Non‐Metal‐Mediated Homogeneous Hydrogenation of CO<sub>2</sub> to CH<sub>3</sub>OH

Ashley, Andrew E.; Thompson, Amber L.; O’Hare, Dermot

doi:10.1002/anie.200905466

Cited by 500 publications

(313 citation statements)

References 54 publications

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“…methanol using non-metal complexes (Ashley et al 2009;Riduan et al 2009). This centres on the activation of H 2 by so-called frustrated Lewis pairs in specifically designed, organometallic complexes (Mömming et al 2009).…”

Section: Synthetic Methanol-a Sustainable Organic Fuel For Transportmentioning

confidence: 99%

Turning carbon dioxide into fuel

Jiang

Xiao

Кузнецов

et al. 2010

Phil. Trans. R. Soc. A.

414

289

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Our present dependence on fossil fuels means that, as our demand for energy inevitably increases, so do emissions of greenhouse gases, most notably carbon dioxide (CO 2 ). To avoid the obvious consequences on climate change, the concentration of such greenhouse gases in the atmosphere must be stabilized. But, as populations grow and economies develop, future demands now ensure that energy will be one of the defining issues of this century. This unique set of (coupled) challenges also means that science and engineering have a unique opportunity-and a burgeoning challenge-to apply their understanding to provide sustainable energy solutions. Integrated carbon capture and subsequent sequestration is generally advanced as the most promising option to tackle greenhouse gases in the short to medium term. Here, we provide a brief overview of an alternative mid-to long-term option, namely, the capture and conversion of CO 2 , to produce sustainable, synthetic hydrocarbon or carbonaceous fuels, most notably for transportation purposes.Basically, the approach centres on the concept of the large-scale re-use of CO 2 released by human activity to produce synthetic fuels, and how this challenging approach could assume an important role in tackling the issue of global CO 2 emissions. We highlight three possible strategies involving CO 2 conversion by physico-chemical approaches: sustainable (or renewable) synthetic methanol, syngas production derived from flue gases from coal-, gas-or oil-fired electric power stations, and photochemical production of synthetic fuels. The use of CO 2 to synthesize commodity chemicals is covered elsewhere (Arakawa et al. 2001 Chem. Rev. 101, 953-996); this review is focused on the possibilities for the conversion of CO 2 to fuels. Although these three prototypical areas differ in their ultimate applications, the underpinning thermodynamic considerations centre on the conversionand hence the utilization-of CO 2 . Here, we hope to illustrate that advances in the science and engineering of materials are critical for these new energy technologies, and specific examples are given for all three examples.With sufficient advances, and institutional and political support, such scientific and technological innovations could help to regulate/stabilize the CO 2 levels in the atmosphere and thereby extend the use of fossil-fuel-derived feedstocks.

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Section: Synthetic Methanol-a Sustainable Organic Fuel For Transportmentioning

confidence: 99%

Turning carbon dioxide into fuel

Jiang

Xiao

Кузнецов

et al. 2010

Phil. Trans. R. Soc. A.

414

289

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“…[1][2][3][4][5][6][7][8][9][10] However, the chemical reduction of CO2 to highly reduced products such as methanol (CH3OH) remains a daunting task. The groups of Fujita, [11][12][13] Kubiak, 3,14 Meyer, 15-17 Savéant [18][19][20] and others [21][22][23][24][25][26][27][28][29][30][31][32] have made significant contributions to this field, particularly in the fundamental understanding of using transition-metal complexes to catalyze CO2's transformation. Despite these advances, many challenges remain: for example, CO2 reduction has largely been confined to 2e -products such as CO and formate, and in many cases large overpotentials are required to drive these reactions.…”

Section: Introductionmentioning

confidence: 99%

Reduction of CO₂ to Methanol Catalyzed by a Biomimetic Organo-Hydride Produced from Pyridine

Lim¹,

Holder²,

et al. 2014

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ABSTRACT:We use quantum chemical calculations to elucidate a viable homogeneous mechanism for pyridine-catalyzed reduction of CO2 to methanol. In the first component of the catalytic cycle, pyridine (Py) undergoes a H + transfer (PT) to form pyridinium (PyH + ) followed by an e -transfer (ET) to produce pyridinium radical (PyH 0 ). Examples of systems to effect this ET to populate PyH + 's LUMO (E 0 calc ~ -1.3V vs. SCE) to form the solution phase PyH 0 via highly reducing electrons include the photo-electrochemical p-GaP system (ECBM ~ -1.5V vs. SCE at pH= 5) and the photochemical [Ru(phen)3] 2+ /ascorbate system. We predict that PyH 0 undergoes further PT-ET steps to form the key closed-shell, dearomatized 1,2-dihydropyridine (PyH2) species. Our proposed sequential PT-ET-PT-ET mechanism transforming Py into PyH2 is consistent with the mechanism described in the formation of related dihydropyridines. Because it is driven by its proclivity to regain aromaticity, PyH2 is a potent recyclable organo-hydride donor that mimics the role of NADPH in the formation of C-H bonds in the photosynthetic CO2 reduction process. In particular, in the second component of the catalytic cycle, we predict that the PyH2/Py redox couple is kinetically and thermodynamically competent in catalytically effecting hydride and proton transfers (the latter often mediated by a proton relay chain) to CO2 and its two succeeding intermediates, namely formic acid and formaldehyde, to ultimately form CH3OH. The hydride and proton transfers for the first reduction step, i.e. reduction of CO2, are sequential in nature; by contrast, they are coupled in each of the two subsequent hydride and proton transfers to reduce formic acid and formaldehyde.

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“…10 Such activation of CO 2 using FLPs has allowed subsequent reduction to methanol and methane. 11,12 There are few, but an increasing number, of transition metal FLP type systems which can activate CO 2 X-ray quality single crystals of 1 were grown by slow diffusion of hexane into a concentrated benzene solution at 298 K over five days. The molecular structure of the Λ-mer enantiomer of 1 is shown alongside equation 1 (the asymmetric unit contains both ∆-mer and Λ-mer enantiomers).…”

mentioning

confidence: 99%