Journal
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
Volume 16, Issue 11, Pages 5423-5433Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c3cp53836b
Keywords
-
Funding
- Texas Christian University
Ask authors/readers for more resources
This work presents a computational mechanistic study of the acid-catalyzed hydrolysis of lignin beta-O-4 linkages in ionic liquid solvents. Model compound 2-hydroyxyethyl phenyl ether undergoes dehydration to vinyl phenyl ether followed by hydrolysis to phenol and Hibbert's ketones. Larger model compound a-hydroxy-phenethyl phenyl ether illustrates an E1 dehydration mechanism involving resonance-stabilized carbocations. Continuum models for ionic liquid solvents indicate that solvation can significantly affect the reaction rates. The tested continuum ionic liquid solvents give similar results, and differ significantly from continuum organic solvents with comparable dielectric constants. The acidic ionic liquid cation 1-H-3-methylimidazolium has lower predicted catalytic activity than hydronium or HCl, consistent with the former's relatively small acid dissociation constant. Calculations with dispersion-corrected density functionals give similar behavior. Calculations on Lewis acidic metal chlorides used experimentally for lignin hydrolysis suggest that the metal chloride may participate in the initial dehydration. These results provide a baseline for future studies of improved hydrolysis catalysts.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available