Catalytic Transfer Hydrogenation and Acid Reactions of Furfural and 5-(Hydroxymethyl)furfural over Hf-TUD-1 Type Catalysts


Heterogeneous catalysis, which has served well the petrochemical industry, may valuably contribute towards a bio-based economy by sustainably enabling selective reactions to renewable chemicals. Carbohydrate-containing matter may be obtained from various widespread sources and selectively converted to furanic platform chemicals: furfural (Fur) and 5-(hydroxymethyl)furfural (Hmf). Valuable bioproducts may be obtained from these aldehydes via catalytic transfer hydrogenation (CTH) using alcohols as H-donors under relatively moderate reaction conditions. Hafnium-containing TUD-1 type catalysts were the first of ordered mesoporous silicates explored for the conversion of Fur and Hmf via CTH/alcohol strategies. The materials promoted CTH and acid reactions leading to the furanic ethers. The bioproducts spectrum was broader for the reaction of Fur than of Hmf. A Fur reaction mechanism based on literature data was discussed and supported by kinetic modelling. The influence of the Hf loading and reaction conditions (catalyst load, type of alcohol H-donor, temperature, initial substrate concentration) on the reaction kinetics was studied. The reaction conditions were optimized to maximize the yields of 2-(alkoxymethyl)furan ethers formed from Fur; up to 63% yield was reached at 88% Fur conversion, 4 h/150 degrees C, using Hf-TUD-1(75), which was a stable catalyst. The Hf-TUD-1(x) catalysts promoted the selective conversion of Hmf to bis(2-alkoxymethyl)furan; e.g., 96% selectivity at 98% Hmf conversion, 3 h/170 degrees C for Hf-TUD-1(50).




Biochemistry & Molecular Biology; Chemistry, Multidisciplinary


Antunes, MM; Silva, AF; Bernardino, CD; Fernandes, A; Ribeiro, F; Valente, AA

nossos autores


This work was developed within the scope of the project CICECO-Aveiro Institute of Materials, UIDB/50011/2020 and UIDP/50011/2020, financed by national funds through the Portuguese Foundation for Science and Technology/MCTES. The positions held by M.M.A. and A.F. were funded by national funds (OE), through FCT, I.P., in the scope of the framework contract foreseen in the numbers 4, 5, and 6 of article 23 of the Decree-Law 57/2016 of 29 August, changed by Law 57/2017 of 19 July. The position held by A.F.S. was funded by Project POCI-01-0145-FEDER-030075 (COMPETE 2020 Operational Thematic Program for Competitiveness and Internationalization) co-financed by national funds through the FCT/MCTES and the European Union through the European Regional Development Fund under the Portugal 2020 Partnership Agreement. The NMR spectrometer used is part of the National NMR Network (PTNMR) and is partially supported by Infrastructure Project No. 022161 (co-financed by FEDER through COMPETE 2020, POCI, and PORL and FCT through PIDDAC).

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