Promoted chemoselective crotonaldehyde hydrogenation on zirconia-doped SiO2 supported Ag catalysts: Interfacial catalysis over ternary Ag-ZrO2-SiO2 interfaces

摘要

In gas-phase chemoselective hydrogenation of crotonaldehyde on Ag-based catalysts, zirconia doping on silica supports was found to improve catalytic performance in terms of unsaturated alcohol selectivity, hydrogenation activity, and stability. The surface modification of silica by zirconia doping favors the fine dispersion of Ag species due to the enhanced quantity and strength of surface acid sites, which enable construction of abundant catalytic sites effective for C=O bond hydrogenation. High crotyl alcohol selectivity, exceeding 80%, and significant inhibition of monohydrogenation on the C=C bond were observed on the optimal Ag/Zr-SiO2 catalyst. Dynamic O-2 chemisorption measurement revealed that the pure Ag powders did not chemisorb O-2 irreversibly under 323 K but SiO2 or Zr-SiO2 supported Ag catalysts did. The amounts of Ag active for O-2 chemisorption, which are at least one order of magnitude lower than that of surface Ag derived from TEM and XRD characterizations, match well with the perimeter interface Ag of hemispherical particles. A strong correlation between hydrogenation activity and O-2 uptake on those Ag/SiO2 and Ag/Zr-SiO2 catalysts with different Ag dispersions and deactivation degrees was observed, implying that the effective catalytic sites for crotonaldehyde chemoselective hydrogenation may originate from accessible interface sites with unique redox properties. Catalyst induction and deactivation were observed on both Ag/SiO2 and Ag/Zr-SiO2 catalysts in real catalytic operation. Changes in metal stable interface structure, rather than metal aggregation and coagulation, are assumed to be the main cause of irreversible catalyst deactivation, because the apparent Ag particle sizes changed slightly, but the oxygen chemisorption ability deteriorated considerably. Electropositive Ag sites interacting with neighboring oxygen from oxide supports at the ternary Ag-ZrO2-SiO2 interface are proposed to account for highly selective C=O bond hydrogenation t