A Process for the Synthesis of Formic Acid by CO<sub>2</sub> Hydrogenation: Thermodynamic Aspects and the Role of CO

Schaub, Thomas; Paciello, Rocco

doi:10.1002/anie.201101292

Cited by 287 publications

(221 citation statements)

References 31 publications

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“…This observation is best explained by two adjacent substrate activation sites, which can be populated to varying extents by changing the electron flux through nitrogenase and the partial pressures of CO 2 and acetylene. Reductive coupling of CO 2 to alkynes yielding oxygenated hydrocarbons (e.g., carboxylic acids) has been reported for metal catalysts (10,47) but, to our knowledge, the production of olefins is unique to the reactions reported here.…”

Section: Discussionmentioning

confidence: 71%

“…Of particular interest are possible routes to reduction of CO 2 by multiple electrons to yield methanol (CH 3 OH) and methane (CH 4 ), which are renewable fuels (2). The reduction of CO 2 is difficult, with a limited number of reports of metal-based compounds able to catalyze these reactions (6)(7)(8)(9)(10)(11)(12)(13). In biology, only a few enzymes are known to reduce CO 2 (14)(15)(16)(17)(18), and none of these can catalyze the eight electron reduction to CH 4 .…”

mentioning

confidence: 99%

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Carbon dioxide reduction to methane and coupling with acetylene to form propylene catalyzed by remodeled nitrogenase

Yang

Moure

Dean

et al. 2012

Proc. Natl. Acad. Sci. U.S.A.

108

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A doubly substituted form of the nitrogenase MoFe protein (α-70 Val→Ala , α-195 His→Gln ) has the capacity to catalyze the reduction of carbon dioxide (CO 2 ) to yield methane (CH 4 ). Under optimized conditions, 1 nmol of the substituted MoFe protein catalyzes the formation of 21 nmol of CH 4 within 20 min. The catalytic rate depends on the partial pressure of CO 2 (or concentration of HCO 3 − ) and the electron flux through nitrogenase. The doubly substituted MoFe protein also has the capacity to catalyze the unprecedented formation of propylene (H 2 C = CH-CH 3 ) through the reductive coupling of CO 2 and acetylene (HC≡CH). In light of these observations, we suggest that an emerging understanding of the mechanistic features of nitrogenase could be relevant to the design of synthetic catalysts for CO 2 sequestration and formation of olefins.is an abundant and stable form of carbon that is the product of respiration and burning of fossil fuels. As a result of these activities, the atmospheric concentration of CO 2 , a greenhouse gas, has been rising over the last century and contributing to global warming (1). There is strong interest in developing methods for sequestering CO 2 either by capturing it or by chemically converting it to valuable chemicals (2-5). Of particular interest are possible routes to reduction of CO 2 by multiple electrons to yield methanol (CH 3 OH) and methane (CH 4 ), which are renewable fuels (2). The reduction of CO 2 is difficult, with a limited number of reports of metal-based compounds able to catalyze these reactions (6-13). In biology, only a few enzymes are known to reduce CO 2 (14-18), and none of these can catalyze the eight electron reduction to CH 4 .The bacterial Mo-dependent nitrogenase enzyme catalyzes the multielectron/proton reduction of dinitrogen (N 2 ) to two ammonia (NH 3 ) at a metal cluster designated FeMo-cofactor [7Fe-9S-1Mo-1C-R-homocitrate] (Fig. 1) in a reaction that requires ATP hydrolysis and evolution of H 2 , with a minimal reaction stoichiometry shown in Eq. 1 (19)(20)(21)(22).Given that nitrogenase is effective at catalyzing the difficult multielectron reduction of N 2 , it was of interest to determine whether this enzyme might also catalyze the reduction of CO 2 to the level of CH 4 . Nitrogenase is known to have the capacity to reduce a variety of other small, relatively inert, doubly or triply bonded compounds, such as acetylene (HC≡CH) (19,23). It has been shown that an alternative form of nitrogenase, which contains V in place of Mo in the active site cofactor, has the remarkable capacity to reduce CO and couple multiple CO molecules, yielding short chain alkenes and alkanes such as ethylene (C 2 H 4 ), ethane (C 2 H 6 ), propylene (C 3 H 6 ), and propane (C 3 H 8 ) (24,25). In contrast, the Mo-nitrogenase is only able to reduce CO at exceedingly low rates (24). However, we have found that the MoFe protein can be remodeled by substitution of amino acid residues that provide the first shell of noncovalent interactions with the active site FeMo cofa...

