Journal of Alloys and Compounds 918 (2022) 165802

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Journal of Alloys and Compounds

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

Mo-doped NiCoP nanowire array grown in situ on Ni foam as a high-

performance bifunctional electrocatalyst for overall water splitting ]]
]]]]]]
]]

Yifan Zhao 1, Ji Chen 1, Shuwen Zhao 1, Weijie Zhou, Ruijie Dai, Xuan Zhao, Zhengang Chen,
⁎ ⁎ ⁎
Tao Sun , Hua Zhang , Anran Chen
School of Materials and Energy, Yunnan University, Kunming 650091, PR China

a r t i cl e i nfo a bstr ac t

Article history: The development and application of durable and efficient non-precious metal-based electrocatalysts are
Received 9 April 2022 particularly crucial for hydrogen production using overall water-splitting technology. Herein, a simple
Received in revised form 17 May 2022 method was employed to synthesize Mo-doped NiCoP nanowires on a metallic 3D Ni foam (Mo-NiCoP/NF)
Accepted 6 June 2022
for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). This long-term stable Mo-
Available online 10 June 2022
NiCoP/NF catalyst demonstrated comparatively low overpotentials and excellent dual-functional catalytic
performances. The overpotentials for the HER and OER were 64 and 262 mV, respectively, to actuate a
Keywords:
Mo-NiCoP current density of 10 mA cm−2 in an alkaline environment (1 M KOH). Meanwhile, when this electrocatalyst
Electrocatalyst was utilized for overall water splitting, a cell voltage of 1.56 V could supply a current density of 10 mA cm−2
Hydrogen evolution for at least 50 h with a negligible performance drop. This work provides an advanced approach to devel­
Oxygen evolution oping non-noble metal phosphide nanostructures as monolithic dual-functional electrocatalysts for overall
Overall water splitting alkaline water splitting.
© 2022 Elsevier B.V. All rights reserved.

1. Introduction [10–12]. To overcome these limitations, numerous highly efficient,

durable, and inexpensive non-noble metal-based catalysts have been
The energy crisis resulting from pollution and shortage of non- developed, including transition metal selenides (TMSe) [13], sulfides
renewable fossil fuels generates an urgent demand for humans to (TMDs) [14,15], carbides (TMCs) [16], nitrides (TMNs) [17,18], and
develop renewable energy techniques [1–3]. At present, hydrogen phosphides (TMPs) [19–21]. TMPs exhibit metal-like properties, such
energy is the most potential renewable energy, which has the ad­ as high mechanical strength, good electrical conductivity, and che­
vantages of zero pollution and high efficiency [4–6]. In recent dec­ mical stability. Therefore, TMPs are particularly suitable for replacing
ades, electrocatalytic water splitting has become a critical process in noble metals to construct HER and OER electrocatalysts [22,23].
hydrogen production [7,8]. A general electrocatalytic water-splitting The electrocatalytic activity also depends on the active site and
system consists of a power source, anode, cathode, and electrolyte. local environment of the electrode [24,25]. Compared to traditional
Driven by electrical energy, the oxygen evolution reaction (OER) electrodes, which use polymer binders to adhere powder electro­
occurs at the anode to generate oxygen, and the hydrogen evolution catalysts to the conducting surface, self-supporting electrodes are
reaction (HER) occurs at the cathode to generate hydrogen. These easy to operate. More importantly, the catalyst on a self-supporting
two reactions often require a high overpotential to overcome slow electrode is in direct contact with the electrolyte, which can increase
multi-electron transfer kinetics, which leads to energy waste [9]. the conductivity and accelerate electron transfer. Additionally, the
Therefore, catalysis is crucial to minimize the overpotentials for OER self-supporting electrode substrate is not only more favorable for
and HER and enhance H2 and O2 production. Currently, the best- active site attachment, but also the 3D interconnected network
performed HER and OER catalysts are Pt and Ru (Ir)-based materials, structure of the self-supporting electrode substrate is more favorable
respectively, but their resources are scarce, and their cost is high for the release of hydrogen and oxygen. [26,27]. The common sub­
strates for self-supporting TMPs include carbon cloth (CC), Ni foam
(NF), and Cu foam (CF). Recent studies have shown that doping
⁎
Corresponding authors.
elements in TMPs can improve the intrinsic activity of catalysts and
E-mail addresses: [email protected] (T. Sun), some doping elements can tune the electronic structure inside the
[email protected] (H. Zhang), [email protected] (A. Chen). catalysts, resulting in a significant change in the physicochemical
1
These authors contributed equally.

