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在铈/钼掺杂的羟基氧化镍中激活表面氧以在安培级电流密度下协同增强糠醛氧化和析氢反应

Activating Surface Oxygen in Ce/Mo-Doped Ni Oxyhydroxide for Synergistically Enhancing Furfural Oxidation and Hydrogen Evolution at Ampere-Level Current Densities.

作者信息

Cao Tian, Cheng Jia, Xiang Yang, Hu Linping, Hu Xiaohua, Li Li, Huang Xun, Wei Zidong

机构信息

Center of Advanced Electrochemical Energy, State Key Laboratory of Advanced Chemical Power Sources, School of Chemistry and Chemical Engineering, Chongqing University, Chongqing, 40004, P.R. China.

出版信息

Angew Chem Int Ed Engl. 2025 Jul 7;64(28):e202506017. doi: 10.1002/anie.202506017. Epub 2025 May 15.

Abstract

The integration of biomass-platform molecule oxidation with water electrolysis is a promising strategy to reduce energy consumption in hydrogen production and obtain high-value chemicals simultaneously, yet the efficiency of organic oxidation requires further improvement. Herein, we developed a highly efficient Ce, Mo co-doped Ni-based (oxy)hydroxide catalyst, where Mo with high spin state promotes the adsorption of furfural (FA), while Ce activates surface lattice oxygen (O), lowering the energy barrier for O─OH coupling to form OOH, the key intermediate for high current densities. The catalyst achieves an industrial-grade current density of 1000 mA cm at a remarkably low potential of 1.46 V versus RHE in furfural oxidation, with exceptional selectivity (99.4%) and Faradaic efficiency (97.7%) for furoic acid. When deployed as anode in an anion-exchange membrane reactor, the NiMoCe/NF catalyst sustains a current density of 500 and 1000 mA cm at a cell voltage of only 1.85 and 2.15 V, respectively, surpassing most reported continuous flow electrolyzers limited to 200 mA cm . Moreover, the system exhibits outstanding durability after 200 h of continuous operation. This work provides critical insights into the rational design of catalysts for energy-efficient biomass valorization coupled with industrial hydrogen production.

摘要

将生物质平台分子氧化与水电解相结合是一种很有前景的策略,可降低制氢过程中的能源消耗并同时获得高价值化学品,然而有机氧化的效率仍需进一步提高。在此,我们开发了一种高效的铈、钼共掺杂镍基(羟基)氧化物催化剂,其中高自旋态的钼促进糠醛(FA)的吸附,而铈激活表面晶格氧(O),降低了O─OH偶联形成OOH(高电流密度的关键中间体)的能垒。该催化剂在糠醛氧化中相对于可逆氢电极(RHE)在1.46 V的极低电位下实现了1000 mA cm 的工业级电流密度,对糠酸具有出色的选择性(99.4%)和法拉第效率(97.7%)。当在阴离子交换膜反应器中用作阳极时,NiMoCe/NF催化剂在电池电压仅为1.85和2.15 V时分别维持500和1000 mA cm 的电流密度,超过了大多数报道的限于200 mA cm 的连续流电解槽。此外,该系统在连续运行200小时后表现出出色的耐久性。这项工作为合理设计用于高效生物质增值与工业制氢相结合的催化剂提供了关键见解。

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