Lead-Free Perovskite Cs3Bi2Br9/Porous BiOCl S-Scheme Heterostructure with Greatly Enhanced Performance for CO2 Reduction

ACS Appl Mater Interfaces. 2025 Jun 29. doi: 10.1021/acsami.5c07834. Online ahead of print.

Abstract

BiOCl has emerged as a promising photocatalyst for CO2 reduction for its non-toxicity and robust stability. However, the wide bandgap and fast recombination of photogenerated electron-hole pairs have hindered its practical application. Herein, a series of photocatalysts based on the heterojunction of porous BiOCl with a bandgap of 2.65 eV and lead-free perovskite Cs3Bi2Br9 are designed and fabricated via a simple method combining hydrothermal and dipping processes. The optimized sample exhibits a greatly improved CO2-CO conversion rate of 25.5 μmol g-1 h-1 with high selectivity and electron consumption value of 64.6 μmol g-1 h-1 under simulated sunlight, which are 9.1 (11.1) and 4.0 (6.0) times higher than those of pristine BiOCl (Cs3Bi2Br9), respectively. In-depth analysis based on experimental results and first-principles calculations reveals that the improved photocatalytic activity is caused by the enhanced charge separation and transfer in the heterojunction via a S-scheme mechanism and the decreased reaction barrier for the CO2 reduction by the heterojunction surface. This work gives insights into the S-scheme photocatalyst based on porous BiOCl and lead-free perovskite and is useful for design and application of environmentally friendly high-performance photocatalysts.

Keywords: BiOCl; CO2 reduction; S-scheme; heterojunction; lead-free perovskite.