Halide precursor reduction strategy to modulate bismuthene with high selectivity and wide potential window for electrochemical CO2 reduction.

Developing high‐performance electrocatalysts for CO2 reduction reaction (CO2RR) is vital in achieving a carbon‐neutral society by converting CO2 into valuable chemicals. CO2RR electrocatalyst with lower overpotential, higher selectivity and wider working potential range is urgently desired, but it is still challenging to realize these factors simultaneously. Here, high‐performance bismuthene‐based electrocatalysts were synthesized by reducing bismuth precursors like BiCl3, BiBr3, and BiI3 in liquid phases. Especially, bismuthene‐I derived from BiI3 showed a nanosheet morphology (around four‐layer) with significantly enhanced (110) surfaces. It enabled an ultrawide potential window (0.7 V) for high formate selectivity (>90%) in a H‐type cell and achieved an ultralow potential (−0.46 V vs. reversible hydrogen electrode) to attain a current density of 200 mA cm−2 in a gas‐diffusion flow cell. The prominent long‐term operational capability of bismuthene‐I was demonstrated in both H‐type and gas‐diffusion cells. Density functional theory calculations revealed that bismuthene‐I possessed abundant topological Bi(110) surfaces states that can reduce the CO2RR overpotential, suppress the competitive hydrogen evolution reaction, and facilitate electron donation during CO2 electrocatalysis. The bismuthene‐I realized low overpotential, high selectivity and wide working potential range simultaneously for electrochemical CO2RR. This work unfolds the broader plausibility of facilely reducing precursors for the scalable fabrication of high‐performing CO2RR electrocatalysts. [ABSTRACT FROM AUTHOR]