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.

CEET Nanotechnology Centre VŠB Technical University of Ostrava 17 listopadu 2172 15 Ostrava Poruba 708 00 Czech Republic

Department of Chemical and Pharmaceutical Sciences Center for Energy Environment and Transport Giacomo Ciamiciam INSTM Trieste Research Unit and ICCOM CNR Trieste Research Unit University of Trieste via L Giorgieri 1 Trieste 1 34127 Italy

Department of Chemistry Faculty of Natural Sciences Matej Bel University Tajovského 40 Banská Bystrica 974 01 Slovak Republic

Department of Industrial and Engineering Chemistry Institute of Chemical Technology Mumbai Marathwada Campus Jalna Maharashtra 431213 India

Department of Inorganic Chemistry Faculty of Science Palacký University Olomouc 17 listopadu 12 Olomouc 779 00 Czech Republic

IT4Innovations VŠB Technical University of Ostrava 17 listopadu 2172 15 Ostrava Poruba 708 00 Czech Republic

Regional Centre of Advanced Technologies and Materials Czech Advanced Technology and Research Institute Palacký University Olomouc Šlechtitelu° 27 Olomouc 779 00 Czech Republic

Synchrotron SOLEIL L'Orme des Merisiers Saint Aubin 91190 France

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