Bi₂O₃/BiO₂ Nanoheterojunction for Highly Efficient Electrocatalytic CO₂ Reduction to Formate.

Abstract

Heterostructure engineering plays a vital role in regulating the material interface, thus boosting the electron transportation pathway in advanced catalysis. Herein, a novel Bi₂O₃/BiO₂ heterojunction catalyst was synthesized via a molten alkali-assisted dealumination strategy and exhibited rich structural dynamics for an electrocatalytic CO₂ reduction reaction (ECO₂RR). By coupling in situ X-ray diffraction and Raman spectroscopy measurements, we found that the as-synthesized Bi₂O₃/BiO₂ heterostructure can be transformed into a novel Bi/BiO₂ Mott-Schottky heterostructure, leading to enhanced adsorption performance for CO₂ and *OCHO intermediates. Consequently, high selectivity toward formate larger than 95% was rendered in a wide potential window along with an optimum partial current density of -111.42 mA cm^-2 that benchmarked with the state-of-the-art Bi-based ECO₂RR catalysts. This work reports the construction and fruitful structural dynamic insights of a novel heterojunction electrocatalyst for ECO₂RR, which paves the way for the rational design of efficient heterojunction electrocatalysts for ECO₂RR and beyond.