Tuning the Electronic Environment of Cu Species in Cu‐ZnO/Sepiolite for Efficient and Selective Hydrogenation of CO ₂ to Methanol

ABSTRACT The ever‐increasing consumption of fossil hydrocarbons has led to elevated CO 2 emissions, causing a serious global energy crisis and environmental challenges. The production of value‐added chemicals via CO 2 hydrogenation represents a highly attractive strategy to address both environmental concerns and energy demands. Methanol, serving as both a chemical feedstock and a fuel, holds significant promise when produced from CO 2 and green hydrogen. In this work, the interaction between Cu‐ZnO and the support was precisely tuned through acid treatment of the sepiolite (ASep). The enriched surface hydroxyl groups on ASep promoted the formation of highly dispersed, small‐sized Cu species. This enhancement strengthened the strong metal–support interaction (SMSI) and hydrogen spillover effect, thereby boosting CO 2 conversion and the space‐time yield (STY) of methanol. Combined characterization and DFT calculations revealed that the modulated electronic state of Cu species leads to a downshift in the d‐band center of Cu, which facilitates hydrogen desorption and dissociation, ultimately promoting hydrogenation activity. This study advances the fundamental understanding of Cu‐based catalysts for CO 2 hydrogenation to methanol and highlights the importance of electronic environment modulation of the active phase.