Acceptorless Alcohol Dehydrogenation Catalysed by Pd/C

• Published in: ChemSusChem 2019-11, Vol.12 (22), p.4953-4961
• Main Authors: Nicolau, Guillermo, Tarantino, Giulia, Hammond, Ceri
• Format: Article
• Language: English
• Subjects: Alcohol; alcohol oxidation; Alcohols; Carbonyl compounds; Carbonyls; Clean energy; Dehydrogenation; heterogeneous catalysis; hydrogen storage; nanoparticles; Oxidation; Oxidizing agents; Selectivity
• ISSN: 1864-5631; 1864-564X
• DOI: 10.1002/cssc.201901313

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 H2, 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(product) mL−1 h−1, 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. Sustainable alcohol dehydrogenation: The acceptorless dehydrogenation of alcohols is achieved with heterogeneous catalysts and continuous reactors, resulting in the continuous production of carbonyl compounds and molecular hydrogen.