Synthesis of 2H/fcc-Heterophase AuCu Nanostructures for Highly Efficient Electrochemical CO₂ Reduction at Industrial Current Densities

Structural engineering of nanomaterials offers a promising way for developing high-performance catalysts towards catalysis. However, the delicate modulation of thermodynamically unfavorable nanostructures with unconventional phases still remains a challenge. Here, we report the synthesis of hierarchical AuCu nanostructures with hexagonal close-packed (2H-type)/face-centered cubic (fcc) heterophase, high-index facets, planar defects (e.g., stacking faults, twin boundaries, and grain boundaries), and tunable Cu content. The obtained 2H/fcc Au99Cu1 hierarchical nanosheets exhibit excellent performance for the electrocatalytic CO₂ reduction to produce CO, outperforming the 2H/fcc Au₉₁Cu₉ and fcc Au₉₉Cu₁. Our experimental results, especially those obtained by in situ differential electrochemical mass spectroscopy and attenuated total reflection Fourier-transform infrared spectroscopy, suggest that the enhanced catalytic performance of 2H/fcc Au₉₉Cu₁ arises from the unconventional 2H/fcc heterophase, high-index facets, planar defects, and appropriate alloying of Cu. Impressively, the 2H/fcc Au₉₉Cu₁ shows CO Faradaic efficiencies of 96.6% and 92.6% at industrial current densities of 300 mA cm⁻² and 500 mA cm⁻², respectively, as well as good durability, placing it among the best CO₂ reduction electrocatalysts for CO production. Our atomically structural regulation based on phase engineering of nanomaterials (PEN) provides an avenue for the rational design and preparation of high-performance electrocatalysts for various catalytic applications. © 2023 Wiley-VCH GmbH