Effect of the ZrO2 phase on the structure and behavior of supported Cu catalysts for ethanol conversion

• Published in: Journal of catalysis Vol. 307; pp. 1 - 17
• Main Authors: Sato, A.G., Volanti, D.P., Meira, D.M., Damyanova, S., Longo, E., Bueno, J.M.C.
• Format: Journal Article
• Language: English
• Published: Amsterdam Elsevier Inc 01.11.2013; Elsevier; Elsevier BV
• Subjects: acetaldehyde; active sites; Catalysis; Catalysts; Characterization; Chemical synthesis; Chemistry; Copper; Cu/ZrO2 catalysts; electron transfer; Ethanol; Ethanol dehydrogenation; Ethyl acetate; Exact sciences and technology; General and physical chemistry; oxygen; Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry; X-ray photoelectron spectroscopy; Characterization; Ethyl acetate; Cu/ZrO2 catalysts; Ethanol dehydrogenation; Binary compound; Ethanol; Cu/ZrO; Transition element compounds; Alcohol; Transition metal; Acetate; Conversion; Supported catalyst; Heterogeneous catalysis; Zirconium oxide; Dehydrogenation; catalysts; Alkanol; Copper; Structure
• ISSN: 0021-9517; 1090-2694
• DOI: 10.1016/j.jcat.2013.06.022

Effect of ZrO2 phases on the formation of acetaldehyde and ethyl acetate from ethanol over Cu/ZrO2 catalysts. [Display omitted] •Cu catalysts supported on am-, m-, and t-ZrO2 for selective ethanol conversion.•Cu/m-ZrO2 catalyst shows a high selectivity to ethyl acetate.•The high rate of ethyl acetate is defined by oxygen mobility from bulk ZrO2 to Cu.•A high rate for acetaldehyde formation is observed for Cu/t-ZrO2 catalyst. The effect of amorphous (am-), monoclinic (m-), and tetragonal (t-) ZrO2 phase on the physicochemical and catalytic properties of supported Cu catalysts for ethanol conversion was studied. The electronic parameters of Cu/ZrO2 were determined by in situ XAS, and the surface properties of Cu/ZrO2 were defined by XPS and DRIFTS of CO-adsorbed. The results demonstrated that the kind of ZrO2 phase plays a key role in the determination of structure and catalytic properties of Cu/ZrO2 catalysts predetermined by the interface at Cu/ZrO2. The electron transfer between support and Cu surface, caused by the oxygen vacancies at m-ZrO2 and am-ZrO2, is responsible for the active sites for acetaldehyde and ethyl acetate formation. The highest selectivity to ethyl acetate for Cu/m-ZrO2 catalyst up to 513K was caused by the optimal ratio of Cu0/Cu+ species and the high density of basic sites (O2−) associated with the oxygen mobility from the bulk m-ZrO2.