Interfacial Engineering of Cu/ZnX ₂ O ₄ (X = Ga, Cr, Al) Spinel‐Supported Catalysts for Enhanced CO ₂ Hydrogenation to Methanol

ABSTRACT Catalytic hydrogenation of carbon dioxide to methanol is a key approach for carbon resource utilization and carbon neutrality. Spinel supports exhibit excellent thermal stability and structural robustness; however, their limited activity and selectivity hinder methanol production. Here, we propose an interface engineering strategy for Cu‐loaded spinel supports by systematically regulating the Cu‐support interface structure. To this end, we loaded Cu onto ZnGa 2 O 4 , ZnCr 2 O 4 , and ZnAl 2 O 4 spinels. The optimized Cu/ZnGa catalyst achieves a CO 2 conversion of 18.7% and a methanol selectivity of 45% (3 MPa, 240°C), while demonstrating excellent stability over 100 h of continuous operation. Characterization results from TEM, XPS, H 2 ‐TPR, and TPD indicate that the strong interaction between Cu and Ga facilitates the formation of highly dispersed Cu‐ZnGa interface sites. These interface sites significantly enhance the metal–support interaction, suppress the reverse water–gas shift (RWGS) side reaction, and thereby improve methanol selectivity. This study reveals the synergistic effects of the spinel support on Cu dispersion, interfacial electronic regulation, and surface adsorption site optimization, providing clear structure‐property guidance for designing highly active, highly selective, and long‐term stable catalysts for CO 2 hydrogenation to methanol.