Сибирский федеральный университет

Тип публикации: статья из журнала

Год издания: 2012

Идентификатор DOI: 10.1039/c2cp23648f

Аннотация: Reverse'' spillover of hydrogen from hydroxyl groups of the support onto supported transition metal clusters, forming multiply hydrogenated metal species, is an essential aspect of various catalytic systems which comprise small, highly active transition metal particles on a support with a high surface area. We review and analyze the results of our computational model studies related to reverse hydrogen spillover, interpreting available structural and spectral data for the supported species and examining the relationship between metal-support and metal-hydrogen interactions. On the examples of small clusters of late transition metals, adsorbed in zeolite cavities, we showed with computational model studies that reverse spillover of hydrogen is energetically favorable for late transition metals, except for Au. This preference is crucial for the chemical reactivity of such bifunctional catalytic systems because both functions, of metal species and of acidic sites, are strongly modified, in some cases even suppressed - due to partial oxidation of the metal cluster and the conversion of protons from acidic hydroxyl groups to hydride ligands of the metal moiety. Modeling multiple hydrogen adsorption on metal clusters allowed us to quantify how (i) the support affects the adsorption capacity of the clusters and (ii) structure and oxidation state of the metal moiety changes upon adsorption. In all models of neutral systems we found that the metal atoms are partially positively charged, compensated by a negative charge of the adsorbed hydrogen ligands and of the support. In a case study we demonstrated with calculated thermodynamic parameters how to predict the average hydrogen coverage of the transition metal cluster at a given temperature and hydrogen pressure. [Roesch, Notker] Tech Univ Munich, Dept Chem, D-85747 Garching, Germany; [Roesch, Notker] Tech Univ Munich, Catalysis Res Ctr, D-85747 Garching, Germany; [Vayssilov, Georgi N.; Petrova, Galina P.; St Petkov, Petko] Univ Sofia, Fac Chem, BU-1126 Sofia, Bulgaria; [Shor, Elena A. Ivanova; Nasluzov, Vladimir A.; Shor, Alexei M.] Russian Acad Sci, Inst Chem & Chem Technol, Krasnoyarsk 660049, Russia; [Shor, Elena A. Ivanova; Nasluzov, Vladimir A.; Shor, Alexei M.] Siberian Fed Univ, Krasnoyarsk 660041, Russia Rosch, N (reprint author), Tech Univ Munich, Dept Chem, D-85747 Garching, Germany. roesch@mytum.de Vayssilov, Georgi/B-9330-2008; Shor, Elena/P-3337-2016; Petkov, Petko/R-4168-2016 Vayssilov, Georgi/0000-0002-5185-8002; Petkov, Petko/0000-0001-6315-8591 Deutsche Forschungsgemeinschaft; Alexander von Humboldt Foundation; Volkswagen Foundation; Fonds der Chemischen Industrie (Germany); Bulgarian National Science Fund [DCVP 02/1, DCVP 02/2]; BeyondEverest; Presidium of the Russian Academy of Sciences This work was supported by Deutsche Forschungsgemeinschaft, Alexander von Humboldt Foundation, Volkswagen Foundation, Fonds der Chemischen Industrie (Germany), and the Bulgarian National Science Fund (Contracts DCVP 02/1 and DCVP 02/2). GNV and PSP are grateful for support by the FP7 project BeyondEverest. The Russian team thanks the Presidium of the Russian Academy of Sciences for financial support (Priority Program 22.51). We also acknowledge generous computing resources at Leibniz Rechenzentrum Munchen. 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Chem. Chem. Phys. 2012 14 17 5879 5890 10.1039/c2cp23648f 12 Chemistry, Physical; Physics, Atomic, Molecular & Chemical Chemistry; Physics 919WU WOS:000302363700001 22353996

Журнал: Physical Chemistry Chemical Physics

Выпуск журнала: Vol. 14, Is. 17

Номера страниц: 5879-5890

ISSN журнала: 14639076

• Vayssilov G.N. (Faculty of Chemistry,University of Sofia)
• Petrova G.P. (Faculty of Chemistry,University of Sofia)
• Petkov P.S. (Faculty of Chemistry,University of Sofia)
• Shor E.A.I. (Siberian Federal University)
• Nasluzov V.A. (Siberian Federal University)
• Shor A.M. (Siberian Federal University)
• Rosch N. (Technische Universitat Munchen,Department Chemie,Catalysis Research Center)

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