Hydrogenolysis through catalytic transfer hydrogenation: Glycerol conversion to 1,2-propanediol

Gandarias, Iñaki; Arias, P.L.; Fernández, S; Requies, J.; Doukkali, M. El; Güemez, M.B.

doi:10.1016/j.cattod.2012.03.067

Cited by 94 publications

(94 citation statements)

References 40 publications

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“…Formic acid is easily handled and it can therefore be applied for hydrogen storage for transportation applications [7]. It is also worth noting that formic acid can be used directly as a hydrogen donor for hydrogenation and deoxygenation reactions instead of molecular hydrogen [6,8,9]. A requirement for this application is that it would provide stable, CO-free hydrogen generation at low temperatures (<373 K).…”

Section: Introductionmentioning

confidence: 99%

Hydrogen production from formic acid vapour over a Pd/C catalyst promoted by potassium salts: Evidence for participation of buffer-like solution in the pores of the catalyst

Liu

Bulushev

Beloshapkin

et al. 2014

Applied Catalysis B: Environmental

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(D.A. Bulushev) 2 A B S T R A C T Doping a 1 wt.% Pd/C catalyst with alkali metal carbonates has a very significant promotional effect on its activity in hydrogen production from the decomposition of formic acid vapour (2 vol.%, 1 bar), potassium and caesium carbonates giving the largest effects. The K carbonate species present on the fresh catalysts react with formic acid to form formate ions, these being dissolved in a formic acid/water solution condensed in the pores of the support. The steadystate activities of the samples containing formate ions were 1-2 orders of magnitude greater than those of the unpromoted Pd/C and CO content was lower than 30 ppm. The activation energies for the reaction increased with doping from 66 to 88-99 kJ mol -1 , relatively independent of the cation of the dopant. Similar but lesser effects were found with unsupported Pd nanocrystals doped with K carbonate. The rate-determining step for the promoted samples appears to be the decomposition of formate ions on the Pd surface.

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Section: Introductionmentioning

confidence: 99%

Hydrogen production from formic acid vapour over a Pd/C catalyst promoted by potassium salts: Evidence for participation of buffer-like solution in the pores of the catalyst

Liu

Bulushev

Beloshapkin

et al. 2014

Applied Catalysis B: Environmental

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“…The most efficient among them use noble metals to activate hydrogen and tungsten or rhenium as additives, 1 but other systems such as Ni-Cu/Al 2 O 3 have also been used. 2 Homogeneous reactions using rhenium catalysts, for which detailed mechanistic information (computational and experimental) is available, [3][4][5][6][7][8][9][10][11][12][13][14][15] are showing great potential in processes ranging from the deoxydehydration of glycols to the deoxygenation of epoxides, alcohols and carbonyl compounds, as does the derivatization of biomass polyols catalyzed by rhodium or iridium complexes. 16 The discovery of the activity of Mo(VI) and V(V) complexes, based on cheaper and more abundant metals, in the DODH of glycols [17][18][19][20][21][22][23][24] led us to focus on the study of the mechanism of these transformations.…”

Section: Introductionmentioning

confidence: 99%

A Radical Mechanism for the Vanadium-Catalyzed Deoxydehydration of Glycols

et al. 2016

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We propose a novel mechanism for the deoxydehydration (DODH) reaction of glycols catalyzed by a [Bu 4 N][VO 2 (dipic)] complex (dipic= pyridine-2,6-dicarboxylate) using triphenylphosphine as a reducing agent. Using density functional theory (DFT) we have confirmed that the preferred sequence of reaction steps involves reduction of the V(V) complex by phosphine, followed by condensation of the glycol into a [VO(dipic)(- (6), which then evolves to the alkene product and the recovery of the catalyst. In contrast to the usually invoked closed-shell mechanism for the latter steps, where 6 suffers a [3+2] retrocycloaddition, we have found that the homolytic cleavage of one of the C-O bonds in 6 is preferred by 12 kcal/mol. The resulting diradical intermediate then collapses to a metallacycle which evolves to the product through an aromatic [2+2] retrocycloaddition. We use this key change in the mechanism to propose ways to design better catalysts for this transformation. The analysis of the mechanisms in both singlet and triplet potential energy surfaces, together with the location of the MECPs between them, showcase this reaction as an interesting example of two-state reactivity.2

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“…On the other hand, by changing the hydrogen donor molecule, it is possible to improve the performance of the CTH of glycerol on using the bimetallic Ni-Cu/Al 2 O 3 catalyst [49]. Gandarias et al performed a study on the effect of the hydrogen donor molecule, by comparing methanol (MeOH), formic acid (FA) and 2-propanol [48]. Formic acid appears to be the most effective hydrogen donor molecule.…”

Section: Glycerol and Other Polyolsmentioning

confidence: 99%

“…Gandarias et al have deeply studied the reactivity of bimetallic catalysts Ni-Cu/Al 2 O 3 , prepared through the sol-gel technique, giving the best performances when pretreated at 450 • C [47][48][49]. At the beginning, the hydrogenolysis of glycerol was studied either in presence of molecular hydrogen or in conditions in which the hydrogen is produced in situ, through the aqueous phase reforming (APR) or through the catalytic transfer hydrogenolysis (CTH) by means of 2-propanol [47].…”

Section: Glycerol and Other Polyolsmentioning

confidence: 99%

Catalytic Transfer Hydrogenolysis as an Effective Tool for the Reductive Upgrading of Cellulose, Hemicellulose, Lignin, and Their Derived Molecules

et al. 2018

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Lignocellulosic biomasses have a tremendous potential to cover the future demand of bio-based chemicals and materials, breaking down our historical dependence on petroleum resources. The development of green chemical technologies, together with the appropriate eco-politics, can make a decisive contribution to a cheap and effective conversion of lignocellulosic feedstocks into sustainable and renewable chemical building blocks. In this regard, the use of an indirect H-source for reducing the oxygen content in lignocellulosic biomasses and in their derived platform molecules is receiving increasing attention. In this contribution we highlight recent advances in the transfer hydrogenolysis of cellulose, hemicellulose, lignin, and of their derived model molecules promoted by heterogeneous catalysts for the sustainable production of biofuels and biochemicals.

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Hydrogenolysis through catalytic transfer hydrogenation: Glycerol conversion to 1,2-propanediol

Cited by 94 publications

References 40 publications

Hydrogen production from formic acid vapour over a Pd/C catalyst promoted by potassium salts: Evidence for participation of buffer-like solution in the pores of the catalyst

Hydrogen production from formic acid vapour over a Pd/C catalyst promoted by potassium salts: Evidence for participation of buffer-like solution in the pores of the catalyst

A Radical Mechanism for the Vanadium-Catalyzed Deoxydehydration of Glycols

Catalytic Transfer Hydrogenolysis as an Effective Tool for the Reductive Upgrading of Cellulose, Hemicellulose, Lignin, and Their Derived Molecules

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