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

Abstract

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.