Voltage-dependent reconstruction of layered Bi$_2$WO$_6$ and Bi$_2$MoO$_6$ photocatalysts and its influence on charge separation for water splitting

TL;DR

This study investigates how voltage influences the surface reconstruction of layered Bi2WO6 and Bi2MoO6 photocatalysts and how this affects their charge separation efficiency for water splitting.

Contribution

It provides a detailed molecular-level analysis of surface stability and charge distribution at the semiconductor–solution interface under different voltages and pH conditions.

Findings

Voltage-dependent surface reconstruction affects charge separation.

Facet-dependent photocatalytic activity explained by surface stability.

Self-consistent continuum solvation model used for interface analysis.

Abstract

We study the surface stability of the layered bismuth-oxide Bi$_2$WO$_6$ and Bi$_2$MoO$_6$ photocatalysts, which belong to the series of Aurivillius (Bi$_2$A$_{n-1}$B$_{n}$O$_{3n+3}$) perovskites and have been proposed as efficient visible-light absorbers, due to favorable electronic hybridization induced by the Bi 6s and 6p orbitals. We present a Newton--Raphson optimization of the charge distribution at the semiconductor--solution interface using the self-consistent continuum solvation (SCCS) model to describe the influence of the aqueous environment. Our analysis provides a description of the charged interface under controlled pH and applied voltage, and offers a molecular interpretation of the competing structural and electrical factors that underlie the facet-dependent photocatalytic activity of layered Bi$_2$A$_{n-1}$B$_{n}$O$_{3n+3}$ compounds.