Synergistic Catalysis of Ce-O _v -Cu Centers Enhances Integrated CO ₂ Capture and Hydrogenation to Methanol

CO 2 hydrogenation to methanol represents a promising pathway for sustainable carbon recycling; however, conventional CO 2 -to-methanol processes face formidable challenges in achieving high CO 2 conversion due to thermodynamic limitations. Herein, we engineered a series of CuZnCe catalysts for methanol synthesis via integrated CO 2 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 CO 2 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 CO 2 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.