Ag/ZnO Composite Structure Modulated by Hybrid Engineering for Efficient Electroreduction of CO₂ to CO

Abstract Electrochemical carbon dioxide reduction reaction (ECO₂RR) act as a green and value‐added technology, which could convert CO₂ into products with circulation value, has a good application prospect. However, the activity of non‐mainstream Zn‐based catalysts has not yet reached satisfactory expectations, and how to further modify them to improve the performance of CO production performance still remains a challenge. In our work, a design of hybrid engineering is proposed to enhance the activity of Zn‐based materials, in which the introduction of slight Ag could not only optimize the electronic structure of Zn‐based materials but also effectively increase their electrochemically active surface area. Compared with pure ZnO, the faraday efficiency of CO (FE_CO) in Ag/ZnO increased by 1.7 times from 45.9 % to 80.3 % at −0.977 V vs. RHE. Moreover, the long‐term and stable output of products in the electrolysis process also confirms the superior stability of the hybrid catalyst According to the in‐situ Raman study, it is confirmed that the main factor for the enhanced CO selectivity after the introduction of Ag is the improvement of the key *COOH intermediates. This study provides an effective strategy for constructing highly active Zn‐based catalysts for industrial‐scale ECO₂RR.