1616980-28-9Relevant academic research and scientific papers
Base-Free Methanol Dehydrogenation Using a Pincer-Supported Iron Compound and Lewis Acid Co-catalyst
Bielinski, Elizabeth A.,F?rster, Moritz,Zhang, Yuanyuan,Bernskoetter, Wesley H.,Hazari, Nilay,Holthausen, Max C.
, p. 2404 - 2415 (2015)
Hydrogen is an attractive alternative energy vector to fossil fuels if effective methods for its storage and release can be developed. In particular, methanol, with a gravimetric hydrogen content of 12.6%, is a promising target for chemical hydrogen storage. To date, there are relatively few homogeneous transition metal compounds that catalyze the aqueous phase dehydrogenation of methanol to release hydrogen and carbon dioxide. In general, these catalysts utilize expensive precious metals and require a strong base. This paper shows that a pincer-supported Fe compound and a co-catalytic amount of a Lewis acid are capable of catalyzing base-free aqueous phase methanol dehydrogenation with turnover numbers up to 51 000. This is the highest turnover number reported for either a first-row transition metal or a base-free system. Additionally, this paper describes preliminary mechanistic experiments to understand the reaction pathway and propose a stepwise process, which requires metal-ligand cooperativity. This pathway is supported by DFT calculations and explains the role of the Lewis acid co-catalyst.(Chemical Equation Presented).
Lewis acid-assisted formic acid dehydrogenation using a pincer-supported iron catalyst
Bielinski, Elizabeth A.,Lagaditis, Paraskevi O.,Zhang, Yuanyuan,Mercado, Brandon Q.,Würtele, Christian,Bernskoetter, Wesley H.,Hazari, Nilay,Schneider, Sven
, p. 10234 - 10237 (2014/08/05)
Formic acid (FA) is an attractive compound for H2 storage. Currently, the most active catalysts for FA dehydrogenation use precious metals. Here, we report a homogeneous iron catalyst that, when used with a Lewis acid (LA) co-catalyst, gives approximately 1,000,000 turnovers for FA dehydrogenation. To date, this is the highest turnover number reported for a first-row transition metal catalyst. Preliminary studies suggest that the LA assists in the decarboxylation of a key iron formate intermediate and can also be used to enhance the reverse process of CO2 hydrogenation.
