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金属有机框架衍生的草酸盐配体修饰的氢氧化镍钴用于增强电化学甘油氧化反应

Metal-organic frameworks-derived oxalate ligand modified NiCo hydroxides for enhanced electrochemical glycerol oxidation reaction.

作者信息

Zou Yizhong, Zhang Wen-Da, Xu Hanwen, Yang Jingguo, Liu Jiangyong, Gu Zhi-Guo, Yan Xiaodong

机构信息

Key Laboratory of Synthetic and Biological Colloids, Ministry of Education, School of Chemical and Material Engineering, Jiangnan University, Wuxi 214122, China.

School of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou 225002, China.

出版信息

J Colloid Interface Sci. 2023 Nov 15;650(Pt A):701-709. doi: 10.1016/j.jcis.2023.07.010. Epub 2023 Jul 4.

Abstract

Glycerol oxidation reaction can be substituted for oxygen evolution reaction for more efficient hydrogen production due to its lower thermodynamic potential. Herein, a series of NiCo hydroxide nanosheets containing abundant Ni species and surface ligands were synthesized by in-situ structural transformation of bimetallic organic frameworks in alkaline media for efficient glycerol oxidation reaction. It is found that the incorporation of Co ions increases the content of the Ni species, and that the Ni/Co ratio of 1.0 lead to the optimal catalytic performance. The oxalate-modified nickel-cobalt hydroxide with the optimized Ni/Co ratio can deliver a current density of 10 mA cm at 1.26 V vs. RHE (reversible hydrogen electrode), and reaches its maximum selectivity and Faradaic efficiency at 1.30 V vs. RHE. A high selectivity of 82.9% and a Faradaic efficiency of 91.0% are achieved. The high catalytic activity can be mainly attributed to the abundant Ni species and surface carboxyl groups.

摘要

由于甘油氧化反应具有较低的热力学电位,因此可以替代析氧反应以实现更高效的制氢。在此,通过在碱性介质中对双金属有机框架进行原位结构转变,合成了一系列含有丰富镍物种和表面配体的氢氧化镍钴纳米片,用于高效甘油氧化反应。研究发现,钴离子的掺入增加了镍物种的含量,且镍/钴比为1.0时催化性能最佳。具有优化镍/钴比的草酸盐修饰氢氧化镍钴在相对于可逆氢电极(RHE)为1.26 V时可提供10 mA cm的电流密度,并在相对于RHE为1.30 V时达到其最大选择性和法拉第效率。实现了82.9%的高选择性和91.0%的法拉第效率。高催化活性主要归因于丰富的镍物种和表面羧基。

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