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用于生物质高效多选择性升级的Ag─Co(OH)串联异质结构电催化剂的构建及其对反应物的协同活化以实现醛氧化

Construction of Ag─Co(OH) Tandem Heterogeneous Electrocatalyst Induced Aldehyde Oxidation and the Co-Activation of Reactants for Biomass Effective and Multi-Selective Upgrading.

作者信息

Zhou Peng, Lv Xingshuai, Huang Huining, Cheng Baixue, Zhan Haoyu, Lu Yankun, Frauenheim Thomas, Wang Shuangyin, Zou Yuqin

机构信息

State Key Laboratory of Bio-fibers and Eco-textiles, College of Materials Science and Engineering, Collaborative Innovation Center of Shandong Marine Biobased Fibers and Ecological Textiles, Institute of Marine Biobased Materials, Qingdao University, Qingdao, 266071, P. R. China.

State Key Laboratory of Chemo/Bio-Sensing and Chemometrics, College of Chemistry and Chemical Engineering, Advanced Catalytic Engineering Research Center of the Ministry of Education, Hunan University, Changsha, 410082, China.

出版信息

Adv Mater. 2024 Jun;36(26):e2312402. doi: 10.1002/adma.202312402. Epub 2024 Mar 14.

Abstract

The electrocatalytic oxidation of 5-hydroxymethylfurfural (HMF) provides a feasible way for utilization of biomass resources. However, how to regulate the selective synthesis of multiple value-added products is still a great challenge. The cobalt-based compound is a promising catalyst due to its direct and indirect oxidation properties, but its weak adsorption capacity restricts its further development. Herein, by constructing Ag─Co(OH) heterogeneous catalyst, the efficient and selective synthesis of 5-hydroxymethyl-2-furanoic acid (HMFCA) and 2,5-furan dicarboxylic acid (FDCA) at different potential ranges are realized. Based on various physical characterizations, electrochemical measurements, and density functional theory calculations, it is proved that the addition of Ag can effectively promote the oxidation of aldehyde group to a carboxyl group, and then generate HMFCA at low potential. Moreover, the introduction of Ag can activate cobalt-based compounds, thus strengthening the adsorption of organic molecules and OH species, and promoting the formation of FDCA. This work achieves the selective synthesis of two value-added chemicals by one tandem catalyst and deeply analyzes the adsorption enhancement mechanism of the catalyst, which provides a powerful guidance for the development of efficient heterogeneous catalysts.

摘要

5-羟甲基糠醛(HMF)的电催化氧化为生物质资源的利用提供了一条可行途径。然而,如何调控多种增值产物的选择性合成仍是一个巨大挑战。钴基化合物因其直接和间接氧化性能而成为一种有前景的催化剂,但其吸附能力较弱限制了其进一步发展。在此,通过构建Ag─Co(OH)多相催化剂,实现了在不同电位范围内高效、选择性地合成5-羟甲基-2-呋喃甲酸(HMFCA)和2,5-呋喃二甲酸(FDCA)。基于各种物理表征、电化学测量和密度泛函理论计算,证明了Ag的添加能有效促进醛基氧化为羧基,进而在低电位下生成HMFCA。此外,Ag的引入可激活钴基化合物,从而增强对有机分子和OH物种的吸附,并促进FDCA的形成。这项工作通过一种串联催化剂实现了两种增值化学品的选择性合成,并深入分析了催化剂的吸附增强机制,为高效多相催化剂的开发提供了有力指导。

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