Linear-Structure Single-Atom Gold(I) Catalyst for Dehydrogenative Coupling of Organosilanes with Alcohols

Ravishankar G. Kadam; Miroslav Medved’; Subodh Kumar; Dagmar Zaoralová; Giorgio Zoppellaro; Zdeněk Bad’ura; Tiziano Montini; Aristides Bakandritsos; Emiliano Fonda; Ondřej Tomanec; Michal Otyepka; Rajender S. Varma; Manoj B. Gawande; Paolo Fornasiero; Radek Zbořil

doi:10.1021/acscatal.3c03937

Linear-Structure Single-Atom Gold(I) Catalyst for Dehydrogenative Coupling of Organosilanes with Alcohols

Ravishankar G. Kadam, Miroslav Medved’, Subodh Kumar, Dagmar Zaoralová, Giorgio Zoppellaro, Zdeněk Bad’ura, Tiziano Montini, Aristides Bakandritsos, Emiliano Fonda, Ondřej Tomanec, Michal Otyepka, Rajender S. Varma, Manoj B. Gawande, Paolo Fornasiero, Radek Zbořil

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Abstract

A strategy for the synthesis of a gold-based single-atom catalyst (SAC) via a one-step room temperature reduction of Au(III) salt and stabilization of Au(I) ions on nitrile-functionalized graphene (cyanographene; G-CN) is described. The graphene-supported G(CN)-Au catalyst exhibits a unique linear structure of the Au(I) active sites promoting a multistep mode of action in dehydrogenative coupling of organosilanes with alcohols under mild reaction conditions as proven by advanced XPS, XAFS, XANES, and EPR techniques along with DFT calculations. The linear structure being perfectly accessible toward the reactant molecules and the cyanographene-induced charge transfer resulting in the exclusive Au(I) valence state contribute to the superior efficiency of the emerging two-dimensional SAC. The developed G(CN)-Au SAC, despite its low metal loading (ca. 0.6 wt %), appear to be the most efficient catalyst for Si-H bond activation with a turnover frequency of up to 139,494 h^-1 and high selectivities, significantly overcoming all reported homogeneous gold catalysts. Moreover, it can be easily prepared in a multigram batch scale, is recyclable, and works well toward more than 40 organosilanes. This work opens the door for applications of SACs with a linear structure of the active site for advanced catalytic applications.

Original language	English
Pages (from-to)	16067-16077
Number of pages	11
Journal	ACS Catalysis
Volume	13
Issue number	24
DOIs	https://doi.org/10.1021/acscatal.3c03937
State	Published - 15 Dec 2023
Externally published	Yes

Bibliographical note

Publisher Copyright:
© 2023 The Authors. Published by American Chemical Society.

Funding

R.G.K. acknowledges the support from ERDF/ESF project TECHSCALE (No. CZ.02.01.01/00/22_008/0004587). S.K. acknowledges financial support from institutional sources of the Department of Inorganic Chemistry, Palacký University Olomouc, Czech Republic. The authors acknowledge SOLEIL for provision of synchrotron radiation facilities. T.M. acknowledges financial support from Ministry for University and Research (PRIN project no. 2017PBXPN4). P.F. acknowledges European Community (Project HORIZON-WIDERA-2021-ACCESS-03-01 grant no. 101079384) for financial support. Z.B. and G.Z. acknowledges Project APPROACH no. 101120397 and HORIZON-WIDERA-2022-TALENTS. M.O. acknowledges the ERC grant (no. 683024) from the H2020. The COST Action CA21101 is also acknowledged. R.Z. and A.B. thanks the Czech Science Foundation for financial support (project no. 19-27454X). We thank D. Milde (ICP), J. Stráská (TEM), J. Kaslik (XRD), and M. Petr (XPS) for the measurements. This article has been produced with the financial support of the European Union under the Research Excellence for Region Sustainability and High-Tech Industries (REFRESH) project no. CZ.10.03.01/00/22_003/0000048 via the Operational Programme Just Transition.

Funders	Funder number
Ministry for University and Research	2017PBXPN4
Horizon 2020 Framework Programme
European Commission	HORIZON-WIDERA-2021-ACCESS-03-01, 101079384, CZ.10.03.01/00/22_003/0000048, 101120397, HORIZON-WIDERA-2022-TALENTS
European Commission	683024
European Cooperation in Science and Technology	CA21101
Grantová Agentura České Republiky	19-27454X
European Social Fund Plus	CZ.02.01.01/00/22_008/0004587
Univerzita Palackého v Olomouci
European Regional Development Fund

Keywords

alkoxysilanes
cyanographene
dehydrogenative coupling
flow chemistry
organosilanes
single-gold-atom catalysis