https://doi.org/10.1016/j.jallcom.2022.165802
0925-8388/© 2022 Elsevier B.V. All rights reserved.
Y. Zhao, J. Chen, S. Zhao et al. Journal of Alloys and Compounds 918 (2022) 165802

The microstructure of Mo-NiCoP/NF was studied using trans­

mission electron microscopy (TEM). It plain demonstrated that the
nanowires were composed by the cumulation of innumerable na­
noparticles, and the diameter of a single nanowire was approxi­
mately 40.0 nm, from the TEM images of Fig. 1c and e. The Fourier-
transformed lattice fringes in the high-resolution TEM (HRTEM)
images showed that the lattice spacing was deduced to be 0.220 nm,
ascribed to the (111) lattice plane of the highly crystalline NiCoP
(Fig. 1d and e) [36]. The selected area electron diffraction (SAED)
pattern in Fig. 1f revealed diffuse diffraction rings, indicating that
Mo-NiCoP/NF was in an amorphous state. Furthermore, high-angle
annular dark-field scanning electron microscopy (HAADF-STEM) and
energy dispersive X-ray spectroscopy (EDS) elemental mapping
showed that Mo, Ni, Co, and P were equably spread all over the Mo-
NiCoP/NF nanowire. These results confirmed that Mo-NiCoP/NF
electrocatalysts were successfully prepared via hydrothermal treat­
ment and subsequent phosphorization.
Scheme 1. Flow diagram of the preparation of Mo-NiCoP/NF.
The crystalline phase of the prepared catalyst was analysed uti­
lizing X-ray diffraction (XRD). The XRD pattern of Mo-NiCoP/NF
properties of catalysts [28,29]. For example, Guan et al. [30]found (Fig. 2a) demonstrates a few definitive diffraction peaks, which
that doping CoP with Mo based on CC could alter the electronic highly agreed with NiCoP (PDF#71–2336). Among them, the peaks at
structure inside CoP and reduce the free energy of hydrogen ad­ 40.9°, 44.9°, 47.5°, and 54.4° were in line with the (111), (201), (210),
sorption on the surface, thereby improving the electrocatalytic hy­ and (300) crystal planes of NiCoP, respectively [36]. The XRD peaks
drogen evolution activity. Du et al. [31]used Ti mesh (TM) as a of the (111), (200), and (220) planes of NF (PDF#04–0850) were
substrate and demonstrated that Al doping effectively modified the located at 44.6°, 52.0°, and 76.6°, respectively, which correspond
electronic environment of Ni2P, thereby promoting its HER electro­ exactly to the one in the figure. Next, to understand the surface
catalytic performance. Zhang et al. [32]reported an Mn-doped Ni2P chemical valence state of the final product, X-ray photoelectron
nanosheet array on an NF substrate that exhibited excellent catalytic spectroscopy (XPS) of Mo-NiCoP/NF and NiCoP/NF were performed.
activity in alkaline electrolytes. The full XPS spectra in Fig. 2b evidences the presence of the con­
Inspired by these previous studies, herein, we developed Mo- stituent elements. The Ni 2p spectrum of Mo-NiCoP/NF could be
doped NiCoP nanowire arrays on a smooth surface of NF via a two- deconvoluted to six peaks at 851.5, 855.3, 860.4, 868.8, 873.3 and
step method. The prepared Mo-NiCoP/NF catalyst possessed bi­ 878.7 eV (Fig. 2c). The peaks at 851.5 and 868.8 eV of Ni 2p3/2 and Ni
functional catalytic activity for HER and OER in an alkaline en­ 2p1/2 were from Ni-P (Ni0); the peaks at 855.3 and 873.3 eV were
vironment. This study demonstrates that elemental doping is an assigned to Ni2+, and the homologous satellite peaks at 860.4 and
effective strategy for constructing bifunctional phosphide catalysts. 878.7 eV may be derived from surface oxidation [37,38]. In the Co 2p
spectrum of Mo-NiCoP/NF (Fig. 2d), two peaks at 776.8 and 791.8 eV
2. Results and discussion were allocated to Co 2p3/2 and Co 2p1/2 in Co-P (Co0), respectively.
