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碳化钼铁-铜杂化物作为用于析氧反应及肉桂醛/苯亚甲基丙酮合成的高效电氧化催化剂。

Molybdenum iron carbide-copper hybrid as efficient electrooxidation catalyst for oxygen evolution reaction and synthesis of cinnamaldehyde/benzalacetone.

作者信息

Li Jinzhou, Du Lan'ge, Guo Songtao, Chang Jiuli, Wu Dapeng, Jiang Kai, Gao Zhiyong

机构信息

School of Chemistry and Chemical Engineering, Collaborative Innovation Center of Henan Province for Green Manufacturing of Fine Chemicals, Key Laboratory of Green Chemical Media and Reactions, Ministry of Education, Henan Normal University, Henan Xinxiang 453007, PR China.

Key Laboratory of Yellow River and Huai River Water Environment and Pollution Control, Ministry of Education, Henan Key Laboratory for Environment Pollution Control, International Joint Laboratory on Key Techniques in Water Treatment, Henan Province, College of International Education, School of Environment, Henan Normal University, Henan Xinxiang 453007, PR China.

出版信息

J Colloid Interface Sci. 2024 Nov;673:616-627. doi: 10.1016/j.jcis.2024.06.122. Epub 2024 Jun 17.

Abstract

Oxygen evolution reaction (OER) is the efficiency limiting half-reaction in water electrolysis for green hydrogen production due to the 4-electron multistep process with sluggish kinetics. The electrooxidation of thermodynamically more favorable organics accompanied by CC coupling is a promising way to synthesize value-added chemicals instead of OER. Efficient catalyst is of paramount importance to fulfill such a goal. Herein, a molybdenum iron carbide-copper hybrid (MoC-FeCu) was designed as anodic catalyst, which demonstrated decent OER catalytic capability with low overpotential of 238 mV at response current density of 10 mA cm and fine stability. More importantly, the MoC-FeCu enabled electrooxidation assisted aldol condensation of phenylcarbinol with α-H containing alcohol/ketone in weak alkali electrolyte to selective synthesize cinnamaldehyde/benzalacetone at reduced potential. The hydroxyl and superoxide intermediate radicals generated at high potential are deemed to be responsible for the electrooxidation of phenylcarbinol and aldol condensation reactions to afford cinnamaldehyde/benzalacetone. The current work showcases an electrochemical-chemical combined CC coupling reaction to prepare organic chemicals, we believe more widespread organics can be synthesized by tailored electrochemical reactions.

摘要

析氧反应(OER)是绿色制氢水电解中效率受限的半反应,这是由于其4电子多步过程动力学迟缓。伴随着碳 - 碳偶联的热力学上更有利的有机物的电氧化是一种有前景的合成增值化学品而非析氧反应的方法。高效催化剂对于实现这一目标至关重要。在此,设计了一种碳化钼铁 - 铜杂化物(MoC - FeCu)作为阳极催化剂,其在10 mA cm的响应电流密度下具有238 mV的低过电位,展现出良好的析氧催化能力和优良的稳定性。更重要的是,MoC - FeCu能够在弱碱性电解质中实现苯甲醇与含α - H的醇/酮的电氧化辅助羟醛缩合反应,在降低的电位下选择性合成肉桂醛/苄叉丙酮。高电位下产生的羟基和超氧中间体自由基被认为是苯甲醇电氧化和羟醛缩合反应生成肉桂醛/苄叉丙酮的原因。当前工作展示了一种电化学 - 化学联合的碳 - 碳偶联反应来制备有机化学品,我们相信通过定制的电化学反应可以合成更多种类的有机物。

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