2026-04-13T01:31:28Zhttps://recercat.cat/oai/request

oai:recercat.cat:2072/3057652026-01-15T14:12:35Zcom_2072_300912com_2072_4427col_2072_301309

RECERCAT author Albani, Davide author Li, Qiang author Vilé, Gianvito author Mitchell, Sharon author Almora-Barrios, Neyvis author Witte, Peter T. author López, Núria author Pérez-Ramírez, Javier 2018-01-15T16:04:19Z2018-02-15T10:27:35Z2024-04-23T10:26:44Z 2018-01-15T16:04:19Z2018-02-15T10:27:35Z2024-04-23T10:26:44Z 2017 http://hdl.handle.net/2072/305765 https://doi.org/10.1039/C6GC02586B Gamma-valerolactone (GVL), a versatile renewable compound listed among the top 10 most promising platform chemicals 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 RuOx species. Aiming at an improved catalyst design, we have prepared ruthenium nanoparticles modified with the water-soluble hexadecyl(2-hydroxyethyl)dimethylammonium dihydrogen phosphate (HHDMA) ligand and supported on TiSi2O6. The hybrid catalyst has been characterised by ICP-OES, elemental analysis, TGA, DRIFTS, H2-TPR, STEM, EDX, 31P and 13C MAS-NMR, and XPS. When evaluated in the continuous-flow hydrogenation of LA, the Ru-HHDMA/TiSi2O6 catalyst (0.24 wt% Ru) displays a fourfold higher reaction rate than the state-of-the-art Ru/C catalyst, while maintaining 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 at 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. eng Copyright © Royal Society of Chemistry 2017 Interfacial acidity in ligand-modified ruthenium nanoparticles boosts the hydrogenation of levulinic acid to gamma-valerolactone info:eu-repo/semantics/article URL https://recercat.cat/bitstream/2072/305765/2/Interfacial%20acidity%20in%20ligand-modified%20ruthenium%20nanoparticles%20boosts%20the%20hydrogenation%20of%20levulinic%20acid%20to%20gamma-valerolactone.pdf File MD5 3f876c087ef1d999cc843c05e79e4c24 1010438 application/pdf Interfacial acidity in ligand-modified ruthenium nanoparticles boosts the hydrogenation of levulinic acid to gamma-valerolactone.pdf URL https://recercat.cat/bitstream/2072/305765/1/Interfacial%20acidity%20in%20ligand-modified%20ruthenium%20nanoparticles%20boosts%20the%20hydrogenation%20of%20levulinic%20acid%20to%20gamma-valerolactone.pdf.txt File MD5 72bd4f70b9151ada540fc78dd6670f92 44606 text/plain Interfacial acidity in ligand-modified ruthenium nanoparticles boosts the hydrogenation of levulinic acid to gamma-valerolactone.pdf.txt