Role of water in metal catalyst performance for ketone hydrogenation: a joint experimental and theoretical study on levulinic acid conversion into gamma-valerolactone

Michel, Carine; Zaffran, Jérémie; Ruppert, Agnieszka M.; Matras-Michalska, Joanna; Jędrzejczyk, Marcin; Grams, Jacek; Sautet, Philippe

doi:10.1039/c4cc04401k

Cited by 180 publications

(190 citation statements)

References 24 publications

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“…Standard reaction conditions were selected based our previous results [19,38,39], and are given in Table 2. The lower reaction temperature selected for the reaction in water (90°C) compared to dioxane (150°C) reflects the surprisingly high activity of Ru-based hydrogenation catalysts under aqueous conditions, for which the underlying reasons have been recently discussed [15,17,19,38,41,42]. The hydrogen pressure was set at 45 bar for all experiments.…”

Section: Hydrogenation Experiments Using the Anatase-supported Ru Catmentioning

confidence: 99%

Hydrogenation of levulinic acid to γ-valerolactone over anatase-supported Ru catalysts: Effect of catalyst synthesis protocols on activity

Piskun

Ftouni

Tang

et al. 2018

Applied Catalysis A: General

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Section: Hydrogenation Experiments Using the Anatase-supported Ru Catmentioning

confidence: 99%

Hydrogenation of levulinic acid to γ-valerolactone over anatase-supported Ru catalysts: Effect of catalyst synthesis protocols on activity

Piskun

Ftouni

Tang

et al. 2018

Applied Catalysis A: General

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“…These high barriers arise from the strong interaction of the metal surface with the bidentate O atoms from COO -which is  2 -O,O coordinated to the surface. Since the reaction is carried out in water, we have investigated the possibility that the solvent assists the C-O cleavage, 63 resulting in a barrier decrease to 1.08 and 1.17 eV, respectively. Since these barriers remain pretty large, only moderate contributions from ring closing reactions are expected from R-COO -species, due to the strong binding of the O of the carboxyl group, inhibiting the internal C-O bond formation.…”

Section: Mechanism Over Bare Ru Nanoparticlesmentioning

confidence: 99%

Interfacial acidity in ligand-modified ruthenium nanoparticles boosts the hydrogenation of levulinic acid to gamma-valerolactone

Albani

Vilé

et al. 2017

Green Chem.

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a Gamma-valerolactone (GVL), a versatile renewable compound listed among the top 10 most promising platform chemical by the US Department of Energy, is produced via hydrogenation of levulinic acid (LA). The traditional high-loading ruthenium-on-carbon catalyst (5 wt.% Ru) employed for this transformation suffers from low metal utilisation and poor resistance to deactivation due to the formation of RuO x species. Aiming at an improved catalyst design, we have prepared ruthenium nanoparticles modified with the water-soluble hydroxyethyl-dimethyl ammonium dihydrogen phosphate (HHDMA) ligand and supported on TiSi 2 O 6 . The hybrid catalyst has been characterised by ICP-OES, elemental analysis, TGA, DRIFTS, H 2 -TPR, STEM, EDX, 31 P and 13 C MAS-NMR, and XPS. When evaluated in the continuous-flow hydrogenation of LA, the Ru-HHDMA/TiSi 2 O 6 catalyst (0.24 wt.% Ru) displays a fourfold higher reaction rate than the stateof-the-art Ru/C catalyst, while maintaining a 100% selectivity to GVL and no sign of deactivation after 15 hours on stream. An in-depth molecular analysis by Density Functional Theory demonstrates that the intrinsic acidic properties of the ligand-metal interface under reaction conditions ensure that the less energy demanding path is followed. The reaction does not obey the expected cascade mechanism and intercalates hydrogenation steps, hydroxyl/water eliminations, and ring closings to ensure high selectivity. Moreover, the interfacial acidity increases the robustness of the material against ruthenium oxide formation. These results provide valuable improvements for the sustainable production of GLV and insights for the rationalisation of the exceptional selectivity of Ru-based catalysts.

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“…16 PCM can not describe any direct solvent effects and might be inaccurate for specific hydrogen bonds, 17 which makes the combination of micro-solvation with PCM particularly attractive. 2,[18][19][20][21] In aprotic solvents, the non-electrostatic solvent effects can become dominating, which is particularly challenging for PCM. 22 In subsequent work, Heyden turned the iSMS approach into an explicit solvent scheme, dubbed eSMS.…”

Section: Introductionmentioning

confidence: 99%

“…Another illustration is, as it has been shown particularly for biomass-related heterogeneous catalysis, that liquid water can modify significantly the catalytic activity of metallic supported catalysts compared to the more traditional gas-phase conditions. [1][2][3] However, first principles modeling of reactions under such conditions is still a great challenge, especially when the adsorbate is chemisorbed, forming covalent bonds with the catalyst.…”

Section: Introductionmentioning

confidence: 99%

Solvation free energies for periodic surfaces: comparison of implicit and explicit solvation models

Steinmann

Sautet

Michel

2016

Phys. Chem. Chem. Phys.

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101

112

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The evaluation of solvation energies is a great challenge. We focus here on an organic molecule chemisorbed at a metal-liquid interface, as a prototypical system, essential in tribology, electrochemistry and heterogeneous catalysis. We compare an established implicit solvation scheme with a strategy based on molecular mechanics (MM) free energy perturbation (FEP) seeded by QM computations. First, we benchmark the approaches against experimental hydration energies of standard (organic) molecules and find acceptable errors in the order of 0.06 eV (1.3 kcal/mol). Then, the impact of various parameters on the solvation energy of an adsorbate have been assessed on a typical system of interest, levulinic acid adsorbed at a Ru(0001)/water interface. We identify the need for dipole corrections or symmetric slabs when including solvation effects on metallic surfaces. The MM-FEP scheme is revealed to be as reliable as the implicit solvent for water. In the case of levulinic acid, both PCM and MM-FEP agree that the bulk solvation effect is not sufficient to change the adsorption mode from bidentate to mono-dentate, despite the fact that the COOH group is desolvated in the bidentate case. MM-FEP has the great advantage of being more easily generalized to other solvents and to be further improved which will be particularly useful to study solvent and (counter-)ion effects on interfacial reactions.

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Role of water in metal catalyst performance for ketone hydrogenation: a joint experimental and theoretical study on levulinic acid conversion into gamma-valerolactone

Abstract: Role of water in metal catalyst performance for ketone hydrogenation: a joint experimental and theoretical study on levulinic acid conversion into gamma-valerolactone

Cited by 180 publications

References 24 publications

Hydrogenation of levulinic acid to γ-valerolactone over anatase-supported Ru catalysts: Effect of catalyst synthesis protocols on activity

Hydrogenation of levulinic acid to γ-valerolactone over anatase-supported Ru catalysts: Effect of catalyst synthesis protocols on activity

Interfacial acidity in ligand-modified ruthenium nanoparticles boosts the hydrogenation of levulinic acid to gamma-valerolactone

Solvation free energies for periodic surfaces: comparison of implicit and explicit solvation models

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