Electrodeposition-Solvothermal Access to Ternary Mixed Metal Ni-Co-Fe Sulfides for Highly Efficient Electrocatalytic Water Oxidation in Alkaline Media

doi:10.1016/j.electacta.2017.01.178

Electrochimica Acta

Volume 230, 10 March 2017, Pages 151-159

https://doi.org/10.1016/j.electacta.2017.01.178 Get rights and content

Highlights

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Ternary Ni-Co-Fe sulfides based on nickel foam were prepared by two-step method.
•
Electrodeposition-solvothermal process is suitable for Ni-Co-Fe sulfides film.
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Ternary NiCoFeS/NF exhibits excellent OER activity for water splitting in alkaline.
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The stability of NiCoFeS/NF can be improved by a secondary electrodeposition of Fe.

Abstract

Ternary mixed metal Ni-Co-Fe sulfides based on three dimensional (3D) nickel foam (NiCoFeS/NF) have been synthesized via facile electrodeposition-solvothermal process. Firstly, a uniform film of Co-Fe oxides has been electrodeposited on the surface of 3D skeleton of NF (CoFe/NF). Secondly, an ethanol solvothermal sulfurization has been adopted to convert CoFe/NF to ternary mixed metal sulfides (NiCoFeS/NF). XRD confirms that ternary NiCoFeS is composed of mixed phases including NiS, Ni₃S₂ and Co₃S₄ phases but no Fe sulfides phase, implying amorphous state of Fe sulfides. SEM images of ternary NiCoFeS films shows uniform film covering on the surface of NF, which is composed of many hill-shaped bulges structures. The OER measurements confirm the excellent performance of ternary NiCoFeS/NF in 1.0 M KOH, providing low overpotential of 40 and 160 mV to drive 10 and 100 mA cm⁻² in 1.0 M KOH, respectively. A further enhancement of the stability of NiCoFeS/NF have been conducted via a secondary electrodeposition of Fe on NiCoFeS/NF to obtain NiCoFeS-Fe/NF, with slightly lower overpotential of 230 mV to drive 100 mA cm⁻² than that (310 mV) of NiCoFeS/NF after stability test. The role of Fe on OER ability and stability of NiCoFeS/NF have been discussed.

Graphical abstract

Introduction

Hydrogen production by water electrolysis is considered as clean and efficient approach to promising renewable energy to resolve energy crisis and severe environmental pollution from fossil fuels [1], [2], [3], [4], [5], [6]. Water oxidation for oxygen evolution reaction (OER) is the most kinetic-sluggish in water electrolysis, meaning large energy consumption in industry [7], [8]. In order to enhance the overall efficiency of water electrolysis, excellent OER electrocatalysts with low cost and high efficiency have been intensely pursued in order to replace noble metal Ru/Ir oxides [9], [10], [11].

Among various earth-abundant elements in the 3d metals species, nickel appears as one of the most promising materials with high activity for OER in alkaline media [12], [13], [14], [15], [16], [17], [18]. More remarkably, heterogeneous metal doping into nickel-based materials can further enhance the OER activity [19], [20], [21], [22], [23], exemplified by Ni-Fe layered double hydroxide (LDH) as a typical case [24], [25], [26], [27], [28], [29]. Recent studies have indicated that both Ni and Fe performs as active sites for OER in Ni-Fe catalysts [28], [30], [31], [32], whereas the active sites of Fe are not conductive unless reaching high overpotential in water electrolysis. Therefore, it is necessary to search for a third metal of doping to further decrease the overpotential of OER. Many rational screening work have been done to select a third proper metal, and Co is confirmed to be conductive to lower the overpotential of Fe as active sites [30], [33], [34]. Sanjeev Mukerjee and co-workers have successfully prove the enhanced OER activity of Ni-Fe-Co mixed-metal oxides (MMO) than that of the state of the art Ni-Fe LDH [34], [35], [36], providing the foundation for the broader exploration of ternary Ni-Co-Fe-based materials for water oxidation.

