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Electrochemical conversion of CO 2  is an attractive alternative to releasing it to the atmosphere. Catalysts derived from electroreduction of metal oxides are often more active than when starting with metallic phase catalyst. The origin of this effect is not yet clear. Using ZnO nanorods, we show that the initial structure of the oxide as well as the electrolyte medium have a profound impact on the structure of the catalytic active Zn phase, and thereby the selectivity of the catalysts. ZnO nanorods with various aspect ratios were electrochemically reduced in different electrolytes leading to metallic Zn with different structures; a sponge‐like structure, nanorods and nanoplates. The sponge‐like Zn produced syngas with H 2  : CO=2, and some formate, the nanorods produced only syngas with H 2  : CO=1, while Zn nanoplates exhibited 85 % selectivity towards CO. These results open a pathway to design new electrocatalysts with optimized properties by modifying the structure of the starting material and the electroreduction medium.

Structure Dependent Product Selectivity for CO 2 Electroreduction on ZnO Derived Catalysts