Oxygen Vacancies Promoted Hydrogenation of MEA‐Captured‐CO₂ to Methanol

Integrated CO 2 capture and hydrogenation to methanol is highly likely an economically advantageous technology for flue gas decarbonization and decentralized energy storage. However, highly efficient hydrogenation catalysts are yet to be explored. Herein, we report an efficient metal oxides‐carbon‐composite supported metal catalyst, Pt/C SAP ‐TiO 2 /CeO 2 , with abundant oxygen vacancies for the highly enhanced hydrogenation of MEA‐captured‐CO 2 to methanol. An increase in the concentration of oxygen vacancies through catalysts Pt/TiO 2 , Pt/TiO 2 ‐CeO 2 , and Pt/C SAP ‐TiO 2 /CeO 2 contributes to an improvement in methanol turnovers and yields, as evidenced by x‐ray diffraction (XRD), Brunauer–Emmett–Teller (BET), scanning electron microscopy (SEM), attenuated total reflectance–Fourier‐transform infrared spectroscopy (ATR–FTIR), CO 2 ‐temperature programmed desorption (CO 2 ‐TPD), O 1s X‐ray photoelectron spectroscopy (XPS), electron paramagnetic resonance (EPR), and catalysis experiments. The optimized supramolecular catalyst Pt/C SAP ‐TiO 2 /CeO 2 exhibited the best activity, with 193% higher TONs than the parent Pt/TiO 2 catalyst (45.3 versus 23.4). A novel supramolecular heterogeneous catalysis mechanism utilizing the surface oxygen vacancies for absorption, preorganization, activation, and conversion of the key challenging formamide intermediate to methanol is proposed.