CO 2 Hydrogenation to Methanol over Cd 4 /TiO 2 Catalyst: Insight into Multifunctional Interface.

Supported metal catalysts have shown to be efficient for CO 2 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 CO 2 hydrogenation to CH 3 OH over a recently reported catalyst of Cd 4 /TiO 2 . Calculations reveal that the metal-oxide interface is the active center for CO 2 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 Cd 4 /TiO 2 is the relevant intermediate for the production of CH 3 OH, and CH 2 O # formation is the rate-determining step. These findings demonstrate the crucial role of the Cd-TiO 2 interface for controlling the CO 2 reduction reactivity and CH 3 OH selectivity.