electron
and NieS are displayed in Fig. 3a. For NieFeeS, the spin-orbit densities at the Ni2þ sites in the NieFeeS. Fig. 3b displays the
doublets appear at 855.4 eV (Ni 2p3/2) and 873.0 eV (Ni 2p1/2) deconvoluted high-resolution XPS spectra of Fe 2p region of
accompanied with their shake-up satellite peaks located at the NieFeeS and FeeS. The Fe 2p3/2 peak can be deconvoluted

Fig. 2 e (a) TEM image and (b) HRTEM image of the NieFeeS, (cef) HAADF image and the corresponding EDS element
mapping images of Ni, Fe, and S.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 4 0 8 4 9 e4 0 8 5 9 40853

Fig. 3 e Deconvoluted high-resolution XPS spectra of the electrodeposited films. (a) Ni 2p, (b) Fe 2p and (c) S 2p regions of the
NieFeeS, NieS, and FeeS; (d) Ni 2p, (e) Fe 2p and (f) P 2p regions of the NieFeeP, NieP, and FeeP.

into two peaks at 706.4 eV and 712.1 eV, which correspond to NieFeeS. The NieFeeS exhibits the lowest Tafel slope value
the Fe2þ and Fe3þ, respectively [35,36]. The deconvoluted high- (56 mV dec1) as shown in Fig. 4c, which indicates that the OER
resolution S 2p spectra in Fig. 3c show that peaks at 161.5 eV (S kinetics is the most facile compared to the NieS (152 mV
2p3/2) and 163.6 eV (S 2p1/2) are originated from the S2, and the dec1) and FeeS (96 mV dec1). The double-layer capacitance
peak at 167.9 eV is originated from the SeO bond due to the values (Cdl) of these electrodes are estimated by collecting the
surface oxidation [37e39]. Therefore, the NieS, FeeS, and CV in the non-faradaic region at various scan rates (Fig.
NieFeeS are sulfides in nature. Fig. 3def display the decon- S7aec). The NieS exhibits the highest Cdl value at
voluted high-resolution XPS spectra of the NieFeeP, NieP, and 14.2 mF cm2 (Fig. 4d), followed by NieFeeS (8 mF cm2) and
FeeP. From the Ni 2p spectra, Ni exists in the form of Ni2þ in FeeS (2.1 mF cm2). The Cdl is proportional to the electro-
both NieFeeP and NieP [25,40,41]. Fe exists as FeeP bond chemically active surface area (ECSA) of the film. However, the
(707.4 eV for Fe 2p3/2) and as Fe3þ (712.3 eV for Fe 2p3/2) [42,43]. factors to covert Cdl to ECSA for sulfides and phosphides are
The P 2p peaks show only bonds originated from PeO species yet undefined [6,49]. Therefore, the OER current is normalized
(133.2 eV) [44]. It is often observed that phosphides are to Cdl to investigate the intrinsic activities of these electrodes
oxidized at the surface [45,46]. Generally, electrodeposited (Fig. 4e). The NieFeeS displays the highest Cdl-normalized
phosphides with high specific surface area tend to be oxidized, current densities, while the NieS exhibits the lowest. This
which leads to the disappearance of the P-M bond in XPS indicates that the OER intrinsic activity is the highest for the
[25,44]. However, considering the strongly reductive environ- NieFeeS. Fig. 4f displays the 500 s 0.05 A cm2 galvanostatic
ment during electrodeposition, and the high phosphorus to test results of NieFeeS, NieS, and FeeS. The overpotential for
metal peak from EDX (Fig. S10), we conclude that metal NieFeeS is the lowest, which suggests its best OER activity.
phosphides are formed in case of NieFeeP, NieP, and FeeP. The electrochemical parameters for these electrodes are
The LSV of NieFeeS, NieS and FeeS in 1 M KOH are shown summarized in Table 2.
in Fig. 4a. The overpotential (h) to reach 0.05 A cm2 OER The LSV of NieFeeP, NieP and FeeP in 1 M KOH are shown
current densities for the NieFeeS is only 230 mV, significantly in Fig. 5a. NieFeeP shows the lowest overpotential to reach
lower than the FeeS (309 mV) and NieS (403 mV). The CV of 0.05 mA cm2 compared to NieP and FeeP. The CV of NieP
NieFeeS (Fig. 4b) displays the Ni2þ/3þ oxidation (Ni(OH)2- (Fig. 5b) shows Ni2þ/3þ redox peaks at 1.39 V (anodic) and
þ OH / Ni(O)OH þ H2O þ e) [47] peak at 1.39 V, with the 1.30 V (cathodic). Only Ni2þ/3þ reduction peak of NieFeeP is
corresponding reduction peak at 1.31 V. For NieS, the Ni2þ/3þ visible in CV, probably caused by the anodic shift induced by
redox peaks emerge at more negative potentials than those in Fe that overlaps the OER current [33]. The Tafel slope (Fig. 5c)
NieFeeS. This suggests that the incorporation of Fe decreases for the NieFeeP is the lowest, which suggests that the OER
the electron density at Ni2þ sites [33,48], consistent with the kinetics is the most facile in comparison to NieP and FeeP. In
shift to higher binding energies of the Ni 2p peaks in XPS of Fig. 5d, the NieP exhibits the Cdl at 9.8 mF cm2, higher than
40854 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 4 0 8 4 9 e4 0 8 5 9

