Interfacial Dynamic Oxygen Exchange Preserves C─O Bonds for Selective CO <sub>2</sub> ‐to‐Ethanol Electrosynthesis
Abstract
ABSTRACT Intermediate‐valence copper (Cu + ) is essential for preserving C─O bonds during the electrochemical reduction of CO 2 to ethanol, yet its progressive over‐reduction to Cu 0 under operating potentials inevitably dictates C─O bond cleavage and shifts selectivity toward ethylene. Herein, we propose an interfacial dynamic oxygen exchange strategy to stabilize Cu + sites and steer the ethanol reaction pathway. We realize this mechanism by engineering a few‐layer ceria‐coated cuprous oxide (Cu 2 O@CeO 2 ) catalyst featuring an oxygen vacancy‐rich heterointerface (Ce−O V −Cu). Operando spectroscopic measurements and density functional theory calculations reveal that these interfacial oxygen vacancies act as core mediators; by continuously capturing and migrating oxygen species derived from CO 2 , they effectively arrest the reduction of adjacent Cu + siteversuss. Crucially, this dynamic interface dictates the asymmetric C─C coupling of *CH 2 and *CHO, successfully preserving the C−O bond during the subsequent protonation of *CH 2 CHO to *CH 3 CHO. Consequently, the optimized catalyst delivers an outstanding ethanol Faradaic efficiency of 68.5% at −1.1 V versus RHE and exhibits robust operational stability exceeding 150 h, substantially outperforming pristine Cu 2 O. This study establishes vacancy‐mediated dynamic oxygen exchange as a robust strategy for preserving key oxygen‐containing functional groups in highly selective CO 2 ‐to‐ethanol electrosynthesis.
Article Details
Authors (12)
Jiwei Li
Jiaying He
School of Chemistry, Engineering Research Center of Energy Storage Materials and Devices of Ministry of Education, National Innovation Platform (Center) for Industry-Education Integration of Energy Storage Technology
Deyu Zhu
School of Basic Medical Sciences
Chenfeng Xia
School of Chemistry and Chemical Engineering, State Key Laboratory of Materials Processing and Die & Mould Technology, Key Laboratory of Material Chemistry for Energy Conversion and Storage (Ministry of Education), Hubei Key Laboratory of Material Chemistry and Service Failure, Wuhan National Laboratory for Optoelectronics, Huazhong University of Science and Technology (HUST), 1037 Luoyu Road, Wuhan 430074, China
Mingzhi Wang
State Key Laboratory of New Textile Materials and Advanced Processing Key Laboratory of Material Chemistry for Energy Conversion and Storage (Ministry of Education) Hubei Key Laboratory of Material Chemistry and Service Failure School of Chemistry and Chemical Engineering Huazhong University of Science and Technology (HUST) Wuhan China
Liang Dong
Lebin Cai
State Key Laboratory of New Textile Materials and Advanced Processing Key Laboratory of Material Chemistry for Energy Conversion and Storage (Ministry of Education) Hubei Key Laboratory of Material Chemistry and Service Failure School of Chemistry and Chemical Engineering Huazhong University of Science and Technology (HUST) Wuhan China
Wensheng Fang
State Key Laboratory of New Textile Materials and Advanced Processing Key Laboratory of Material Chemistry for Energy Conversion and Storage (Ministry of Education) Hubei Key Laboratory of Material Chemistry and Service Failure School of Chemistry and Chemical Engineering Huazhong University of Science and Technology (HUST) Wuhan China
Yaqiong Su
Engineering Research Center of Energy Storage Materials and Devices, Ministry of Education School of Chemistry
Fei Song
Shanghai Synchrotron Radiation Facility, Shanghai Advanced Research Institute
Wei Guo
Bao Yu Xia
State Key Laboratory of New Textile Materials and Advanced Processing, Key Laboratory of Material Chemistry for Energy Conversion and Storage (Ministry of Education), Hubei Key Laboratory of Material Chemistry and Service Failure, School of Chemistry and Chemical Engineering