Regulating CO ₂ hydrogenation pathways to methanol over Cu‐based catalysts via Y modification

Precise modulation of Cu‐based catalysts is crucial yet challenging. Herein, Y was introduced into Cu‐ZnO catalysts to tune their electronic and structural features. Characterizations including in situ XRD, N 2 O titration, and TEM‐EDS revealed that Y addition reduced metallic Cu nanoparticle size and enhanced dispersion within a Y‐modified ZnO matrix, suggesting increased density of Cu + –O–Zn δ+ interfacial sites. Quasi‐ in situ XPS revealed that Y incorporation induces charge transfer, decreasing the electron density on surface Cu 0 and Cu + . In situ DRIFTS analysis identified the *CO pathway on Cu 0 and the formate pathway on Cu + –O–Zn δ+ sites. The reduced charge density of Cu 0 suppressed the *CO pathway, while electron–deficient Cu + promoted the transformation of bidentate formate into a more active monodentate configuration. Consequently, Y‐induced electronic modification enhanced methanol turnover frequency from 15.3 to 19.2 h −1 by regulating CO 2 hydrogenation pathways. This strategy may guide rational catalyst design and provide insights into CO2 hydrogenation.