A homogeneous transition metal complex for clean hydrogen production from methanol–water mixtures
Author: ["Rafael E. Rodríguez-Lugo","Mónica Trincado","Matthias Vogt","Friederike Tewes","Gustavo Santiso-Quinones","Hansjörg Grützmacher"]
Publication: Nature Chemistry
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Abstract
The development of an efficient catalytic process that mimics the enzymatic function of alcohol dehydrogenase is critical for using biomass alcohols for both the production of H2 as a chemical energy carrier and fine chemicals under waste-free conditions. Dehydrogenation of alcohol–water mixtures into their corresponding acids with molecular hydrogen as the sole by-product from the reaction can be catalysed by a ruthenium complex with a chelating bis(olefin) diazadiene ligand. This complex, [K(dme)2][Ru(H)(trop2dad)], stores up to two equivalents of hydrogen intramolecularly, and catalyses the production of H2 from alcohols in the presence of water and a base under homogeneous conditions. The conversion of a MeOH–H2O mixture proceeds selectively to CO2/H2 gas formation under neutral conditions, thereby allowing the use of the entire hydrogen content (12% by weight). Isolation and characterization of the ruthenium complexes from these reactions suggested a mechanistic scenario in which the trop2dad ligand behaves as a chemically ‘non-innocent’ co-operative ligand. A ruthenium complex bearing a chemically and redox-non-innocent tetradentate diolefin diazadiene ligand is shown to be an efficient homogeneous catalyst for the conversion of a 1:1 mixture of methanol and water to hydrogen and carbon dioxide. Development of this process is an important step in the production of hydrogen for use as a fuel from biomass.
Cite this article
Rodríguez-Lugo, R., Trincado, M., Vogt, M. et al. A homogeneous transition metal complex for clean hydrogen production from methanol–water mixtures. Nature Chem 5, 342–347 (2013). https://doi.org/10.1038/nchem.1595