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  Di- and Tetrameric Molybdenum Sulfide Clusters Activate and Stabilize Dihydrogen as Hydrides

Khare, R., Weindl, R., Jentys, A., Reuter, K., Shi, H., & Lercher, J. A. (2022). Di- and Tetrameric Molybdenum Sulfide Clusters Activate and Stabilize Dihydrogen as Hydrides. JACS Au, 2(3), 613-622. doi:10.1021/jacsau.1c00507.

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 Creators:
Khare, Rachit1, Author
Weindl, Roland1, Author
Jentys, Andreas1, Author
Reuter, Karsten1, 2, Author           
Shi, Hui3, Author
Lercher, Johannes A.1, 4, Author
Affiliations:
1Department of Chemistry and Catalysis Research Center, Technical University of Munich, 85747 Garching, Germany, ou_persistent22              
2Theory, Fritz Haber Institute, Max Planck Society, ou_634547              
3School of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou, 225009 Jiangsu China, ou_persistent22              
4Institute for Integrated Catalysis, Pacific Northwest National Laboratory, , Richland, Washington 99354, United States, ou_persistent22              

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 Abstract: NaY zeolite-encapsulated dimeric (Mo2S4) and tetrameric (Mo4S4) molybdenum sulfide clusters stabilize hydrogen as hydride binding to Mo atoms. Density functional theory (DFT) calculations and adsorption measurements suggest that stabilization of hydrogen as sulfhydryl (SH) groups, as typical for layered MoS2, is thermodynamically disfavored. Competitive adsorption of H2 and ethene on Mo was probed by quantifying adsorbed CO on partly hydrogen and/or ethene covered samples with IR spectroscopy. During hydrogenation, experiment and theory suggest that Mo is covered predominately with ethene and sparsely with hydride. DFT calculations further predict that, under reaction conditions, each MoxSy cluster can activate only one H2, suggesting that the entire cluster (irrespective of its nuclearity) acts as one active site for hydrogenation. The nearly identical turnover frequencies (24.7 ± 3.3 molethane·h–1·molcluster–1), apparent activation energies (31–32 kJ·mol–1), and reaction orders (∼0.5 in ethene and ∼1.0 in H2) show that the active sites in both clusters are catalytically indistinguishable.

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Language(s): eng - English
 Dates: 2021-11-102022-03-28
 Publication Status: Published online
 Pages: 10
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 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/jacsau.1c00507
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Title: JACS Au
  Abbreviation : JACS Au
Source Genre: Journal
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Publ. Info: Washington, DC : American Chemical Society
Pages: 10 Volume / Issue: 2 (3) Sequence Number: - Start / End Page: 613 - 622 Identifier: ISSN: 2691-3704
CoNE: https://pure.mpg.de/cone/journals/resource/2691-3704