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Highly robust hydrogen generation by bio-inspired Ir complexes for dehydrogenation of formic acid in water [electronic resource] : Experimental and theoretical mechanistic investigations at different pH.

Published
Washington, D.C. : United States. Dept. of Energy. Office of Basic Energy Sciences, 2015.
Oak Ridge, Tenn. : Distributed by the Office of Scientific and Technical Information, U.S. Dept. of Energy
Physical Description
pages 5,496-5,504 : digital, PDF file
Additional Creators
Brookhaven National Laboratory, United States. Department of Energy. Office of Basic Energy Sciences, and United States. Department of Energy. Office of Scientific and Technical Information
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Summary
Hydrogen generation from formic acid (FA), one of the most promising hydrogen storage materials, has attracted much attention due to the demand for the development of renewable energy carriers. Catalytic dehydrogenation of FA in an efficient and green manner remains challenging. Here, we report a series of bio-inspired Ir complexes for highly robust and selective hydrogen production from FA in aqueous solutions without organic solvents or additives. One of these complexes bearing an imidazoline moiety (complex 6) achieved a turnover frequency (TOF) of 322,000 h−1 at 100 °C, which is higher than ever reported. The novel catalysts are very stable and applicable in highly concentrated FA. For instance, complex 3 (1 μmol) affords an unprecedented turnover number (TON) of 2,050,000 at 60 °C. Deuterium kinetic isotope effect experiments and density functional theory (DFT) calculations employing a “speciation” approach demonstrated a change in the rate-determining step with increasing solution pH. This study provides not only more insight into the mechanism of dehydrogenation of FA but also offers a new principle for the design of effective homogeneous organometallic catalysts for H2 generation from FA.
Report Numbers
E 1.99:bnl--108268-2015-ja
bnl--108268-2015-ja
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Note
Published through SciTech Connect.
07/30/2015.
"bnl--108268-2015-ja"
"KC0304030"
ACS Catalysis 3 36 ISSN 2155-5435 AM
Wang, Wan; Fujita, Etsuko; Ertem, Mehmed; Xu, Shaoan; Onishi, Naoya; Manaka, Yuichi; Suna, Yuki; Kambayashi, Hide; Muckerman, James; Himeda, Yuichiro.
Funding Information
SC00112704
CO026
View MARC record | catkey: 24046665