The peaks at 780.3 and 796.1 eV were accredited to the Co-O states
The diagram of the production recipe of the Mo-NiCoP/NF cata­ (Co2+/3+), and the homologous satellite peaks at 784.7 and 800.4 eV
lyst is shown in Scheme 1. First, a mixture of Mo, Ni, and Co pre­ were caused by the inevitable surface oxidation in the air [38–40].
cursors was subject to a hydrothermal process to obtain the Fig. 2e revealed the P 2p spectrum of Mo-NiCoP/NF, where the two
nanowire structure on the NF surface. The nanowires were then peaks at 128.3 and 129.2 eV were in line with P 2p3/2 and P 2p1/2,
converted into Mo-NiCoP/NF by phosphorization at 300 °C under an respectively, and the occurrence of surface oxidation caused the
N2 atmosphere. An optical photograph of the Mo-NiCoP/NF catalyst peak at 132.8 eV to change to P-O [39,41]. Compared with NiCoP/NF,
is shown in Fig. S1, and a color change was observed during the the peaks of Ni 2p, Co 2p, and P 2p in Mo-NiCoP/NF were sig­
formation of this catalyst. For the sake of clarity explore the real nificantly shifted to lower binding energy, indicating that the elec­
situation of the prepared catalysts, we used a scanning electron tronic properties of NiCoP were altered after doping Mo, which may
microscope (SEM) to peek into their microscopic semblance. The conduce to the aggrandizement of electrocatalytic performance [42].
bare NF surface was smooth with no impurities (Fig. S2a and b). The Next, the Mo 3d spectrum of Mo-NiCoP/NF was analyzed (Fig. 2f).
rapid movement of charges and rapid discharge of air bubbles are The peaks at 231.4 eV and 234.5 eV were in line with Mo 3d5/2 and
significant advantages of 3D interconnected metal frameworks Mo 3d3/2, respectively, which can be subdivided into Mo4+ (226.1 and
[33,34]. The surface of the NF was completely covered by nanowires 231.4 eV), Mo5+ (229.2 and 233.5 eV) and Mo6+ (230.5 and 234.6 eV)
after the hydrothermal reaction (Fig. S2c and d). Notably, the na­ [43,44]. Above XRD and XPS results agreed well with the morpho­
nowire structures were well maintained after the phosphorization logical characterization, confirming that Mo-NiCoP/NF electro­
under an N2 atmosphere (Fig. 1a and b). By adjusting the atomic ratio catalyst was successfully prepared.
between Mo and Co from 1:10, 1:20, 1:30–1:50, various Mo-NiCoP/ The HER capabilities of the as-prepared Mo-NiCoP/NF and re­
NF nanowires were synthesized (Fig. S3). Their crystallinity and ference catalysts were evaluated after 90% iR compensation using a
morphology were similar (Fig. 1a and b). However, the nanowire regular three-electrode system in an alkaline environment. Fig. 3a
structures of NiCoP/NF without any Mo doping were very hetero­ indicated the linear sweep voltammetry (LSV) curves of various
geneous (Fig. S2e and f), indicating that proper Mo atomic doping is electrocatalysts at a scan rate of 5 mV−1 in 1 M KOH electrolyte [45].
the key factor for nanowire growth. Meanwhile, a number of pores Sure enough, Mo-NiCoP/NF exhibited outstanding HER performance
and gaps were observed between the nanowires, which supplied at the current densities of 10 mA cm−2 and 100 mA cm−2, which could
sufficient sites for reactants and promoted the release of oxygen/ be driven with only 64 mV and 160 mV of overpotential, respectively.
hydrogen bubbles. This unique structure was expected to expedite This overpotential was significantly better than NiCoP/NF (109 and
the electron transfer rate and improve the catalytic efficiency to a 189 mV), Mo-NiCo/NF (229 and 335 mV), NiCo/NF (260 and 365 mV),
certain extent [35]. and NF (Fig. 3a and b). As shown in Fig. 3c, Mo-NiCoP/NF possessed a

