Symmetry‐Broken Au–Cu Heterostructures and their Tandem Catalysis Process in Electrochemical CO2 Reduction

Symmetry‐breaking synthesis of colloidal nanocrystals with desired structures and properties has aroused widespread interest in various fields, but the lack of robust synthetic protocols and the complex growth kinetics limit their practical applications. Herein, a general strategy is developed to synthesize the Au–Cu Janus nanocrystals (JNCs) through the site‐selective growth of Cu nanodomains on Au nanocrystals, which is directed by the substantial lattice mismatch between them, with the assistance of judicious manipulation of the growth kinetics. This strategy can work on Au nanocrystals with different architectures for the achievement of diverse asymmetric Au–Cu hybrid nanostructures. Of particular note, the obtained Au nanobipyramids (Au NBPs)‐based JNCs facilitate the conversion of CO2 to C2 hydrocarbon production during electrocatalysis, with the Faradaic efficiency and maximum partial current density being 4.1‐fold and 6.4‐fold higher than those of their monometallic Cu counterparts, respectively. The excellent electrocatalytic performances benefit from the special design of the Au–Cu Janus architectures and their tandem catalysis mechanism as well as the high‐index facets on Au nanocrystals. This research provides a new approach to synthesize various hybrid Janus nanostructures, facilitating the study of structure‐function relationship in the catalytic process and the rational design of efficient heterogeneous electrocatalysts. A general strategy is developed to grow Cu nanodomains site selectively on Au nanocrystals. This strategy works on Au nanocrystals from 0D, 1D, to 2D for the achievement of diverse asymmetric Au−Cu hybrid nanostructures. This spatial‐separation design with high‐index facets on Au nanocrystals facilitates the conversion of CO2 to C2 product through the tandem catalysis mechanism.