The higher electron availability at TiO1.69 strengthens the interaction with Rh, leading to more robust binding compared to the less-reduced TiO1.98 surface, where fewer Ti 3+ On the Rh/TiO1.98 surface, the surface oxygen vacancy at the bridge site serves as the primary binding site for the CO2 molecule. Here, one oxygen atom of CO2 binds at the vacancy site while the carbon atom coordinates with the Rh atom. This interaction induces a bent configuration of the CO2 molecule, a structural prerequisite for its activation. On the more reduced Rh/TiO1.69 surface, CO2 also adopts a bent geometry.