A‑Site Doping Promotes CO2 Activation and Prolongs Charge Carrier Lifetimes in SrTiO3: Insight from Quantum Dynamics

Using time-dependent density functional theory and nonadiabatic molecular dynamics, we systematically investigated the effect of A-site doping on the CO2 activation and charge carrier lifetimes in SrTiO3(STO). Our simulations revealed that A-site doping significantly enhances the chemical adsorption of CO2 on SrTiO3 surfaces, which is beneficial for promoting CO2 activation. Moreover, we found that A-site doping can efficiently stabilize the lowest unoccupied molecular orbital (LUMO) of CO2 near the conduction band minimum of STO, promoting the photogenerated electron transfer from the conduction band of STO to the CO2 LUMO. Importantly, A-site doping causes a significant nonadiabatic coupling reduction and prolongs the charge recombination time by a factor of 1.86 compared to the pristine STO. Our study clarifies the influencing mechanism of A-site doping on CO2 activation and charge carrier lifetimes and suggests important principles for the design of high-performance photocatalytic semiconductors.