Synergistic Catalysis of Ce-Ov-Cu Centers Enhances Integrated CO2 Capture and Hydrogenation to Methanol

Abstract CO2 hydrogenation to methanol represents a promising pathway for sustainable carbon recycling; however, conventional CO2-to-methanol processes face formidable challenges in achieving high CO2 conversion due to thermodynamic limitations. Herein, we engineered a series of CuZnCe catalysts for methanol synthesis via integrated CO2 capture and utilization (ICCU) strategy. The ICCU process achieved a methanol yield of 1.66 mmol/g (selectivity 36.5%) at 300 °C, which is close to the performance of Cu-based catalysts currently being studied, and showed an improvement in the utilization ratio of captured CO2 compared to the tested co-feeding mode. Ce incorporation into the CuZn catalyst intensified the electron transfer and generated abundant oxygen vacancies, and the resulting oxygen vacancy-rich surface promoted CO2 adsorption and conversion to formate intermediates, while the enriched Cu+ sites accelerated the rate-determining formate hydrogenation. Mechanistic investigations combining in situ DRIFTs and DFT calculations revealed that CuZnCe surfaces facilitate the rate-determining hydrogenation of HCO* intermediates. Moreover, the stabilized Cu+ sites under ICCU conditions promoted subsequent hydrogenation of CO-derived intermediates and suppressed CO desorption, realizing an increase in methanol selectivity from 23.8% to 36.5% compared to conventional processes.