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Counting of Oxygen Defects versus Metal Surface Sites in Methanol Synthesis Catalysts by Different Probe Molecules
Authors:Matthias B Fichtl  Julia Schumann  Igor Kasatkin  Nikolas Jacobsen  Malte Behrens  Robert Schlögl  Martin Muhler  Olaf Hinrichsen
Institution:1. Catalysis Research Center and Chemistry Department, Technische Universit?t München, Lichtenbergstrasse 4, 85748 Garching bei München (Germany);2. Department of Inorganic Chemistry, Fritz‐Haber‐Institut der Max‐Planck‐Gesellschaft, Faradayweg 4–6, 14195 Berlin (Germany);3. Saint Petersburg State University, Research Centre for X‐ray Diffraction Studies, 199155 Decabristov lane 16, St. Petersburg (Russia);4. Clariant Produkte (Deutschland) GmbH, BU Catalysts, Waldheimer Strasse 13, 83052 Bruckmühl (Germany);5. Ruhr‐Universit?t Bochum, Fakult?t für Chemie und Biochemie, Universit?tsstrasse 150, 44780 Bochum (Germany)
Abstract:Different surface sites of solid catalysts are usually quantified by dedicated chemisorption techniques from the adsorption capacity of probe molecules, assuming they specifically react with unique sites. In case of methanol synthesis catalysts, the Cu surface area is one of the crucial parameters in catalyst design and was for over 25 years commonly determined using diluted N2O. To disentangle the influence of the catalyst components, different model catalysts were prepared and characterized using N2O, temperature programmed desorption of H2, and kinetic experiments. The presence of ZnO dramatically influences the N2O measurements. This effect can be explained by the presence of oxygen defect sites that are generated at the Cu‐ZnO interface and can be used to easily quantify the intensity of Cu‐Zn interaction. N2O in fact probes the Cu surface plus the oxygen vacancies, whereas the exposed Cu surface area can be accurately determined by H2.
Keywords:catalyst–  support interactions  copper  heterogeneous catalysis  methanol  oxygen defect sites
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