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Journal Article

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


Reuter,  Karsten
Department of Chemistry and Catalysis Research Center, Technical University of Munich;
Theory, Fritz Haber Institute, Max Planck Society;

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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.

Cite as: https://hdl.handle.net/21.11116/0000-000A-0489-7
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.