Synergistic Effect of Fe Doping and Oxygen Vacancies on the Optical Properties and CO₂ Reduction Mechanism of Bi₄O₅Br₂

In this study, the synergistic effects of Fe doping and oxygen vacancies on the structural, electronic, and optical properties of Bi₄O₅Br₂, as well as their influence on the photocatalytic CO₂ reduction mechanism, were systematically explored through first-principles calculations. The results reveal that Fe-doped, oxygen-defective, and Fe–Vo co-modified Bi₄O₅Br₂ systems exhibit excellent thermodynamic and dynamic stability. Oxygen vacancies introduce defect states near the Fermi level, narrowing the band gap and enhancing charge localization and CO₂ adsorption, while Fe doping induces strong spin polarization and introduces Fe <i>3d</i> impurity levels that effectively couple with O <i>2p</i> orbitals, promoting charge transfer and visible-light absorption. The coexistence of Fe dopants and oxygen vacancies produces a significant synergistic effect, forming a continuous energy-level bridge that enhances charge separation and broadens the light absorption range. Gibbs free energy analyses further demonstrate that the Fe–Vo–BOB system exhibits the lowest energy barriers and the most favorable thermodynamics for CO₂-to-CO conversion. This study provides deep insight into the defect–dopant synergy in Bi₄O₅Br₂ and offers valuable theoretical guidance for engineering highly efficient visible-light-driven photocatalysts in solar energy conversion and environmental remediation.