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10.1021/acscatal.3c03937

Cite this

Kadam, R. G., Medved’, M., Kumar, S., Zaoralová, D., Zoppellaro, G., Bad’ura, Z., Montini, T., Bakandritsos, A., Fonda, E., Tomanec, O., Otyepka, M., Varma, R. S., Gawande, M. B., Fornasiero, P., & Zbořil, R. (2023). Linear-Structure Single-Atom Gold(I) Catalyst for Dehydrogenative Coupling of Organosilanes with Alcohols. ACS Catalysis, 13(24), 16067-16077. https://doi.org/10.1021/acscatal.3c03937

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title = "Linear-Structure Single-Atom Gold(I) Catalyst for Dehydrogenative Coupling of Organosilanes with Alcohols",

abstract = "A strategy for the synthesis of a gold-based single-atom catalyst (SAC) via a one-step room temperature reduction of Au(III) salt and stabilization of Au(I) ions on nitrile-functionalized graphene (cyanographene; G-CN) is described. The graphene-supported G(CN)-Au catalyst exhibits a unique linear structure of the Au(I) active sites promoting a multistep mode of action in dehydrogenative coupling of organosilanes with alcohols under mild reaction conditions as proven by advanced XPS, XAFS, XANES, and EPR techniques along with DFT calculations. The linear structure being perfectly accessible toward the reactant molecules and the cyanographene-induced charge transfer resulting in the exclusive Au(I) valence state contribute to the superior efficiency of the emerging two-dimensional SAC. The developed G(CN)-Au SAC, despite its low metal loading (ca. 0.6 wt %), appear to be the most efficient catalyst for Si-H bond activation with a turnover frequency of up to 139,494 h-1 and high selectivities, significantly overcoming all reported homogeneous gold catalysts. Moreover, it can be easily prepared in a multigram batch scale, is recyclable, and works well toward more than 40 organosilanes. This work opens the door for applications of SACs with a linear structure of the active site for advanced catalytic applications.",

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doi = "10.1021/acscatal.3c03937",

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Kadam, RG, Medved’, M, Kumar, S, Zaoralová, D, Zoppellaro, G, Bad’ura, Z, Montini, T, Bakandritsos, A, Fonda, E, Tomanec, O, Otyepka, M, Varma, RS, Gawande, MB, Fornasiero, P & Zbořil, R 2023, 'Linear-Structure Single-Atom Gold(I) Catalyst for Dehydrogenative Coupling of Organosilanes with Alcohols', ACS Catalysis, vol. 13, no. 24, pp. 16067-16077. https://doi.org/10.1021/acscatal.3c03937

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T1 - Linear-Structure Single-Atom Gold(I) Catalyst for Dehydrogenative Coupling of Organosilanes with Alcohols

AU - Kadam, Ravishankar G.

AU - Medved’, Miroslav

AU - Kumar, Subodh

AU - Zaoralová, Dagmar

AU - Zoppellaro, Giorgio

AU - Bad’ura, Zdeněk

AU - Montini, Tiziano

AU - Bakandritsos, Aristides

AU - Fonda, Emiliano

AU - Tomanec, Ondřej

AU - Otyepka, Michal

AU - Varma, Rajender S.

AU - Gawande, Manoj B.

AU - Fornasiero, Paolo

AU - Zbořil, Radek

PY - 2023/12/15

Y1 - 2023/12/15

N2 - A strategy for the synthesis of a gold-based single-atom catalyst (SAC) via a one-step room temperature reduction of Au(III) salt and stabilization of Au(I) ions on nitrile-functionalized graphene (cyanographene; G-CN) is described. The graphene-supported G(CN)-Au catalyst exhibits a unique linear structure of the Au(I) active sites promoting a multistep mode of action in dehydrogenative coupling of organosilanes with alcohols under mild reaction conditions as proven by advanced XPS, XAFS, XANES, and EPR techniques along with DFT calculations. The linear structure being perfectly accessible toward the reactant molecules and the cyanographene-induced charge transfer resulting in the exclusive Au(I) valence state contribute to the superior efficiency of the emerging two-dimensional SAC. The developed G(CN)-Au SAC, despite its low metal loading (ca. 0.6 wt %), appear to be the most efficient catalyst for Si-H bond activation with a turnover frequency of up to 139,494 h-1 and high selectivities, significantly overcoming all reported homogeneous gold catalysts. Moreover, it can be easily prepared in a multigram batch scale, is recyclable, and works well toward more than 40 organosilanes. This work opens the door for applications of SACs with a linear structure of the active site for advanced catalytic applications.

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KW - dehydrogenative coupling

KW - flow chemistry

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Linear-Structure Single-Atom Gold(I) Catalyst for Dehydrogenative Coupling of Organosilanes with Alcohols

Abstract

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Keywords

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