4f-Electron localization in Ce-embedded Co₆Te₈ clusters for enhanced CO₂ reduction catalysis

Area of Science:

• Computational chemistry
• Materials science
• Catalysis

Background:

• The CO2 reduction reaction (CO2RR) is crucial for sustainable energy.
• Developing efficient molecular catalysts for CO2RR remains a challenge.

Purpose of the Study:

• Investigate CO2RR on metal-embedded Co6Te8(PH3)5 chalcogenide clusters.
• Understand the role of f and d orbitals in catalytic activity.
• Identify high-performance molecular catalysts for CO2RR.

Main Methods:

• Density Functional Theory (DFT) calculations.
• Systematic analysis of electronic structure and orbital interactions.
• Evaluation of reaction pathways and energy barriers for CO2RR.

Main Results:

• Metal embedding tuned the electronic structure and reactivity of Co6Te8 clusters.
• Cerium (Ce) embedding (Ce@Co6Te8(PH3)5) showed the lowest endothermic energy for CO2RR.
• Ce 4f states enhanced π* antibonding population and Pauli repulsion, facilitating CO desorption.
• 4f electron localization narrowed the HOMO-LUMO gap, increasing electronic reactivity.

Conclusions:

• 4f electron localization is a key descriptor for designing efficient molecular catalysts.
• Ce@Co6Te8(PH3)5 demonstrates superior catalytic performance for CO2RR.
• Metal-embedded chalcogenide clusters offer a promising platform for CO2RR catalyst development.