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Y. Zhao, J. Chen, S. Zhao et al. Journal of Alloys and Compounds 918 (2022) 165802

Fig. 1. Morphology and structure characterization of Mo-NiCoP/NF. (a and b) SEM images, (c) TEM image, (d) HRTEM image of a single nanowire, (e) SAED pattern of partial area in
(d), (f) SAED pattern, and (g) HAADF-STEM and EDS elemental mapping.

Tafel slope as low as 57.3 mV dec−1, which was close to 20% Pt/C evaluate the electrochemically active surface area (ECSA) of each
(45.8 mV dec−1) and significantly lower than NiCoP/NF, Mo-NiCo/NF, electrocatalyst, cyclic voltammetry (CV) curves were measured at
NiCo/NF, and NF. The Tafel slopes for these four samples were 82.3, the same voltage interval at different scan rates. As shown in Fig. 3e
89.0, 100.0, and 141.3 mV dec−1, respectively. Thus, under alkaline and S6, the mean value of the difference between the cathode and
conditions, the Mo-NiCoP/NF catalyst proceeds with the rate-de­ anode currents for these CVs followed a linear relationship with the
termining step of hydrogen absorption via the Volmer-Heyrovsky scan rate [49,50]. Mo-NiCoP/NF had the highest double-layer capa­
mechanism (H2O + M + e- → OH- + M – Had and H2O + M – Had + e- citance (Cdl) value (33.66 mF cm−2) compared to NiCoP/NF (30.37 mF
→ OH- + M + H2) [46,47]. By comparing the Tafel slopes of Mo-NiCoP/ cm−2), Mo-NiCo/NF (1.41 mF cm−2) and NiCo/NF (1.14 mF cm−2). This
NF and Mo-NiCo/NF, the values after phosphating decreased sig­ showed that abundant active sites were generated after the phos­
nificantly, indicating that phosphating could accelerate the dis­ phating treatment, thereby enhancing the HER activity. In practical
sociation kinetics in the Volmer stage. The low overpotential and applications, long-term stability tests are required to assess catalyst
Tafel slope suggested that Mo-NiCoP/NF had a strong charge transfer performance. The catalytic stability of Mo-NiCoP/NF was verified
rate and a large specific surface area. The effect of different Mo/Co after 5000 cycles, and negligible changes were observed in the po­
ratios on the HER activity was also investigated. Fig. S5 and Table S1 larization curve (Fig. 3f). The Mo-NiCoP/NF catalyst demonstrated
show that the highest HER catalytic performance was obtained when good HER stability at the current density of 10 mA cm−2 with no sign
the ratio between Mo and Co was 1:20. In addition, from the data in of degradation in the time-potential test for 24 h (Fig. 3f, inset). The
Table S3, Mo-NiCoP/NF outperformed other recently reported TMP SEM, XRD, and XPS characterizations after the long-term stability
catalysts. test are shown in Figs. S7, S8, and S9, respectively. We can see that
To further assess the kinetic changes, we compared the electro­ the microstructure of Mo-NiCoP/NF was preserved to the greatest
chemical impedance spectroscopy (EIS) curves of each catalyst by extent. And the XPS results of Ni 2p, Co 2p, Mo 3d, and P 2p showed
the AC impedance method. As shown in Fig. 3d, Mo-NiCoP/NF ex­ that the chemical quantivalence of the Ni, Co, Mo, and P atoms were
hibited the smallest charge transfer resistance (Rct) among the five also unchanged. Overall, these tested results demonstrated that the
tested catalysts, indicating that its interfacial electron transfer was Mo-NiCoP/NF electrode exhibited remarkable catalytic activity and
accelerated and its HER kinetics was prompted [48]. In addition, to durability under alkaline conditions.

