Plasmonic Hot-Carrier Generation and Catalysis in Ti₃C₂O₂ from Real-Time TDDFT Simulations

Photoinduced hot electrons are central to plasmon-driven catalysis. Atomically thin Ti₃C₂O₂, with high carrier density and broad optical absorption, offers a promising platform for plasmon-driven reactions. However, comprehensive investigations of its plasmon resonance, hot-carrier generation, and plasmonic catalytic performance remain limited. In this work, real-time time-dependent density functional theory (rt-TDDFT) was employed to study Ti₃C₂O₂'s plasmon excitation and hot-carrier generation from nonradiative plasmon damping. The temporal evolution of the dipole moment reveals plasmon resonance in Ti₃C₂O₂, followed by strong plasmon damping that redistributes the stored energy to generate hot carriers. Ti₃C₂O₂ with low oxygen vacancy concentration (O_v-Ti₃C₂O₂) exhibits plasmonic behavior resembling the pristine surface, and the plasmon-generated hot electrons can markedly reduce the dissociation barrier of CO₂ at the oxygen vacancy. These findings provide fundamental insights into the plasmonic properties of Ti₃C₂O₂ and how they drive its catalytic performance in surface reactions, which is valuable for advancing plasmon-driven catalysis.