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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.

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A Stable Manganese Pincer Catalyst for the Selective Dehydrogenation of Methanol

2016-12-2, Andérez-Fernández, María, Vogt, Lydia K., Fischer, Steffen, Zhou, Wei, Jiao, Haijun, Garbe, Marcel, Elangovan, Saravanakumar, Junge, Kathrin, Junge, Henrik, Ludwig, Ralf, Beller, Matthias

For the first time, structurally defined manganese pincer complexes catalyze the dehydrogenation of aqueous methanol to hydrogen and carbon dioxide, which is a transformation of interest with regard to the implementation of a hydrogen and methanol economy. Excellent long-term stability was demonstrated for the Mn-PNPiPr catalyst, as a turnover of more than 20 000 was reached. In addition to methanol, other important hydrogen carriers were also successfully dehydrogenated.

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Cobalt-Catalyzed Aqueous Dehydrogenation of Formic Acid

2019, Zhou, Wei, Wei, Zhihong, Spannenberg, Anke, Jiao, Haijun, Junge, Kathrin, Junge, Henrik, Beller, Matthias

Among the known liquid organic hydrogen carriers, formic acid attracts increasing interest in the context of safe and reversible storage of hydrogen. Here, the first molecularly defined cobalt pincer complex is disclosed for the dehydrogenation of formic acid in aqueous medium under mild conditions. Crucial for catalytic activity is the use of the specific complex 3. Compared to related ruthenium and manganese complexes 7 and 8, this optimal cobalt complex showed improved performance. DFT computations support an innocent non-classical bifunctional outer-sphere mechanism on the triplet state potential energy surface. © 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.