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

Area of Science:

• Materials Science
• Surface Chemistry
• Computational Chemistry

Background:

• Photoinduced hot electrons are crucial for plasmon-driven catalysis.
• Atomically thin Ti3C2O2 possesses high carrier density and broad optical absorption, making it a potential plasmonic material.
• Limited studies exist on Ti3C2O2's plasmon resonance, hot-carrier generation, and catalytic activity.

Purpose of the Study:

• Investigate plasmon excitation and hot-carrier generation in Ti3C2O2 using computational methods.
• Explore the role of oxygen vacancies in Ti3C2O2's plasmonic catalytic performance.
• Provide fundamental insights into Ti3C2O2's plasmon-driven surface reactions.

Main Methods:

• Real-time time-dependent density functional theory (rt-TDDFT) was employed.
• Analysis of temporal dipole moment evolution to identify plasmon resonance and damping.
• Computational study of CO2 dissociation on Ti3C2O2 surfaces with varying oxygen vacancy concentrations.

Main Results:

• Plasmon resonance and strong nonradiative damping were observed in Ti3C2O2.
• Nonradiative damping effectively generates hot carriers from plasmonic excitation.
• Low oxygen vacancy concentration in Ti3C2O2 (Ov-Ti3C2O2) facilitates CO2 dissociation via hot electrons, significantly lowering the barrier.

Conclusions:

• Ti3C2O2 exhibits significant plasmonic properties suitable for catalysis.
• Hot carriers generated from plasmon damping play a key role in reducing CO2 dissociation barriers at oxygen vacancies.
• This work offers valuable insights for developing advanced plasmon-driven catalytic systems based on Ti3C2O2.