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

Developing high‐performance electrocatalysts for CO 2 reduction reaction (CO 2 RR) is vital in achieving a carbon‐neutral society by converting CO 2 into valuable chemicals. CO 2 RR 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 BiCl 3 , BiBr 3 , and BiI 3 in liquid phases. Especially, bismuthene‐I derived from BiI 3 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 CO 2 RR overpotential, suppress the competitive hydrogen evolution reaction, and facilitate electron donation during CO 2 electrocatalysis. The bismuthene‐I realized low overpotential, high selectivity and wide working potential range simultaneously for electrochemical CO 2 RR. This work unfolds the broader plausibility of facilely reducing precursors for the scalable fabrication of high‐performing CO 2 RR electrocatalysts.