Strong P-D Orbital Hybridization on Bismuth Nanosheets for High Performing CO 2 Electroreduction.

Single-atom alloys (SAAs) show great potential for a variety of electrocatalytic reactions. However, the atomic orbital hybridization effect of SAAs on the electrochemical reactions is unclear yet. Herein, we show the in situ confinement of vanadium/molybdenum atoms on bismuth nanosheet to create SAAs with rich grain boundaries. With the detailed analysis of microstructure and composition, the strong p-d orbital hybridization between bismuth and vanadium enables the exceptional electrocatalytic performance for carbon dioxide (CO 2 ) reduction with the Faradaic efficiency nearly 100% for C1 products in a wide potential range from -0.6 to -1.4 V, and a long-term electrolysis stability for 90 h. In-depth in situ investigations with theoretical computations reveal that the electron delocalization towards vanadium atoms via the p-d orbital hybridization evokes the bismuth active centers for efficient CO 2 activation via the σ-donation of O-to-Bi, thus reduces protonation energy barriers for formate production. With such fundamental understanding, SAA electrocatalyst was employed to fabricated the solar-driven electrolytic cell of CO 2 reduction and 5-hydroxymethylfurfural oxidation, achieving an outstanding 2,5-furandicarboxylic acid yield of 90.5%. This study demonstrates a feasible strategy to rationally design advanced SAA electrocatalysts via the basic principles of p-d orbital hybridization. This article is protected by copyright. All rights reserved.