Sun Ruiyan, Kann Anna, Hartmann Heinrich, Besmehn Astrid, Hausoul Peter J C, Palkovits Regina
Institut für Technische und Makromolekulare Chemie, RWTH Aachen University, Worringerweg 2, 52074, Aachen, Germany.
Zentralinstitut für Engineering, Elektronik und Analytik ZEA-3, Forschungszentrum Jülich GmbH, 52425, Jülich, Germany.
ChemSusChem. 2019 Jul 19;12(14):3278-3285. doi: 10.1002/cssc.201900808. Epub 2019 May 21.
Methyl formate was produced in one pot through the hydrogenation of CO to formic acid/formate followed by an esterification step. The route offers the possibility to integrate renewable energy into the fossil-based chemical value chain. In this work, a phosphine-polymer-anchored Ru complex was shown to be an efficient solid catalyst for the direct hydrogenation of CO to methyl formate. The 1,2-bis(diphenylphosphino)ethane-like polymer presented the highest activity with a turnover number (TON) of up to 3401 at 160 °C. The reaction parameters were systemically investigated to optimize the reaction towards the formation of methyl formate. This catalyst could be reused seven times without a significant decrease in activity. Evolution of the catalytic Ru center during the reaction was revealed, and a possible reaction mechanism was proposed.
甲酸甲酯通过将CO加氢生成甲酸/甲酸盐，随后进行酯化步骤，在一步反应中制备而成。该路线为将可再生能源整合到基于化石的化学价值链中提供了可能性。在这项工作中，一种膦聚合物锚定的Ru配合物被证明是将CO直接氢化为甲酸甲酯的高效固体催化剂。类似1,2-双（二苯基膦基）乙烷的聚合物表现出最高活性，在160°C下的转化数（TON）高达3401。系统研究了反应参数以优化生成甲酸甲酯的反应。该催化剂可以重复使用七次，活性没有显著降低。揭示了反应过程中催化Ru中心的演变，并提出了可能的反应机理。