Fig. 4 e (a) Anodic LSV at 3 mV s¡ 1, (b) CV at 5 mV s¡ 1, (c) the Tafel plots, (d) plots to calculate Cdl values, (e) the LSV with I
normalized by Cdl, and (f) the galvanostatic results at 0.05 A cm¡ 2 of the NieFeeS, NieS, and FeeS in 1 M KOH.

FeeP (3.4 mF cm2) and NieFeeP (2.7 mF cm2). After and FeeP films electrodeposited on carbon fiber paper
normalizing the LSV current to Cdl (Fig. 5e), the NieFeeP (Fig. S8). As bare Ni foam is active towards MOR, we used
shows the highest intrinsic OER activity among the carbon substrate to avoid the interference. The MOR onset
phosphide-derived films. Fig. 5f displays the results of the potentials (E Onset MOR) are summarized in Table 2. The
500 s 0.05 A cm2 galvanostatic test. Consistent with the LSV, experimentally determined MOR onset potential is related to
NieFeeP exhibits the lowest stabilized overpotential, indica- the adsorption energy of hydroxyl group (DG*OH) on the elec-
tive of its best OER activity. trochemically active sites [51]. Therefore, the DG*OH for the
The EIS Nyquist plots of these electrodes are shown in NieFeeS, NieFeeP, NieS, NieP, FeeS, and FeeP films are
Fig. 6a and b. All electrodes show semicircular shape, which is determined to be 1.370 eV, 1.403 eV, 1.335 eV, 1.348 eV,
consistent with the reported EIS Nyquist plots of phosphide 1.621 eV, and 1.587 eV, respectively. Based on the model pro-
and sulfide materials in the OER potential [40,50]. The equiv- posed by Bin Liu, the optimum OER electrocatalysts should
alent circuit used for fitting is shown at the inset of Fig. 6a. The have the DG*OH at 1.371 eV [51,52]. Therefore, the NieFeeS
charge transfer resistances (Rct) acquired from the fitting are shows the closest to optimum DG*OH. The DG*OH for the
summarized in Table 2. The NieFeeS and NieFeeP show NieFeeP is slightly higher than the optimum. According to
approximately the same Rct, and are the lowest in comparison XPS, the surface ratios of Ni to Fe for the NieFeeS (1.66) and
to other electrodes, which suggests their most facile kinetics NieFeeP (1.70) are close, therefore, the difference between the
of OER. In contrast, NieS exhibits higher Rct than NieP, FeeS, DG*OH for the NieFeeS and NieFeeP is probably originated
and NieS. from the electron interaction induced by the core sulfide/
We further probed the methanol oxidation reaction (MOR) phosphide and surface (oxy)hydroxide layer [7,53]. In contrast,
onset potential of the NieFeeS, NieFeeP, NieS, NieP, FeeS, the NieS and NieP show lower DG*OH, suggesting that the

Table 2 e Summary of the electrochemical parameters of the electrodes.

hOnset OER/mV h0.05 A cm-2 Tafel Cdl/mF cm2 Rct/U a
E Onset MOR
/mV slope/mV dec1 /V
NieFeeS 192 230 56 8 0.51 1.370
NieS 259 403 152 14.2 3.98 1.335
FeeS 194 309 96 2.1 0.94 1.621
NieFeeP 210 267 63 2.7 0.56 1.403
NieP 254 410 168 9.8 3.20 1.348
FeeP 215 291 88 3.4 0.73 1.587
a
Films are electrodeposited on carbon fiber paper.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 4 0 8 4 9 e4 0 8 5 9 40855

Fig. 5 e (a) Anodic LSV at 3 mV s¡ 1, (b) CV at 5 mV s¡ 1, (c) the Tafel plots, (d) plots to calculate Cdl values, (e) the LSV with I
normalized by Cdl, and (f) the galvanostatic results at 0.05 A cm¡ 2 of the NieFeeP, NieP, and FeeP in 1 M KOH.

