2026-10-14T15:20:40Z https://www.scidb.cn/oai

10.57760/sciencedb.010ds 2026-08-31T10:55:37Z

2026-08-31 Boosting methanol synthesis in CO2 hydrogenation via modulating Cu Ce electronic interactions: Reactive hydroxyl-mediated HCO3* generation and enhanced HCOO* pathway doi:10.57760/sciencedb.010ds en Multi-component copper-based catalysts hold great promise for CO2 hydrogenation to methanol, yet the intricatecorrelation between catalyst structural features, the generation and transformation mechanism of key intermediates,and catalytic activity remains elusive. Herein, the intensity of Cu–Ce electronic interactions wasmodulated to synergistically optimize the distribution of active Cu species, oxygen vacancies (Oᵥ) and reactivesurface hydroxyl groups (OH*). Comprehensive characterizations (H2-TPR, Raman, and XPS) confirmed that anoptimal Cu–Ce electronic coupling, achieved via 5% Ce doping, promotes the formation of Ce3+ (Ce3+/(Ce3++Ce4+) = 43.6%), enriches Cu+ species (Cu+/(Cu0 + Cu+) = 61.4%), and increases the Oᵥ density (OII/(OII+ OI) = 76%) in the reduced catalyst. These structural and electronic optimizations synergistically enhance CO2activation and H2 dissociation, notably inducing the formation of reactive OH*. Mechanistic studies reveal thatthe reactive OH* directly mediates the reaction with adsorbed CO2 to generate HCO3* intermediates, whichfurther hydrogenate to HCOO* and *OCH3 via the formate pathway. Consequently, the optimized CZCe-5%catalyst achieves the superior methanol selectivity of 45.5%, a space-time yield (STYCH3OH) of 171.2 mg/gcat./hand excellent stability over 320 h of continuous reaction. This work reveals the reactive hydroxyl-mediatedHCO3* generation mechanism in CO2 hydrogenation and establishes a clear structure-mechanism-activity relationshipfor rational catalyst design. Copper-based catalysts; Active copper species; Multi-component catalytic systems; CO2 hydrogenation; Oxygen vacancies Peixiang Shi Liqiang Deng Ziyu Zhang Qian Jia Yanchun Li Yongzhen Wang Lei Li Congming Li PUBLIC https://creativecommons.org/licenses/by-sa/4.0/ dataset Science Data Bank