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Ambient Hydrogenation and Deuteration of Alkenes Using a Nanostructured Ni-Core-Shell Catalyst

2021, Gao, Jie, Ma, Rui, Feng, Lu, Liu, Yuefeng, Jackstell, Ralf, Jagadeesh, Rajenahally V., Beller, Matthias

A general protocol for the selective hydrogenation and deuteration of a variety of alkenes is presented. Key to success for these reactions is the use of a specific nickel-graphitic shell-based core–shell-structured catalyst, which is conveniently prepared by impregnation and subsequent calcination of nickel nitrate on carbon at 450 °C under argon. Applying this nanostructured catalyst, both terminal and internal alkenes, which are of industrial and commercial importance, were selectively hydrogenated and deuterated at ambient conditions (room temperature, using 1 bar hydrogen or 1 bar deuterium), giving access to the corresponding alkanes and deuterium-labeled alkanes in good to excellent yields. The synthetic utility and practicability of this Ni-based hydrogenation protocol is demonstrated by gram-scale reactions as well as efficient catalyst recycling experiments. © 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH

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Cobalt Single-Atom Catalysts with High Stability for Selective Dehydrogenation of Formic Acid

2020, Li, Xiang, Surkus, Annette-Enrica, Rabeah, Jabor, Anwar, Muhammad, Dastigir, Sarim, Junge, Henrik, Brückner, Angelika, Beller, Matthias

Metal–organic framework (MOF)-derived Co-N-C catalysts with isolated single cobalt atoms have been synthesized and compared with cobalt nanoparticles for formic acid dehydrogenation. The atomically dispersed Co-N-C catalyst achieves superior activity, better acid resistance, and improved long-term stability compared with nanoparticles synthesized by a similar route. High-angle annular dark-field–scanning transmission electron microscopy, X-ray photoelectron spectroscopy, electron paramagnetic resonance, and X-ray absorption fine structure characterizations reveal the formation of CoIINx centers as active sites. The optimal low-cost catalyst is a promising candidate for liquid H2 generation. © 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.