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Understanding the Mechanocatalytic Conversion of Biomass: A Low‐Energy One‐Step Reaction Mechanism by Applying Mechanical Force
Author(s) -
Amirjalayer Saeed,
Fuchs Harald,
Marx Dominik
Publication year - 2019
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201811091
Subject(s) - depolymerization , renewable energy , mechanism (biology) , cellulose , reaction mechanism , chemistry , glycosidic bond , potential energy , nanotechnology , biochemical engineering , materials science , catalysis , organic chemistry , engineering , physics , electrical engineering , quantum mechanics , enzyme
Abstract On the way to establishing biomass as a renewable and environmentally friendly source to cover the ever‐increasing global demand on energy and chemicals, one great challenge is the efficient depolymerization of cellulose. Enhanced conversion rates have been discovered in ball‐milling experiments, thus opening a mechanocatalytic approach. However, an understanding of the impact of mechanical forces on the acid‐catalyzed cleavage of glycosidic bonds at the molecular level is still missing. Herein, we contribute such fundamental insight based on atomistic modeling. Mechanically stressing the macromolecular backbone radically changes the depolymerization pathway from a complex high‐barrier reaction upon thermal activation to a low‐energy single‐step mechanocatalytic process. In addition to revealing a regioselective increase in basicity under a mechanical force, our results provide molecular‐level explanations of the experimental findings and might therefore guide rational ways to improve such mechanocatalytic processes.