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

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 i...

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Bibliographic Details
Published in:Nature chemistry 2013-04, Vol.5 (4), p.342-347
Main Authors: Rodríguez-Lugo, Rafael E., Trincado, Mónica, Vogt, Matthias, Tewes, Friederike, Santiso-Quinones, Gustavo, Grützmacher, Hansjörg
Format: Article
Language:English
Subjects:
639/638/406/911
639/638/77/885
Alcohol
Alcohols
Analytical Chemistry
Aza Compounds - chemistry
Biochemistry
Carbon
Carbon dioxide
Carbon Dioxide - chemistry
Catalysis
Chemistry
Chemistry/Food Science
Dehydrogenase
Electric currents
Gases
Hydrogen
Hydrogen - chemistry
Hydrogen production
Inorganic Chemistry
Ligands
Methanol - chemistry
Models, Molecular
Molecular Structure
Organic Chemistry
Organometallic Compounds - chemical synthesis
Organometallic Compounds - chemistry
Oxidation-Reduction
Phase Transition
Physical Chemistry
Renewable Energy
Ruthenium
Ruthenium - chemistry
Water - chemistry
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Summary: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–H 2 O mixture proceeds selectively to CO 2 /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. 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.
ISSN:1755-4330
1755-4349
DOI:10.1038/nchem.1595