Cardiff Catalysis Institute, Cardiff University, Main Building, Park Place, Cardiff, CF10 3AT, UK.
ChemSusChem. 2019 Nov 22;12(22):4953-4961. doi: 10.1002/cssc.201901313. Epub 2019 Oct 4.
Although the selective oxidation of alcohols to carbonyl compounds is a critical reaction, it is often plagued by several challenges related to sustainability. Here, the continuous, acceptorless dehydrogenation of alcohols to carbonyl compounds over heterogeneous catalysts was demonstrated, in the absence of oxidants, bases or acceptor molecules. In addition to improving selectivity and atom efficiency, the absence of an acceptor resulted in the co-production of molecular H , a clean energy source, and permitted dehydrogenation to proceed at >98 % selectivity at turnover frequency values amongst the highest in the literature. Moreover, excellent durability was observed during continuous operation over 48 h, reaching space-time yields of 0.683 g mL h , better than the state of the art by over two orders of magnitude. Alongside these breakthroughs, the basic kinetic parameters of the reaction were also determined, allowing some of the elementary reaction steps to be identified.
尽管醇的选择性氧化为羰基化合物是一个关键反应，但它常常受到与可持续性相关的几个挑战的困扰。在这里，在没有氧化剂、碱或受体分子的情况下，通过多相催化剂实现了醇的连续、无受体脱氢转化为羰基化合物。除了提高选择性和原子效率外，由于不存在受体，导致共同生成了清洁的能源分子氢气，并且在文献中最高的转化频率值下，脱氢反应的选择性超过 98%。此外，在连续运行 48 小时期间观察到了出色的耐久性，时空收率达到了 0.683 g mL h ，比最先进的技术高出两个数量级以上。除了这些突破之外，还确定了反应的基本动力学参数，从而可以确定一些基本反应步骤。
