Borane cluster-based porous covalent networks, named activated borane (ActB), were prepared by cothermolysis of decaborane(14) (nido-B10H14) and selected hydrocarbons (toluene, ActB-Tol; cyclohexane, ActB-cyHx; and n-hexane, ActB-nHx) under anaerobic conditions. These amorphous solid powders exhibit different textural and Lewis acid (LA) properties that vary depending on the nature of the constituent organic linker. For ActB-Tol, its LA strength even approaches that of the commonly used molecular LA, B(C6F5)3. Most notably, ActBs can act as heterogeneous LA catalysts in hydrosilylation/deoxygenation reactions with various carbonyl substrates as well as in the gas-phase dehydration of ethanol. These studies reveal the potential of ActBs in catalytic applications, showing (a) the possibility for tuning catalytic reaction outcomes (selectivity) in hydrosilylation/deoxygenation reactions by changing the material's composition and (b) the very high activity toward ethanol dehydration that exceeds the commonly used γ-Al2O3 by achieving a stable conversion of ∼93% with a selectivity for ethylene production of ∼78% during a 17 h continuous period on stream at 240 °C.

Department of Chemistry Masaryk University Kotlářská 2 611 37 Brno Czech Republic

Department of Materials Chemistry Institute of Inorganic Chemistry of the Czech Academy of Sciences Husinec Řež 1001 250 68 Řež Czech Republic

Department of Molecular Electrochemistry and Catalysis J Heyrovsky Institute of Physical Chemistry of the Czech Academy of Sciences Dolejškova 2155 182 00 Prague 8 Czech Republic

Department of Structural Analysis Institute of Macromolecular Chemistry of the Czech Academy of Sciences Heyrovského nám 2 162 06 Prague 6 Czech Republic

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