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Y. Zhao, J. Chen, S. Zhao et al. Journal of Alloys and Compounds 918 (2022) 165802

Fig. 2. (a) XRD pattern of Mo-NiCoP/NF, (b) full XPS spectra of Mo-NiCoP/NF and NiCoP/NF and high-resolution spectra of (c) Ni 2p, (d) Co 2p, (e) P 2p and (f) Mo 3d core level.

Fig. 3. HER performance of different catalysts. (a) polarization curves, (b) overpotentials at different current densities, (c) Tafel slopes, (d) EIS Nyquist plots, (e) fitted electro­
chemical Cdl of the current density change (∆j = ja - jc) at different scan rates, (f) polarization curves of Mo-NiCoP/NF before and after 5000 cycle stability test (inset: chron­
oamperometry curve recorded at 10 mA cm−2 for 24 h).

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Y. Zhao, J. Chen, S. Zhao et al. Journal of Alloys and Compounds 918 (2022) 165802

Fig. 4. OER performance of different catalysts. (a) polarization curves, (b) overpotentials at different current densities, (c) Tafel slopes, (d) EIS Nyquist plots, (e) fitted electro­
chemical Cdl of the current density change (∆j = ja - jc) at different scan rates, (f) polarization curves of Mo-NiCoP/NF before and after 5000 cycle stability tests (inset: chron­
oamperometry curve recorded at 10 mA cm−2 for 24 h).

