Interfacial Thermoconvection and Atomic Relay Catalysis Enable Equilibrium Shifting and Rapid Glucose-to-Fructose Isomerization.

Autor: Huang J; State Key Laboratory of Green Pesticide, Key Laboratory of Green Pesticide & Agricultural Bioengineering, Ministry of Education, State-Local Joint Laboratory for Comprehensive Utilization of Biomass, Center for R&D of Fine Chemicals, Guizhou University, 550025, Guiyang, Guizhou, China., Li H; State Key Laboratory of Green Pesticide, Key Laboratory of Green Pesticide & Agricultural Bioengineering, Ministry of Education, State-Local Joint Laboratory for Comprehensive Utilization of Biomass, Center for R&D of Fine Chemicals, Guizhou University, 550025, Guiyang, Guizhou, China., Saravanamurugan S; Laboratory of Bioproduct Chemistry, Centre of Innovative and Applied Bioprocessing (CIAB), 140306, Mohali, Punjab, India., Su Y; School of Chemistry, Engineering Research Center of Energy Storage Materials and Devices of Ministry of Education, National Innovation Platform (Center) for Industry-Education Integration of Energy Storage Technology, Xi'an Jiaotong University, 710049, Xi'an, China., Yang S; State Key Laboratory of Green Pesticide, Key Laboratory of Green Pesticide & Agricultural Bioengineering, Ministry of Education, State-Local Joint Laboratory for Comprehensive Utilization of Biomass, Center for R&D of Fine Chemicals, Guizhou University, 550025, Guiyang, Guizhou, China., Riisager A; Centre for Catalysis and Sustainable Chemistry, Department of Chemistry, Technical University of Denmark, DK-2800, Kgs. Lyngby, Denmark.
Jazyk: angličtina
Zdroj: Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2024 Dec 09; Vol. 63 (50), pp. e202411544. Date of Electronic Publication: 2024 Nov 06.
DOI: 10.1002/anie.202411544
Abstrakt: The aqueous glucose-to-fructose isomerization is controlled by thermodynamics to an equilibrium limit of ~50 % fructose yield. However, here we report an in situ fructose removal strategy enabled by an interfacial local photothermal effect in combination with relay catalysis of geminal and isolated potassium single atoms (K SAs) on graphene-type carbon (K sg /GT) to effectively bypass the equilibrium limit and markedly speed up glucose-to-fructose isomerization. At 25 °C, an unprecedented fructose yield of 68.2 % was obtained over K sg /GT in an aqueous solution without any additives under 30-min solar-like irradiation. Mechanistic studies expounded that the interfacial thermoconvection caused by the local photothermal effect of the graphene-type carbon and preferable glucose adsorption on single-atom K could facilitate the release of in situ formed fructose. The geminal K SAs were prone to form a stable metal-glucose complex via bidentate coordination, and could significantly reduce the C-H bond electron density by light-driven electron transfer toward K. This facilitated the hydride shift rate-determining step and expedited glucose isomerization. In addition, isolated K SAs favored the subsequent protonation and ring-closure process to furnish fructose. The integration of the interfacial thermoconvection-enhanced in situ removal protocol and tailored atomic catalysis opens a prospective avenue for boosting equilibrium-limited reactions under mild conditions.
(© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)
Databáze: MEDLINE
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