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  Metal-Specific Reactivity in Single-Atom Catalysts: CO Oxidation on 4d and 5d Transition Metals Atomically Dispersed on MgO

Sarma, B. B., Plessow, P. N., Agostini, G., Concepción, P., Pfänder, N., Kang, L., et al. (2020). Metal-Specific Reactivity in Single-Atom Catalysts: CO Oxidation on 4d and 5d Transition Metals Atomically Dispersed on MgO. Journal of the American Chemical Society, 142(35), 14890-14902. doi:10.1021/jacs.0c03627.

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Item Permalink: http://hdl.handle.net/21.11116/0000-0007-43BB-B Version Permalink: http://hdl.handle.net/21.11116/0000-0007-43BC-A
Genre: Journal Article

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 Creators:
Sarma, Bidyut B.1, Author              
Plessow, Philipp N.2, Author
Agostini, Giovanni3, Author
Concepción, Patricia4, Author
Pfänder, Norbert5, Author              
Kang, Liqun6, Author
Wang, Feng R.6, Author
Studt, Felix2, Author
Prieto, Gonzalo4, 7, Author              
Affiliations:
1Research Department Schüth, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1445589              
2Institute of Catalysis Research and Technology, Karlsruhe Institute of Technology, Hermann-von-Helmholtz-Platz 1, D-76344 Eggenstein-Leopoldshafen, Germany, ou_persistent22              
3ALBA Synchrotron Light Source, Carrer de la Llum 2-26, 08290, Cerdanyola del Vallès, Barcelona, Spain, ou_persistent22              
4ITQ Instituto de Tecnologı́a Quı́mica, Universitat Politècnica de València-Consejo Superior de Investigaciones Cientı́ficas (UPV-CSIC), Avenida de los Naranjos s/n, 46022 Valencia, Spain, ou_persistent22              
5Research Department Schlögl, Max Planck Institute for Chemical Energy Conversion, Max Planck Society, ou_3023874              
6Department of Chemical Engineering, University College London, Torrington Place, London, WC1E 7JE, United Kingdom, ou_persistent22              
7Research Group Prieto, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_2243639              

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 Abstract: Understanding and tuning the catalytic properties of metals atomically dispersed on oxides are major stepping-stones toward a rational development of single-atom catalysts (SACs). Beyond individual showcase studies, the design and synthesis of structurally regular series of SACs opens the door to systematic experimental investigations of performance as a function of metal identity. Herein, a series of single-atom catalysts based on various 4d (Ru, Rh, Pd) and 5d (Ir, Pt) transition metals has been synthesized on a common MgO carrier. Complementary experimental (X-ray absorption spectroscopy) and theoretical (Density Functional Theory) studies reveal that, regardless of the metal identity, metal cations occupy preferably octahedral coordination MgO lattice positions under step-edges, hence highly confined by the oxide support. Upon exposure to O2-lean CO oxidation conditions, FTIR spectroscopy indicates the partial deconfinement of the monatomic metal centers driven by CO at precatalysis temperatures, followed by the development of surface carbonate species under steady-state conditions. These findings are supported by DFT calculations, which show the driving force and final structure for the surface metal protrusion to be metal-dependent, but point to an equivalent octahedral-coordinated M4+ carbonate species as the resting state in all cases. Experimentally, apparent reaction activation energies in the range of 96 ± 19 kJ/mol are determined, with Pt leading to the lowest energy barrier. The results indicate that, for monatomic sites in SACs, differences in CO oxidation reactivity enforceable via metal selection are of lower magnitude than those evidenced previously through the mechanistic involvement of adjacent redox centers on the oxide carrier, suggesting that tuning of the oxide surface chemistry is as relevant as the selection of the supported metal.

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Language(s): eng - English
 Dates: 2020-04-022020-08-122020-09-02
 Publication Status: Published in print
 Pages: 13
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/jacs.0c03627
 Degree: -

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Title: Journal of the American Chemical Society
  Other : JACS
  Abbreviation : J. Am. Chem. Soc.
Source Genre: Journal
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Publ. Info: Washington, DC : American Chemical Society
Pages: - Volume / Issue: 142 (35) Sequence Number: - Start / End Page: 14890 - 14902 Identifier: ISSN: 0002-7863
CoNE: https://pure.mpg.de/cone/journals/resource/954925376870