surface hydroxyl groups bind too strong to the active sites, NiOO / Ni þ O2 þ e (7)
and the formation of adsorbed peroxyl group is rate-limiting
[51]. Under the OER conditions, the surface of the phos- Ni þ OH / NiOH þ e (8)
phides or sulfides are oxidized, with the anions (phosphate
and sulfate) leached into solution, and conversion to metal NiOH þ OH / NiO þ H2O þ e (9)
oxyhydroxides is observe by various in-situ studies [54,55].
Also, the recently updated Pourbaix diagram for Ni suggests The existence of NiOO species are observed by in-situ
that the thermodynamic stable phase during at OER in alka- Raman spectroscopy during OER for the Ni oxide and NiFe
line is NiO [56]. Therefore, we adopt the following OER oxide catalysts [58,59]. The 120 mV dec1 Tafel slope values
mechanism proposed by Banks et al. for the nickel oxide suggests that the first proton-coupled electron transfer step
catalysts as shown in Eqs. 5-7 [57]. (Eq. (5)) is rate-limiting. In our case, for NieS and NieP, the
higher than 120 mV dec1 Tafel slope values are not-typical,
NiO þ OH / NiOOH þ e (5) and are possibly caused by other processes coupled with
OER, for example the surface restructuring [60]. For the
NiOOH þ OH / NiOO þ H2O (6) NieFeeS that has the optimum DG*OH, the Tafel slope is at
56 mV dec1. This suggests that the chemical step following

Fig. 6 e (a) Nyquist plots (dots) and the fitting curves (line) of NieFeeS, NieS, and FeeS in 1 M KOH at 1.46 V; (b) Nyquist plots
(dots) and the fitting curves (line) of NieFeeP, NieP, and FeeP in 1 M KOH at 1.50 V.
40856 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 4 0 8 4 9 e4 0 8 5 9

the initial electrochemical step (Eq. (6)) is rate-limiting [61,62]. Cdl-normalized current densities, Fig. S6b) for NieP is higher
Therefore, incorporation of Fe optimizes the adsorption pro- than NieS. Also, the DG*OH of the NieP is closer to optimum,
cess of hydroxyl groups on the surface of NieP and NieS, and and the Rct for NieP is lower than NieS. These indicate that the
accelerates the OER rates. The critical role of Fe in the OER is nickel phosphides are better pre-catalysts than sulfides for the
identified by various in-situ studies [63] and by calculation OER. The Ni2þ/3þ oxidation peak potential of NieP (1.39 V) is
[64,65] as facilitating the formation of high-valent Ni species higher than NieS (1.36 V), which indicates electron interaction
and the OH attack to form peroxyl intermediate [66]. Alter- exists that leads to decreased electron densities at Ni2þ sites
natively, the incorporated Fe could also serve as the active site for the NieP than NieS. As both nickel phosphides and sulfides
[59,67], or follow the bifunction mechanism to catalyze OER would undergo surface restructuring to form (oxy)hydroxides
[68]. For the FeeP and FeeS, hydroxyl groups bind weaker than during OER in alkaline, it is possible that better electron con-
optimum to the active site, and the rate-limiting step would be ductivity of phosphide core and appropriate electron interac-
the adsorption of hydroxyl group or the conversion of adsor- tion between the core and the surface (oxy)hydroxide layer
bed hydroxyl groups to oxo groups [61,69]. Note that this Tafel accounts for the higher intrinsic activity for phosphides than
analysis is tentative, and further in-situ studies combined with sulfides.
calculation and isotope labeling could aid the identification of The long-term 0.05 A cm2 galvanostatic test was carried
the possible OER mechanistic pathways for OER [57,70]. out for 30 h using NieFeeS, with the NieS and FeeS as control.
The electrocatalytic activity of NieP and NieS is then Fig. 7a shows the results. All electrodes sustained the long-
compared. Though the NieS exhibits a lower overpotential term galvanostatic test, and the NieFeeS exhibits the lowest
to reach 0.05 mA cm2, the intrinsic OER activity (from the overpotential. A slight increase of 17 mV in the overpotential

