Atomic Layer Deposition ZnO Over-Coated Cu/SiO2 Catalysts for Methanol Synthesis from CO2 Hydrogenation

Abstract

Cu-ZnO-based catalysts are of importance for CO2 utilization to synthesize methanol. However, the mechanisms of CO2 activation, the split of the C=O double bond, and the formation of C-H and O-H bonds are still debatable. To understand this mechanism and to improve the selectivity of methanol formation, the combination of strong electronic adsorption (SEA) and atomic layer deposition (ALD) was used to form catalysts with Cu nanoparticles surrounded by a non-uniform ZnO layer, uniform atomic layer of ZnO, or multiple layers of ZnO on porous SiO2. N2 adsorption, H2 temperature-programmed reduction (H2-TPR) X-ray diffraction (XRD), transmission electron microscope (TEM), energy-dispersive X-ray spectroscopy (EDX), CO-chemisorption, CO2 temperature-programmed desorption (CO2-TPD), X-ray adsorption near edge structure (XANES), and extended X-ray absorption fine structure (EXAFS) were used to characterize the catalysts. The catalyst activity was correlated to the number of metallic sites. The catalyst of 5 wt% Cu over-coated with a single atomic layer of ZnO exhibited higher methanol selectivity. This catalyst has comparatively more metallic sites (smaller Cu particles with good distribution) and basic site (uniform ZnO layer) formation, and a stronger interaction between them, which provided necessary synergy for the CO2 activation and hydrogenation to form methanol.