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Direct synthesis of formic acid from carbon dioxide by hydrogenation in acidic media.

ABSTRACT: The chemical transformation of carbon dioxide into useful products becomes increasingly important as CO2 levels in the atmosphere continue to rise as a consequence of human activities. In this article we describe the direct hydrogenation of CO2 into formic acid using a homogeneous ruthenium catalyst, in aqueous solution and in dimethyl sulphoxide (DMSO), without any additives. In water, at 40 °C, 0.2 M formic acid can be obtained under 200 bar, however, in DMSO the same catalyst affords 1.9 M formic acid. In both solvents the catalysts can be reused multiple times without a decrease in activity. Worldwide demand for formic acid continues to grow, especially in the context of a renewable energy hydrogen carrier, and its production from CO2 without base, via the direct catalytic carbon dioxide hydrogenation, is considerably more sustainable than the existing routes.

SUBMITTER: Moret S

PROVIDER: S-EPMC4059918 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:Hydrogenation reactions can be used to store energy in chemical bonds, and if these reactions are reversible, that energy can be released on demand. Some of the most effective transition metal catalysts for CO2 hydrogenation have featured pyridin-2-ol-based ligands (e.g., 6,6'-dihydroxybipyridine (6,6'-dhbp)) for both their proton-responsive features and for metal-ligand bifunctional catalysis. We aimed to compare bidentate pyridin-2-ol based ligands with a new scaffold featuring an N-heterocyclic carbene (NHC) bound to pyridin-2-ol. Toward this aim, we have synthesized a series of [Cp*Ir(NHC-pyOR)Cl]OTf complexes where R = t Bu (1), H (2), or Me (3). For comparison, we tested analogous bipy-derived iridium complexes as catalysts, specifically [Cp*Ir(6,6'-dxbp)Cl]OTf, where x = hydroxy (4Ir ) or methoxy (5Ir ); 4Ir was reported previously, but 5Ir is new. The analogous ruthenium complexes were also tested using [(?6-cymene)Ru(6,6'-dxbp)Cl]OTf, where x = hydroxy (4Ru ) or methoxy (5Ru ); 4Ru and 5Ru were both reported previously. All new complexes were fully characterized by spectroscopic and analytical methods and by single-crystal X-ray diffraction for 1, 2, 3, 5Ir , and for two [Ag(NHC-pyOR)2]OTf complexes 6 (R = t Bu) and 7 (R = Me). The aqueous catalytic studies of both CO2 hydrogenation and formic acid dehydrogenation were performed with catalysts 1-5. In general, NHC-pyOR complexes 1-3 were modest precatalysts for both reactions. NHC complexes 1-3 all underwent transformations under basic CO2 hydrogenation conditions, and for 3, we trapped a product of its transformation, 3SP , which we characterized crystallographically. For CO2 hydrogenation with base and dxbp-based catalysts, we observed that x = hydroxy (4Ir ) is 5-8 times more active than x = methoxy (5Ir ). Notably, ruthenium complex 4Ru showed 95% of the activity of 4Ir . For formic acid dehydrogenation, the trends were quite different with catalytic activity showing 4Ir ? 4Ru and 4Ir ? 5Ir . Secondary coordination sphere effects are important under basic hydrogenation conditions where the OH groups of 6,6'-dhbp are deprotonated and alkali metals can bind and help to activate CO2. Computational DFT studies have confirmed these trends and have been used to study the mechanisms of both CO2 hydrogenation and formic acid dehydrogenation.

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Direct synthesis of formic acid from carbon dioxide by hydrogenation in acidic media.

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