La‐Promoted Conversion of Reaction Intermediates Over H 3 BTC‐Modified ZrO X /Cu Catalysts for Methanol Synthesis From CO 2 Hydrogenation

ABSTRACT Given the growing importance of CO 2 hydrogenation to methanol for future energy systems, extensive research focuses on identifying the active sites, interactions, and reaction pathways. However, the formation and conversion of intermediates are unavoidable in this process. In this study, a series of La‐ZrO X /Cu catalysts are synthesized by co‐precipitation followed by treatment with H 3 BTC. In situ XAS and in situ XPS results demonstrate that the coordination environment of Cu and the Cu° fraction are significantly modified upon H 3 BTC treatment, rendering the catalysts highly sensitive to the reaction atmosphere and conditions. This improvement is lead not only to the significant enhancement of CO 2 adsorption and activation on the La‐modified Cu surface, together with the increased proportion of Cu + and low‐coordinated Cu, but also to the synergistic effect between an appropriate proportion of Zr q+ and the enriched Cu‐ZrO 2 interface with oxygen vacancies. As a result, a high methanol selectivity of 92.98% is obtained, while the CO 2 conversion is increased by 2.38 times compared with that of the ZrO X /Cu. This work therefore provides a viable strategy for generating uniformly dispersed active sites and, with the assistance of La, improving the conversion of intermediates in CO 2 hydrogenation, rather than creating new reaction pathways.