CO₂ Hydrogenation to Methanol over Cd₄/TiO₂ Catalyst: Insight into Multifunctional Interface

Supported metal catalysts have shown to be efficient for CO₂ conversion due to their multifunctionality and high stability. Herein, we have combined density functional theory calculations with microkinetic modeling to investigate the catalytic reaction mechanisms of CO₂ hydrogenation to CH₃OH over a recently reported catalyst of Cd₄/TiO₂. Calculations reveal that the metal-oxide interface is the active center for CO₂ hydrogenation and methanol formation via the formate pathway dominates over the reverse water-gas shift (RWGS) pathway. Microkinetic modeling demonstrated that formate species on the surface of Cd₄/TiO₂ is the relevant intermediate for the production of CH₃OH, and CH₂O^# formation is the rate-determining step. These findings demonstrate the crucial role of the Cd-TiO₂ interface for controlling the CO₂ reduction reactivity and CH₃OH selectivity.