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Effects of chloride ions in acid-catalyzed biomass dehydration reactions in polar aprotic solvents
- Source :
- Nature Communications, Vol 10, Iss 1, Pp 1-10 (2019), Nature Communications
- Publication Year :
- 2019
- Publisher :
- Nature Portfolio, 2019.
-
Abstract
- The use of polar aprotic solvents in acid-catalyzed biomass conversion reactions can lead to improved reaction rates and selectivities. We show that further increases in catalyst performance in polar aprotic solvents can be achieved through the addition of inorganic salts, specifically chlorides. Reaction kinetics studies of the Brønsted acid-catalyzed dehydration of fructose to hydroxymethylfurfural (HMF) show that the use of catalytic concentrations of chloride salts leads to a 10-fold increase in reactivity. Furthermore, increased HMF yields can be achieved using polar aprotic solvents mixed with chlorides. Ab initio molecular dynamics simulations (AIMD) show that highly localized negative charge on Cl− allows the chloride anion to more readily approach and stabilize the oxocarbenium ion that forms and the deprotonation transition state. High concentrations of polar aprotic solvents form local hydrophilic environments near the reactive hydroxyl group which stabilize both the proton and chloride anions and promote the dehydration of fructose.<br />Despite the potential advantages of using polar aprotic solvents for biomass upgrading reactions, fundamental understanding of these solvation effects is limited at present. Here, the authors show that further increases in catalyst performance in polar aprotic solvents can be achieved through the addition of inorganic salts.
- Subjects :
- 0301 basic medicine
Science
Inorganic chemistry
Oxocarbenium
General Physics and Astronomy
02 engineering and technology
Chloride
Article
General Biochemistry, Genetics and Molecular Biology
Catalysis
Chemical kinetics
03 medical and health sciences
chemistry.chemical_compound
Deprotonation
medicine
Reactivity (chemistry)
lcsh:Science
Multidisciplinary
Solvation
General Chemistry
021001 nanoscience & nanotechnology
030104 developmental biology
chemistry
lcsh:Q
0210 nano-technology
Hydroxymethylfurfural
medicine.drug
Subjects
Details
- Language :
- English
- ISSN :
- 20411723
- Volume :
- 10
- Issue :
- 1
- Database :
- OpenAIRE
- Journal :
- Nature Communications
- Accession number :
- edsair.doi.dedup.....3d9a82b10a732f9839e712304aef5a99