化学镀法制备NiCoP/rGO/NF高效电解水析氢催化剂

doi:10.16085/j.issn.1000-6613.2022-1846

摘要/Abstract

摘要：

电解水制氢是一项制取绿色氢能的重要技术，而开发具有低成本、高活性的催化剂作为电极材料是当前的研究重点。本文以负载石墨烯的泡沫镍（rGO/NF）为基底，应用化学镀法制备了NiCoP/rGO/NF新型析氢（HER）电解水催化剂。比较NiCoP/NF和引入石墨烯后的NiCoP/rGO/NF的电催化性能。三电极体系的测试结果表明，在1mol/L KOH电解液中，在电流密度为10mA/cm²时，NiCoP/rGO/NF电极具有最优的过电位98mV。塔菲尔斜率（Tafel）、循环伏安（CV）和电化学阻抗（EIS）分析表明，NiCoP/rGO/NF电极优异的HER性能是快速反应动力学、高效电化学活性比表面积（ECSA）和小反应电阻（R_ct）综合作用的结果。结构测试表明：NiCoP均匀沉积于rGO和泡沫镍表面，并且rGO形成的三维网络结构增加了催化剂比表面积，暴露出丰富的活性边缘，催化剂中Ni—P/Co—P键的形成是HER性能提升的关键。

关键词: 电化学, 制氢, 催化剂, 化学镀, 过渡金属磷化物, 三维石墨烯

Abstract:

Electrochemical water splitting is an important green hydrogen technology. The development of efficient and cost-effective electrocatalyst is the focus of current research. A novel hydrogen evolution reaction (HER) electrocatalyst NiCoP/rGO/NF was constructed by electroless plating on nickel foam substrate that was loaded with three-dimensional reduced graphene oxide (rGO). The electrocatalysis performance of NiCoP/NF and that with the introduction of rGO (NiCoP/rGO/NF) was compared. The test results of the three-electrode system showed that, in 1mol/L KOH electrolyte and under the current density of 10mA/cm², the NiCoP/rGO/NF electrode gave the highest overpotential of 98mV. The remarkable performance of NiCoP/rGO/NF electrode in HER might be the comprehensive result of fast reaction kinetics, large electrochemical active specific surface area (ECSA) and small reaction resistance (R_ct) as indicated by the Tafel, cyclic voltammetry (CV) and impedance (EIS) analysis. The structure characterization confirmed that NiCoP was deposited uniformly on the surface of rGO and NF, and the three-dimensional network structure formed by rGO increased the catalyst surface area and exposed rich active edges. The formation of the Ni—P/Co—P bond in NiCoP/rGO/NF was key of HER performance improvement.

Key words: electrochemistry, hydrogen production, catalyst, electroless plating, transition metal phosphide, three-dimensional graphene

中图分类号:

TQ15

张亚娟, 徐惠, 胡贝, 史星伟. 化学镀法制备NiCoP/rGO/NF高效电解水析氢催化剂[J]. 化工进展, 2023, 42(8): 4275-4282.

ZHANG Yajuan, XU Hui, HU Bei, SHI Xingwei. Preparation of NiCoP/rGO/NF electrocatalyst by eletroless plating for efficient hydrogen evolution reaction[J]. Chemical Industry and Engineering Progress, 2023, 42(8): 4275-4282.

图/表 11

图1 NiCoP/NF和NiCoP/rGO/NF催化剂SEM图像

图2 NiCoP/NF和NiCoP/rGO/NF催化剂的N2吸/脱附曲线图和对应的孔径分布图

表1 NiCoP/NF和NiCoP/rGO/NF催化剂的比表面积和孔径数据

样品	S_BET/m²·g^-1	V/m³·g^-1
NiCoP/NF	8.21	0.026
NiCoP/rGO/NF	19.97	0.038

图3 NiCoP/rGO/NF的EDS谱图分布信息

图4 NiCoP/rGO/NF的XRD图（NiP-PDF#74-1382、Ni12P5-PDF#22-1190、Co2P-PDF#32-0306）

图5 NiCoP/rGONF电极XPS谱图

图6 不同催化剂LSV曲线和过电位图

图7 不同催化剂电化学测试谱图

表2 催化剂EIS拟合参数

	NiCoP/rGO/NF	NiCoP/NF	CoP/NF	NiP/NF
R_s/Ω	1.09	1.32	1.03	1.46
R_ct/Ω	6.75	9.46	14.65	18.17
CPE-T/Ω	0.009	0.006	0.006	0.005
CPE-P/Ω	0.79	0.84	0.79	0.79

图8 Ni/NF、CoP/NF、NiCoP/NF和NiCoP/rGO/NF催化剂CV曲线图

图9 NiCoP/rGO/NF电压-时间（CP）测试结果图

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