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A prolific catalyst for dehydrogenation of neat formic acid.

Celaje JJ, Lu Z, Kedzie EA, Terrile NJ, Lo JN, Williams TJ - Nat Commun (2016)

Bottom Line: While many catalysts exist for both formic acid dehydrogenation and carbon dioxide reduction, solutions to date on hydrogen gas release rely on volatile components that reduce the weight content of stored hydrogen and/or introduce fuel cell poisons.These are avoided here.The catalyst utilizes an interesting chemical mechanism, which is described on the basis of kinetic and synthetic experiments.

View Article: PubMed Central - PubMed

Affiliation: Donald P. and Katherine B. Loker Hydrocarbon Institute and Department of Chemistry, University of Southern California, Los Angeles, California 90089-1661, USA.

ABSTRACT
Formic acid is a promising energy carrier for on-demand hydrogen generation. Because the reverse reaction is also feasible, formic acid is a form of stored hydrogen. Here we present a robust, reusable iridium catalyst that enables hydrogen gas release from neat formic acid. This catalysis works under mild conditions in the presence of air, is highly selective and affords millions of turnovers. While many catalysts exist for both formic acid dehydrogenation and carbon dioxide reduction, solutions to date on hydrogen gas release rely on volatile components that reduce the weight content of stored hydrogen and/or introduce fuel cell poisons. These are avoided here. The catalyst utilizes an interesting chemical mechanism, which is described on the basis of kinetic and synthetic experiments.

No MeSH data available.


Related in: MedlinePlus

Catalyst initiation and molecular structure of active catalyst homologue 3b.3b={[(tBu2PCH2(2-py))Ir(H)]2(μ2-H)(μ2-κ,κ′-O2CCH3)2}+. Hydrogen atoms omitted. Ellipsoids are drawn at the 50% probability level. counterion, trifluoromethanesulfonate; solv, solvent.
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f3: Catalyst initiation and molecular structure of active catalyst homologue 3b.3b={[(tBu2PCH2(2-py))Ir(H)]2(μ2-H)(μ2-κ,κ′-O2CCH3)2}+. Hydrogen atoms omitted. Ellipsoids are drawn at the 50% probability level. counterion, trifluoromethanesulfonate; solv, solvent.

Mentions: Equally remarkable as the reactivity of this new catalytic system is the unique, two-metal mechanism through which it operates. We used three approaches to gain insight into this mechanism: stoichiometric model reactions, reaction kinetics and isotope labelling studies. Figures 3 and 4 present a sketch of a possible mechanism for our system.


A prolific catalyst for dehydrogenation of neat formic acid.

Celaje JJ, Lu Z, Kedzie EA, Terrile NJ, Lo JN, Williams TJ - Nat Commun (2016)

Catalyst initiation and molecular structure of active catalyst homologue 3b.3b={[(tBu2PCH2(2-py))Ir(H)]2(μ2-H)(μ2-κ,κ′-O2CCH3)2}+. Hydrogen atoms omitted. Ellipsoids are drawn at the 50% probability level. counterion, trifluoromethanesulfonate; solv, solvent.
© Copyright Policy - open-access
Related In: Results  -  Collection

License
Show All Figures
getmorefigures.php?uid=PMC4834634&req=5

f3: Catalyst initiation and molecular structure of active catalyst homologue 3b.3b={[(tBu2PCH2(2-py))Ir(H)]2(μ2-H)(μ2-κ,κ′-O2CCH3)2}+. Hydrogen atoms omitted. Ellipsoids are drawn at the 50% probability level. counterion, trifluoromethanesulfonate; solv, solvent.
Mentions: Equally remarkable as the reactivity of this new catalytic system is the unique, two-metal mechanism through which it operates. We used three approaches to gain insight into this mechanism: stoichiometric model reactions, reaction kinetics and isotope labelling studies. Figures 3 and 4 present a sketch of a possible mechanism for our system.

Bottom Line: While many catalysts exist for both formic acid dehydrogenation and carbon dioxide reduction, solutions to date on hydrogen gas release rely on volatile components that reduce the weight content of stored hydrogen and/or introduce fuel cell poisons.These are avoided here.The catalyst utilizes an interesting chemical mechanism, which is described on the basis of kinetic and synthetic experiments.

View Article: PubMed Central - PubMed

Affiliation: Donald P. and Katherine B. Loker Hydrocarbon Institute and Department of Chemistry, University of Southern California, Los Angeles, California 90089-1661, USA.

ABSTRACT
Formic acid is a promising energy carrier for on-demand hydrogen generation. Because the reverse reaction is also feasible, formic acid is a form of stored hydrogen. Here we present a robust, reusable iridium catalyst that enables hydrogen gas release from neat formic acid. This catalysis works under mild conditions in the presence of air, is highly selective and affords millions of turnovers. While many catalysts exist for both formic acid dehydrogenation and carbon dioxide reduction, solutions to date on hydrogen gas release rely on volatile components that reduce the weight content of stored hydrogen and/or introduce fuel cell poisons. These are avoided here. The catalyst utilizes an interesting chemical mechanism, which is described on the basis of kinetic and synthetic experiments.

No MeSH data available.


Related in: MedlinePlus