Amorphous Phosphates Tailor Local Proton Supply for Alkaline Hydrogen Evolution Electrocatalysis

IF 27.4 1区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY
Jie Liang, Zixiao Li, Min Zhang, Hefeng Wang, Zhengwei Cai, Yongsong Luo, Fengming Luo, Tongwei Wu, Yongchao Yao, Bo Tang, Xuping Sun
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Abstract

Hydrogen (H2) is irreplaceable as a feedstock in varied industrial scenarios, and alkaline water electrolysis allows for H2 production without costly proton exchange membrane and noble metals with limited reserves. However, alkaline solution is devoid of directly available protons, leading to suboptimal electrochemical H2-evolving kinetics even on catalysts with high intrinsic activities like CoP. On the other hand, high local acidity (i.e., superfluous protons) can lead to undesirable catalyst corrosion and active site blocking by excessive hydrogen coverage. Herein, a “cobalt phosphate-clothed-CoP (CoPi@CoP)” nanoarray catalyst is developed for proof of concept to explore a possible proton supply design principle. The nanometer-thick amorphous CoPi appears to serve multiple functions: facilitating water dissociation/H–O cleavage, buffering excess protons, and accelerating proton transfer/donation, thus optimizing the local proton supply to H-consuming sites. As expected, CoPi@CoP demonstrates state-of-the-art hydrogen evolution reaction performance in alkaline electrolytes, surpassing that of intrinsically active CoP. Online differential mass spectrometry, dynamic potential decay transients, spectroscopy data, and theoretical calculations reveal possible (atomic scale) reaction mechanisms.

Abstract Image

无定形磷酸盐为碱性析氢电催化调整局部质子供应
在各种工业场景中,氢(H2)作为原料是不可替代的,而碱性电解可以在不需要昂贵的质子交换膜和储量有限的贵金属的情况下生产氢气。然而,碱性溶液缺乏直接可用的质子,导致即使在CoP等具有高内在活性的催化剂上,电化学h2演化动力学也不理想。另一方面,高局部酸度(即,多余的质子)可能导致不希望的催化剂腐蚀和活性位点阻塞过多的氢覆盖。本文开发了一种“磷酸钴包覆cop (CoPi@CoP)”纳米阵列催化剂,用于概念验证,以探索可能的质子供应设计原理。纳米厚的无定形CoPi似乎具有多种功能:促进水解离/氢氧裂解,缓冲多余的质子,加速质子转移/给予,从而优化局部质子向h -消耗位点的供应。正如预期的那样,CoPi@CoP在碱性电解质中展示了最先进的析氢反应性能,超过了内在活性CoP。在线微分质谱,动态电位衰变瞬态,光谱数据和理论计算揭示了可能的(原子尺度)反应机制。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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来源期刊
Advanced Materials
Advanced Materials 工程技术-材料科学:综合
CiteScore
43.00
自引率
4.10%
发文量
2182
审稿时长
2 months
期刊介绍: Advanced Materials, one of the world's most prestigious journals and the foundation of the Advanced portfolio, is the home of choice for best-in-class materials science for more than 30 years. Following this fast-growing and interdisciplinary field, we are considering and publishing the most important discoveries on any and all materials from materials scientists, chemists, physicists, engineers as well as health and life scientists and bringing you the latest results and trends in modern materials-related research every week.
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