Fig. 7 e (a) Long-term 0.05 A cm¡ 2 galvanostatic results of the NieFeeS, NieS, and FeeS in 1 M KOH; (b) LSV before and after
the galvanostatic test of the NieFeeS; (c) Nyquist plots before and after the galvanostatic test of the NieFeeS at 1.46 V in 1 M
KOH; High-resolution XPS spectra of (d) Ni 2p, (e) Fe 2p, (f) S 2p,and (g) O 1s region of the NieFeeS after the long-term
galvanostatic test; (h) SEM image and (i) EDX spectrum of the NieFeeS after the long-term galvanostatic test.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 4 0 8 4 9 e4 0 8 5 9 40857

is observed during the 30 h. Fig. 7b compares LSV before and intrinsic activity than NieS, which suggests that amorphous
after the 30 h galvanostatic test of the NieFeeS. Decrease in nickel phosphide is a better pre-catalyst than nickel sulfide
OER current is observed after the long-term test, consistent for OER. This study offers a facile route to electrodeposit
with the rise in overpotential during the long-term test. Also, amorphous nickel-iron phosphides and sulfides and com-
the shape for the Ni2þ/3þ oxidation peak changes, which in- pares the OER activity of these electrodes. The NieFeeS
dicates that the surface restructuring of the NieFeeS hap- shows close to optimum binding energy for the OER inter-
pens. Fig. 7c compares the EIS spectra of the NieFeeS before mediate hydroxyl group. Further improvement on the OER
and after the long-term galvanostatic test. The solution activities can be achieved through tuning the electron
resistance remains the same, while the Rct increases by 0.1 U structure of the active sites and developing catalysts that
after the galvanostatic test. Similar increase in the Rct has follow other OER mechanistic pathways, like involvement of
been observed for nickel phosphide-based materials towards lattice oxygen or dual-site mechanism.
OER, and is proposed to originate from the surface trans-
formation that leads to hindered kinetic process [33,40].
Deconvoluted high-resolution XPS spectra of the NieFeeS Declaration of competing interest
after the 30 h 0.05 mA cm2 galvanostatic OER are shown in
Fig. 7deg. The surface Ni exists as Ni2þ, and Fe exists as Fe3þ, The authors declare that they have no known competing
respectively. The intensity of the S 2p peaks decreased financial interests or personal relationships that could have
significantly, which suggests that the sulfur at the surface is appeared to influence the work reported in this paper.
oxidized during OER, and is leached into solution. The
deconvoluted high-resolution O 1s spectra show peaks that
can be assigned to oxide (MO), hydroxide (MOH), and
adsorbed water or SeO bonds, respectively [41]. The presence Acknowledgments
of metal oxide and hydroxide indicates that the surface layer
of the sulfides is transformed to (oxy)hydroxides, with sulfate Authors thank the funding from the Shaanxi University of
ions adsorbed at the surface. The remaining sulfate ions at the Science and Technology Scientific Research Foundation for
surface can serve as the proton acceptor that facilitates the the PhD (No. 2019QNBJ-05), Natural Science Foundation of
deprotonation process of peroxyl intermediate and accelerate Shaanxi Province of China (No. 2021JQ-540 and 2018JM2036),
the OER kinetics [71]. Fig. 7h shows the SEM images of the and China Postdoctoral Science Foundation (No.
NieFeeS after the 30 h 0.05 A cm2 galvanostatic test. The film 2020M683666XB). This work is also supported by the Open
maintained its structure, while small pores formed at the Foundation of Key Laboratory of Auxiliary Chemistry and
surface of the films, which is originated from the sulfide Technology for Chemical Industry, Ministry of Education,
oxidation and the dissolution of sulfate. Fig. 7i shows the EDX Shaanxi University of Science and Technology (No. KFKT2022-
after long-term galvanostatic test. Ni, Fe, and S all exist in the 12), and Shaanxi Collaborative Innovation Center of Industrial
bulk, while the atomic ratio of total metal to S increased from Auxiliary Chemistry and Technology, Shaanxi University of
1.97 before OER (Fig. S9) to 5.37 after OER. This indicates the Science and Technology (No. KFKT2022-12), China.
oxidation of sulfide and leaching of sulfate happen, but there
is still sulfide remaining in the bulk, in contrast to some of the
reports on metal sulfide nanoparticles, where complete Appendix A. Supplementary data
leaching of sulfur is observed after OER [72]. Our observation is
consistent with the reported metal sulfides, where conversion Supplementary data to this article can be found online at
of sulfide to (oxy)hydroxide is observed during the long-term https://doi.org/10.1016/j.ijhydene.2022.09.200.
OER [6,73]. Therefore, metal (oxy)hydroxide, rather than sul-
fur, is the real active site towards OER [37,74]. In summary, the
electrodeposited NieFeeS film on Ni foam can convert to references
active and stable OER catalysts in alkaline solution.

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