Hydrogenation of Carbon Dioxide to Methanol by Using a Homogeneous Ruthenium–Phosphine Catalyst

Wesselbaum, Sebastian; Stein, Thorsten vom; Klankermayer, Jürgen; Leitner, Walter

doi:10.1002/anie.201202320

Cited by 492 publications

(262 citation statements)

References 43 publications

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“…FA and pFA are prepared industrially by silver or metal oxide-catalysed dehydrogenation of methanol (Formox process). Methanol itself is accessible from carbon monoxide, from renewable sources 41 , or via carbon dioxide hydrogenation 19 . Therefore, an envisioned CO 2 neutral approach would be to complete the circuit of our presented system by including the extruded CO 2 through hydrogenation into methanol (ref.…”

Section: Discussionmentioning

confidence: 99%

“…Therefore, an envisioned CO 2 neutral approach would be to complete the circuit of our presented system by including the extruded CO 2 through hydrogenation into methanol (ref. 19), which can be subsequently oxidized to FA or pFA via the Formox process, note that partial reduction of CO 2 to FA is an unresolved issue (Fig. 5).…”

Section: Discussionmentioning

confidence: 99%

“…Therefore, one alternative is chemical hydrogen storage in molecular materials in which the dihydrogen is stored in the form of hydridic and protic hydrogen. Examples are metal hydrides [4][5][6] , ammonia borane derivatives 2,3,7 , formic acid 2,[8][9][10][11][12][13][14][15][16][17] and methanol [18][19][20][21] . Ammonia borane derivatives have a good weight efficiency (r19.4 wt% H 2 ) 2,3,7 , but the solid spentfuels are hardly recyclable.…”

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Selective and mild hydrogen production using water and formaldehyde

et al. 2014

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With the increased efforts in finding new energy storage systems for mobile and stationary applications, an intensively studied fuel molecule is dihydrogen owing to its energy content, and the possibility to store it in the form of hydridic and protic hydrogen, for example, in liquid organic hydrogen carriers. Here we show that water in the presence of paraformaldehyde or formaldehyde is suitable for molecular hydrogen storage, as these molecules form stable methanediol, which can be easily and selectively dehydrogenated forming hydrogen and carbon dioxide. In this system, both molecules are hydrogen sources, yielding a theoretical weight efficiency of 8.4% assuming one equivalent of water and one equivalent of formaldehyde. Thus it is potentially higher than formic acid (4.4 wt%), as even when technical aqueous formaldehyde (37 wt%) is used, the diluted methanediol solution has an efficiency of 5.0 wt%. The hydrogen can be efficiently generated in the presence of air using a ruthenium catalyst at low temperature.

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Section: Discussionmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

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confidence: 99%

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Selective and mild hydrogen production using water and formaldehyde

et al. 2014

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“…Although organocatalyzed CO 2 reduction to MeOH is still not as powerful as transition metal based methodologies, [130][131][132][133] organocatalysis offers tangible and diverse approaches to reduced forms of carbon. For example, NHC catalysts have been employed for the reduction of CO 2 to methanol.…”

Section: Organocatalysed Co 2 Reductionmentioning

confidence: 99%

Sustainable conversion of carbon dioxide: the advent of organocatalysis

2015

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The conversion of carbon dioxide (CO 2 ), an abundant renewable carbon reagent, into chemicals of academic and industrial interest is of imminent importance to create a higher degree of sustainability in chemical processing and production. Recent progress in this field is characterised by a plethora of organic molecules able to mediate the conversion of suitable substrates in the presence of CO 2 into a variety of value-added commodities with advantageous features combining cost-effectiveness, metalfree transformations and general substrate activation profiles. In this review, the latest developments are discussed in the field of CO 2 catalysis with a focus on organo-mediated conversions and their increasing importance as to serve as practicable alternatives for metal-based processes. Also a critical assessment of the state-of-the-art is presented with attention on those features that need further attention to lift the usefulness of organocatalysis in the production of organic molecules of potential commercial interest.

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“…12 Homogeneous ruthenium-phosphine complex has been successfully employed in the hydrogenation of carbon dioxide to form ethanol. 13 Phosphine complexes of Ni, Pd and Pt have been used in the catalytic hydrogenolysis of biphenylene under H 2 at moderate temperature. 14 In view of the immense applications of metal complexes of phosphines R.N.…”

Section: Introductionmentioning

confidence: 99%

Multi-Nuclear NMR Investigation of Nickel(II), Palladium(II), Platinum(II) and Ruthenium(II) Complexes of an Asymmetrical Ditertiary Phosphine

Gerald

Raj

Pathak³

et al. 2013

Journal of the Korean Chemical Society

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ABSTRACT. Complexes synthesized by reacting alkyl and aryl phosphines with different transition metals are of great interest due to their catalytic properties. Many of the phosphine complexes are soluble in polar solvents as a result they find applications in homogeneous catalysis. In our present work we report, four transition metal complexes of Ni(II), Pd(II), Pt(II) and Ru(II) with an asymmetrical ditertiaryphosphine ligand. The synthesized ligand bears a less electronegative substituent such as methyl group on the aromatic nucleus hence makes it a strong σ-donor to form stable complexes and thus could effectively used in catalytic reactions. The complexes have been completely characterized by elemental analyses, FTIR, 1 HNMR, 31 PNMR and FAB Mass Spectrometry methods. Based on the spectroscopic evidences it has been confirmed that Ni(II), Pd(II) and Pt(II) complexes with the ditertiaryphosphine ligand showed cis whereas the Ru(II) complex showed trans geometry in their molecular structure.

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Hydrogenation of Carbon Dioxide to Methanol by Using a Homogeneous Ruthenium–Phosphine Catalyst

Cited by 492 publications

References 43 publications

Selective and mild hydrogen production using water and formaldehyde

Selective and mild hydrogen production using water and formaldehyde

Sustainable conversion of carbon dioxide: the advent of organocatalysis

Multi-Nuclear NMR Investigation of Nickel(II), Palladium(II), Platinum(II) and Ruthenium(II) Complexes of an Asymmetrical Ditertiary Phosphine

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