A homogeneous transition metal complex for clean hydrogen production from methanol-water mixtures

作者：Rodriguez-Lugo, Rafael E.; Trincado, Monica^*; Vogt, Matthias; Tewes, Friederike; Santiso-Quinones, Gustavo; Gruetzmacher, Hansjoerg

来源：Nature Chemistry, 2013, 5(4): 342-347.

DOI：10.1038/NCHEM.1595

• ALCOHOLS
• DEHYDROGENATION
• LIGAND
• ACID
• CONVERSION
• RHODIUM
• SYSTEM
• AMINES
• ESTERS

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 H-2 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)(trop(2)dad)], stores up to two equivalents of hydrogen intramolecularly, and catalyses the production of H-2 from alcohols in the presence of water and a base under homogeneous conditions. The conversion of a MeOH-H2O mixture proceeds selectively to CO2/H-2 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 trop(2)dad ligand behaves as a chemically 'non-innocent' co-operative ligand.

• 出版日期2013-4