Abstract

Abstract Electrochemical CO 2 reduction reaction (CO 2 RR) holds a great potential for converting CO 2 into valuable carbon‐based chemicals and fuels. A promising strategy for enhancing CO 2 RR performance is the deliberate structural design of electrocatalysts, which can maximize the utilization of inherent structural advantages. In this work, SnO 2 nanocubes (NCs) and nanorods (NRs) are synthesized using a surface energy‐driven growth orientation method, where the stable (110) facet and the highly energetic (001) facet constitute the SnO 2 nanostructures. Leveraging the inherent structural merits of different facets on SnO 2 , theoretical calculations reveal that the (001) facet plays a primary role in inhibiting hydrogen evolution reaction (HER), while both (110) and (001) facets are highly favorable for CO 2 ‐to‐formate conversion under the external bias. As a result, SnO 2 NCs with a higher facet ratio of (001)/(110) achieve nearly 100% selectivity for the formation of carbonaceous products during CO 2 RR. More importantly, a maximum partial current density of about 1 A cm −2 with a formate Faradaic efficiency (FE) of over 90% is achieved in a flow cell, distinguishing it from most of the reported Sn‐based electrocatalysts. These results highlight the strategic advantages of leveraging the inherent structure of nanomaterials for efficient CO 2 RR.