On the other hand, metal sulfides tends to own better catalytic performances than oxides or hydroxides, due to superior electronic conductivity of most sulfides [37], [38]. More specifically, nickel sulfides proved outstanding OER activity such as NiS [39] and Ni₃S₂ [40] with low overpotential to reach high current density and superior stability. Thus it can be inferred that ternary Ni-Co-Fe sulfides may hold promising for water oxidation compared with Ni-Co-Fe oxides, yet few research have focused on this issue. Our recent work of binary Ni–Fe sulfides have proved great OER activity than Ni–Fe hydroxides [41], and its further improvements for OER may be realized by incorporating the third metal of Co.

Herein, a facile fabrication of ternary Ni-Co-Fe sulfides has been realized by electrodeposition of Fe-Co on nickel foam (NF) followed by solvothermal sulfurization. The as-obtained ternary NiCoFeS/NF sample provides low overpotential of 40 and 160 mV to drive 10 and 100 mA cm⁻², respectively, which exceeds our previous work of binary NiFeS/NF requiring 65 and 189 mV to reach 10 and 100 mA cm⁻², respectively [41]. In order to further stabilize the long-term OER performance of ternary NiCoFeS/NF, a secondary electrodeposition of Fe on the surface of NiCoFeS/NF have been conducted to obtain NiCoFeS-Fe/NF based on previous report [35], [38], [42], [43]. A slight activity loss for water oxidation of NiCoFeS-Fe/NF can be observed compared with NiCoFeS/NF. It implies a possible balance between activity and stability with secondary electrodeposition of Fe to realize optimal OER performance in alkaline solution. Our work may provide a facile access to ternary mixed transition metal sulfides in catalyzing water oxidation process.

Section snippets

Experimental section

Prior to the synthesis, NF (thickness: 1.0 mm, surface density: 350 g m⁻², Shenzhen Poxon Machinery Technology Co., Ltd.) was consecutively sonicated in acid, acetone, ethanol and deionized water for 0.5 h, respectively. The electrodeposition was undertaken on a typical three-electrode system (Gamry Reference 600 Instrument). The three-electrode system includes pre-cleaned NF as the working electrode, Ag/AgCl (in saturated KCl) as reference electrode and Pt foil as counter electrode. The

Results and discussions

XRD patterns of CoFe/NF, NiCoFeS/NF and NiCoFeS-Fe/NF are shown in Fig. 1. CoFe/NF contain only Ni peaks (PDF no. 01-070-0989) from metallic NF as substrate, implying that the as-electrodeposited CoFe on NF is amorphous state. XRD patterns of Fe/NF in Fig. S1 only contain Ni peaks from metallic NF, suggesting that the electrodeposited Fe is amorphous. After solvothermal sulfurization process, the as-obtained NiCoFeS/NF contains mixed structure of Ni_xS_y phase including NiS (PDF no. 00-001-1286)

Conclusions

Ternary mixed-metal NiCoFeS/NF have been synthesized through a facile electrodeposition of CoFe/NF followed by solvothermal sulfurization using NF as support and Ni resources. The OER measurements confirm the highly active ternary NiCoFeS/NF with low overpotential of 40 and 160 mV to reach 10 and 100 mA cm⁻² in 1.0 M KOH, respectively. To further stabilize long-term OER performances of NiCoFeS/NF, a second electrodeposition of Fe oxides on NiCoFeS/NF demonstrates less activity loss of NiCoFeS-Fe/NF

Acknowledgement

This work is financially supported by the Fundamental Research Funds for the Central Universities (15CX05031A).

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Electrodeposition-Solvothermal Access to Ternary Mixed Metal Ni-Co-Fe Sulfides for Highly Efficient Electrocatalytic Water Oxidation in Alkaline Media

Highlights

Abstract

Graphical abstract

Introduction

Section snippets

Experimental section

Results and discussions

Conclusions

Acknowledgement

Chem. Eng. J.

Chem. Eng. J.

Electrochim. Acta

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