Co/NiCoP纳米异质结构催化剂的构建及其析氢性能

doi:10.16085/j.issn.1000-6613.2023-0946

摘要/Abstract

摘要：

开发价格便宜、高效稳定的析氢反应（HER）电催化剂是实现电解水制氢技术工业规模化的关键问题之一。本文利用低温电化学沉积法成功地在碳布表面原位生长了Co/NiCoP异质纳米结构的自支撑催化电极，结合表征技术、以1mol/L NaOH溶液为碱性电解质的理论计算和以三电极体系电化学工作站为基础的实验测试对该材料进行了HER性能评估。结果表明，Co/NiCoP异质结构催化剂具有优异的析氢性能，在碱性介质中，获取10mA/cm²的催化电流密度所需要的过电位仅为54mV，Tafel斜率为78.5mV/dec。这主要归因于：①Co/NiCoP纳米催化剂在碳布表面良好的分散性增加了暴露的催化活性位点数；②异质结构的存在促进了Co与NiCoP之间电子的相互作用，加快了电荷转移速率并提高了材料的导电性；③理论计算表明，Co/NiCoP异质结构的构建能有效地降低水的解离势垒，促进水的解离，进而加快HER动力学反应过程。因此，Co/NiCoP纳米异质结构催化剂的构建丰富了非贵金属纳米材料在电解水制氢领域的应用。

关键词: 制氢, 催化剂, 纳米结构, 复合材料

Abstract:

The development of cost-effective and efficient electrocatalysts for hydrogen evolution reaction (HER) is one of the key factors to meet the industrial-scale application demand. Herein, heterostructure Co/NiCoP nanoparticles grown on carbon cloth were successfully fabricated via low temperature electrochemical deposition method, and characterized and theoretically calculated. Moreover, the HER performance of the obtained samples were investigated in 1mol/L NaOH alkaline electrolyte with a three-electrode electrochemical workstation. The heterostructure Co/NiCoP composite showed excellent catalytic performance, with a low overpotential of 54mV at a current density of 10mA/cm² and Tafel slope of 78.5mV/dec. Based on the theoretical calculations and characterized results, the high electrocatalytic activity of Co/NiCoP was attributed to the following three points: ① The well dispersed Co/NiCoP nanoparticles on carbon cloth increased the exposure of surface active sites; ② The electron interaction between Co and NiCoP was promoted via heterostructure, which accelerated the charge transfer rate and increased the conductivity of the material; ③ The construction of Co/NiCoP heterostructure boosted the alkaline HER kinetics by accelerating the water dissociation step. Therefore, the construction of Co/NiCoP nano-heterogeneous catalysts has enriched the applications of non-noble metal based electrocatalysts in electrolysis of water.

Key words: hydrogen production, catalyst, nanostructure, composites

中图分类号:

O643.36

姜楠, 李佳优, 蒋博龙, 高伟俊, 谭明. Co/NiCoP纳米异质结构催化剂的构建及其析氢性能[J]. 化工进展, 2023, 42(12): 6345-6353.

JIANG Nan, LI Jiayou, JIANG Bolong, GAO Weijun, TAN Ming. Construction of heterostructure Co/NiCoP nanoparticles for hydrogen evolution[J]. Chemical Industry and Engineering Progress, 2023, 42(12): 6345-6353.

图/表 8

图1 催化剂的XRD图谱

图2 Co/NiCoP催化剂的形貌表征图

图3 NiCoP和Co/NiCoP催化剂材料的XPS谱图

图4 催化剂在1.0mol/L NaOH中的HER性能图

表1 Co/NiCoP催化剂碱性条件HER活性与最新报道非贵金属催化剂对比

催化剂样品	电流密度/mA·cm^-2	过电位/mV	参考文献
Mo-NiCoP	10	76	[13]
Co-VO _x -P	10	98	[24]
Fe-CoP	10	79	[25]
NiCo₂S₄	10	90	[26]
Ni-Cu-C	10	87	[27]
NiCoP	10	71	[28]
CoP₃/CoMoP	10	110	[29]
MoC/VN	10	87	[30]
CoN/MoC/NMCNFs	10	92.5	[31]
CoP@CoOOH/CP	10	81.7	[32]
CoP@3DOM-FeP	10	67.2	[33]
Co/NiCoP	10	54	本研究

图5 催化剂样品的循环伏安曲线图

图6 双电层电容拟合曲线图

图7 水分裂自由能图

参考文献 33

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