Multi-species defect engineering synergistic localized surface plasmon resonance boosting photocatalytic CO₂ reduction

Inadequate charge carrier kinetics and a scarcity of active sites still challenge photocatalytic CO₂ reduction reaction (CO₂RR). We exploit the synergy between multi-species defect engineering and the localized surface plasmon resonance (LSPR) effect in Bi/BiV_1-mO_4-m to address these limitations. Theoretical calculations show that V and O defects collectively modulate the work function of BiVO₄, which induces hot electrons to transfer from Bi nanoparticles to BiV_1-mO_4-m. These electrons are then captured by O defects, confirmed by femtosecond transient absorption spectroscopy. Electron density is significantly increased at the O defects, enhancing CO₂ adsorption and establishing it as a new reaction site. Bi/BiV_1-mO_4-m achieves photocatalytic CO₂RR in pure water; Bi/BiV_1-mO_4-m achieves direct solar-driven photocatalytic CO₂RR with a CO yield of 501 μmol/g/h under concentrated sunlight.