Site-Selective Growth of fcc-2H-fcc Copper on Unconventional Phase Metal Nanomaterials for Highly Efficient Tandem CO₂ Electroreduction

Copper (Cu) nanomaterials are a unique kind of electrocatalysts for high-value multi-carbon production in carbon dioxide reduction reaction (CO₂RR), which holds enormous potential in attaining carbon neutrality. However, phase engineering of Cu nanomaterials remains challenging, especially for the construction of unconventional phase Cu-based asymmetric heteronanostructures. Here the site-selective growth of Cu on unusual phase gold (Au) nanorods, obtaining three kinds of heterophase fcc-2H-fcc Au–Cu heteronanostructures is reported. Significantly, the resultant fcc-2H-fcc Au–Cu Janus nanostructures (JNSs) break the symmetric growth mode of Cu on Au. In electrocatalytic CO₂RR, the fcc-2H-fcc Au–Cu JNSs exhibit excellent performance in both H-type and flow cells, with Faradaic efficiencies of 55.5% and 84.3% for ethylene and multi-carbon products, respectively. In situ characterizations and theoretical calculations reveal the co-exposure of 2H-Au and 2H-Cu domains in Au–Cu JNSs diversifies the CO* adsorption configurations and promotes the CO* spillover and subsequent C–C coupling toward ethylene generation with reduced energy barriers. © 2024 The Author(s). Advanced Materials published by Wiley-VCH GmbH.