The OER capabilities of the as-prepared Mo-NiCoP/NF and re­ cycles, and negligible changes were observed in the polarization
ference catalysts after 90% iR compensation in 1 M KOH electrolyte curve (Fig. 4f). Mo-NiCoP/NF also exhibited good OER stability at a
were evaluated in an alkaline environment using a regular three- current density of 10 mA cm−2 with no sign of degradation in the
electrode system. From Fig. 4a and b, the overpotentials requested time-potential test for 24 h (Fig. 4f, inset). The SEM and XRD results
for Mo-NiCoP/NF to actuate current densities of 10 mA cm−2 and (Figs. S12 and S8) after the 24 h long-term durability test showed
100 mA cm−2 were 262 mV and 326 mV, respectively, smaller than that the microstructure of Mo-NiCoP/NF was preserved. As shown in
those demanded for NiCoP/NF (297 and 368 mV), Mo-NiCo/NF (301 Fig. S13, the XPS spectrum after the OER stability test suggested that
and 372 mV), NiCo/NF (312 and 391 mV), and NF. The OER capability the Ni atoms were in the Ni2+ oxidation state, and Ni-P (Ni0) com­
of Mo-NiCoP/NF was also better than that of the commercial RuO2 pletely disappeared. Likewise, Co-P (Co0) disappeared completely,
(290 and 360 mV). In addition, the corresponding Tafel slopes of the and the Co atoms were in the Co2+ and Co3+ oxidation states. These
LSV curves were also calculated, which further proved the excellent results indicated that some oxyhydroxides (NiOOH and CoOOH)
OER capability of Mo-NiCoP/NF. In Fig. 4c, Mo-NiCoP/NF exhibited a were generated on the surface of the nanowires during the OER,
Tafel slope as small as 49.4 mV dec−1, which was uncommonly which might be the real active sites for OER reaction [51–53].
stronger than commercial RuO2, NiCoP/NF, Mo-NiCo/NF, NiCo/NF, The Mo-NiCoP/NF catalyst exhibited excellent HER and OER
and NF. And the Tafel slopes of these five tested samples were 59.1, capability in an alkaline environment with 1 M KOH electrolyte, so
73.1, 90.1, 96.1 and 108.9 mV dec−1, respectively. The effect of dif­ two sheets of Mo-NiCoP/NF catalysts were used as HER and OER
ferent ratios between Mo and Co on the OER activity was also in­ electrodes to construct an alkaline overall water-splitting electro­
vestigated in detail. It was inferred that the best catalytic activity for lyzer (Mo-NiCoP/NF//Mo-NiCoP/NF) [54]. As shown in Fig. 5a, the
both HER and OER was obtained when the ratio was 1:20 (Figs. S4 Mo-NiCoP/NF//Mo-NiCoP/NF electrolyzer exhibited outstanding
and S10, Tab. S1 and S2). Likewise, compared with the other recently overall water splitting performance, requiring battery voltages as
reported TMP electrocatalysts, Mo-NiCoP/NF exhibited advantages in low as 1.56 V and 1.70 V at current densities of 10 mA cm−2 and
OER catalysis (Table S4). 100 mA cm−2, respectively, which were unmistakably stronger than
The EIS of the as-prepared catalysts was measured, and the re­ Pt/C//RuO2/NF noble metal dual electrodes (1.65 V and 1.84 V at
sults are shown in Fig. 4d. Mo-NiCoP/NF possessed the lowest Rct, current densities of 10 mA cm−2 and 100 mA cm−2, respectively). To
indicating its faster OER kinetics. The Cdl value was calculated using gain further insight into the durability of the electrocatalysts for
the same fitting method for HER (Fig. 4e and S11). The Cdl values of overall water splitting, we performed stability tests for 50 h at both
NiCoP/NF, Mo-NiCo/NF and NiCo/NF were 7.05, 1.99, and 0.68 mF current densities of 10 and 100 mA cm−2. The I-t curves remained
cm−2, respectively, while Mo-NiCoP/NF had the highest Cdl value stable after 50 h (Fig. 5b). Importantly, the Mo-NiCoP/NF catalyst for
(16.00 mF cm−2). The catalytic stability was verified after 5000 overall water splitting outperformed some recently reported

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Y. Zhao, J. Chen, S. Zhao et al. Journal of Alloys and Compounds 918 (2022) 165802

Fig. 5. Performance of Mo-NiCoP/NF overall water-splitting electrolyzer. (a) polarization curves for overall water splitting; (b) chronopotentiometry curves recorded for 50 h in
the electrolyzer at different current densities; (c) electrolyzer for splitting water; (d) comparison of Mo-NiCoP/NF catalyst with the other bifunctional catalysts in the literature in
1 M KOH electrolyte and a current density of 10 mA cm−2.

bifunctional electrocatalysts (Fig. 5d and Tab. S5) [55–74]. In sum­ Acknowledgments

mary, the Mo-NiCoP/NF catalyst is a highly versatile non-noble
metal bifunctional electrocatalyst. This work was financially supported by the Double Tops Joint
Fund of the Yunnan Science and Technology Bureau and Yunnan
3. Conclusions University (2019FY003025), Yunnan Applied Basic Research Projects
(202001BB050006). Authors thank Advanced Analysis and
In this study, Mo-doped NiCoP/NF electrocatalysts with nanowire Measurement Center of Yunnan University for the sample testing
arrays were fabricated using a classical two-step method involving service.
hydrothermal and phosphating processes. In 1 M KOH electrolyte,
after various tests, the Mo-NiCoP/NF catalyst demonstrated extra­ Appendix A. Supporting information
ordinary catalytic liveness for HER and OER and had outstanding
long-term stability. The overpotentials of 64 and 262 mV were de­ Supplementary data associated with this article can be found in
manded to actuate 10 mA cm−2 current density for the HER and OER, the online version at doi:10.1016/j.jallcom.2022.165802.
respectively. Furthermore, the Mo-NiCoP/NF electrode system
needed to extrude cell voltage of 1.56 V and 1.70 V at current den­ References
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