DOI: 10.1002/chem.71570 ISSN: 0947-6539

Electrocatalytic Ethanol‐to‐Acetate Conversion With Nearly 100% Faradaic Efficiency Enabled by Cu‐Doping Strategy for Enhancing Selective and Cooperative Adsorption

Zihui Zhu, Wenjing Zhang, Maolin Han, Yichen Zhu, Qiang Peng

ABSTRACT

Electrocatalytic biomass‐based ethanol coupled with water electrolysis for hydrogen production can significantly reduce hydrogen production energy consumption while generating high‐valued acetate. However, nickel‐based non‐precious metal electrocatalysts exhibit low selectivity and stability due to imbalanced adsorption of ethanol reactants and OH . Herein, Cu‐doped Ni(OH) 2 nanosheets were prepared for the selective electrooxidation of ethanol to acetate, achieving nearly 100% Faradaic efficiency (FE) and 108 h stability. In situ electrochemical testing and theoretical calculations indicated that Cu doping promoted the cooperative of OH at Cu sites, thereby effectively switching the rate‐determining step from *CH 3 CHO dehydrogenation to *CH 3 CO─OH coupling. This synergistically adsorption mechanism reduces the thermodynamic barrier to 1.56 eV. Additionally, the constructed dual‐electrode system delivered a current density of 50 mA cm −2 at a cell voltage of 1.54 V, along with over 55 h stability and high FEs. This work demonstrates the importance of cooperative adsorption behavior of ethanol and OH in the ethanol oxidation process, which is beneficial to enhancing the production efficiency of green hydrogen and acetate through electrochemical methods.

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