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Section: Discussionmentioning

confidence: 71%

mentioning

confidence: 99%

Carbon dioxide reduction to methane and coupling with acetylene to form propylene catalyzed by remodeled nitrogenase

Yang

Moure

Dean

et al. 2012

Proc. Natl. Acad. Sci. U.S.A.

108

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“…In contrast to the direct reaction of H 2 with CO 2 , the hydrogenation of carbonate and bicarbonate are well-established reactions282930 that have been achieved in a wide variety of organic solvents, ionic liquids, water and supercritical CO 2 (ref. 20).…”

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confidence: 99%

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

2014

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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.

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“…Multi-step processes have been developed to enable the separation of the adduct from the catalyst and subsequent isolation of the free acid [106]. Several studies describe processes in which the adduct of formic acid and NEt 3 is transformed into a thermally cleavable salt by exchange of the base [107 -110].…”

Section: Hydrogenation Of Co 2 To Formic Acidmentioning

confidence: 99%

“…Furthermore, multiphase reaction systems were used to investigate the separation of the adduct from the catalyst. Very recently a novel process was introduced by BASF in which trihexylamine was used as the base together with a ruthenium catalyst in protic media [106,110]. The corresponding adduct formed from formid acid and the amine could be separated form the aqueous phase and cleaved by distillation.…”

Section: Hydrogenation Of Co 2 To Formic Acidmentioning

confidence: 99%

Carbon Dioxide as a Carbon Resource – Recent Trends and Perspectives

Hölscher

Gürtler

Keim

et al. 2012

Zeitschrift Für Naturforschung B

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Dedicated to Professor Heribert Offermanns on the occasion of his 75 th birthdayWith the growing perception of industrialized societies that fossil raw materials are limited resources, academic chemical research and chemical industry have started to introduce novel catalytic technologies which aim at the development of economically competitive processes relying much more strongly on the use of alternative carbon feedstocks. Great interest is given world-wide to carbon dioxide (CO 2 ) as it is part of the global carbon cycle, nontoxic, easily available in sufficient quantities anywhere in the industrialized world, and can be managed technically with ease, and at low cost. In principle carbon dioxide can be used to generate a large variety of synthetic products ranging from bulk chemicals like methanol and formic acid, through polymeric materials, to fine chemicals like aromatic acids useful in the pharmaceutical industry. Owing to the high thermodynamic stability of CO 2 , the energy constraints of chemical reactions have to be carefully analyzed to select promising processes. Furthermore, the high kinetic barriers for incorporation of CO 2 into C-H or C-C bond forming reactions require that any novel transformation of CO 2 must inevitably be associated with a novel catalytic technology. This short review comprises a selection of the most recent academic and industrial research developments mainly with regard to innovations in CO 2 chemistry in the field of homogeneous catalysis and processes.

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A Process for the Synthesis of Formic Acid by CO₂ Hydrogenation: Thermodynamic Aspects and the Role of CO

Cited by 287 publications

References 31 publications

Carbon dioxide reduction to methane and coupling with acetylene to form propylene catalyzed by remodeled nitrogenase

Carbon dioxide reduction to methane and coupling with acetylene to form propylene catalyzed by remodeled nitrogenase

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

Carbon Dioxide as a Carbon Resource – Recent Trends and Perspectives

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A Process for the Synthesis of Formic Acid by CO2 Hydrogenation: Thermodynamic Aspects and the Role of CO

Cited by 287 publications

References 31 publications

Carbon dioxide reduction to methane and coupling with acetylene to form propylene catalyzed by remodeled nitrogenase

Carbon dioxide reduction to methane and coupling with acetylene to form propylene catalyzed by remodeled nitrogenase

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

Carbon Dioxide as a Carbon Resource – Recent Trends and Perspectives

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A Process for the Synthesis of Formic Acid by CO₂ Hydrogenation: Thermodynamic Aspects and the Role of CO