Investigating and exploiting surface cooperativity in multifunctional solid catalysts for carbohydrates reactions
Final Report Abstract
Heterogeneous acid catalysts play a key role in the sustainable production of valuable chemicals from non-edible carbohydrate-enriched biomass in biorefinaries. However, the high oxygen content of biomass and the complexity of their reactions create challenges to the development of efficient catalysts. The objective of this project was the development of active multifunctional acid catalysts based on metal oxides, by exploiting the cooperation between different surface entities (different catalytic sites or sites and other functional groups). Several catalysts having Brønsted acid sites, Lewis acid sites or both were prepared in organic solvents (acetophenone, benzyl alcohol, and ethanol), namely Nb2O5 nanoparticles (NP), Nb2O5-highly oxidized graphene oxide composites, niobium and tungsten silicates, niobium silicates functionalized with propylsulfonic acid groups, WO3, tungsten oxide functionalized with phosphonic acids, TiO2 NPs functionalized with phosphonic acids, and core-shell TiO2-WO3- phosphonic acid NPs. These materials showed high activity for one or several of the biomass catalytic transformations studied: fructose dehydration to 5-hydroxymethylfurfural (HMF), glucose isomerization, glucose isomerization-dehydration to HMF, etherification and/or esterification of HMF, α-angelica lactone, and furfuryl alcohol with ethanol. All these reactions are important transformations in the context of biorefineries for the production of valuable industrial compounds, including biofuels. A thorough characterization of the catalysts allowed to establish correlations between their structure, acid sites, and activity, and cooperations between different surface species. During the execution of the project, it was found that ketones have high potential as solvents and oxygen donors for the synthesis at low temperatures of metal oxides catalysts with controlled structure, as well as functionalized oxides, hybrids and composite catalysts. This route offers a broad window of synthetic possibilities for developing active catalytic materials in future work.
Publications
- ACS Appl. Mater. Interfaces 2017, 9, 14013
R. Zhang, P. A. Russo, M. Feist, P. Amsalem, N. Koch, N. Pinna
(See online at https://doi.org/10.1021/acsami.7b01178) - Adv. Funct. Mater. 2017, 27, 1703158
R. Zhang, P. A. Russo, A. G. Buzanich, T. Jeon, N. Pinna
(See online at https://doi.org/10.1002/adfm.201703158) - J. Nanopart. Res. 2018, 20, 146
R. Zhang, S. M. El-Refaei, P. A. Russo, N. Pinna
(See online at https://doi.org/10.1007/s11051-018-4246-y) - Nanomaterials 2018, 8, 249
X. Han, S. Wahl, P. A. Russo, N. Pinna
(See online at https://doi.org/10.3390/nano8040249) - Adv. Energy Mater. 2019, 9, 1902813
X. Han, P. A. Russo, N. Goubard-Bretesché, S. Patanè, S. Santangelo, R. Zhang, N. Pinna
(See online at https://doi.org/10.1002/aenm.201902813) - Commun. Chem. 2019, 2, 129
K. Skrodczky, M. M. Antunes, X. Han, S. Santangelo, G. Scholz, A. A. Valente, N. Pinna, P. A. Russo
(See online at https://doi.org/10.1038/s42004-019-0231-3)
