Mechanistic understanding of salt-assisted autocatalytic hydrolysis of cellulose

Zhicheng Jiang; Jiajun Fan; Vitaliy L. Budarin; Duncan J. Macquarrie; Yang Gao; Tianzong Li; Changwei Hu; James H. Clark

doi:10.1039/C8SE00045J

Mechanistic understanding of salt-assisted autocatalytic hydrolysis of cellulose

Zhicheng Jiang, Jiajun Fan, Vitaliy L. Budarin, Duncan J. Macquarrie, Yang Gao, Tianzong Li, Changwei Hu^*, James H. Clark

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

Abstract

Depolymerisation of cellulose is a critical step for biomass-based bio-refining processes to produce valuable chemicals. Herein, we propose the mechanism of the promoting effect of NaCl on the cellulose hydrolysis process based on a systematic kinetic study involving variable temperature studies and the use of deuterated agents. It has been found that the presence of NaCl simultaneously enhances the generation of acidic products from cellulose decomposition and pushes the generated protons to the surface of cellulose, dramatically increasing surface acidity and facilitating the autocatalytic hydrolysis of cellulose. Cl ^- disrupted the intermolecular hydrogen bonding of cellulose, especially in the first surface layer. Thus, the solid cellulose chains were peeled off layer-by-layer, leading to an accelerated hydrolysis of cellulose by the adsorbed protons. Without the need for traditional acidic catalysts, this autocatalytic depolymerisation of cellulose in water, assisted by salt provides a practically viable route to the enhanced conversion of biomass to chemicals.

Original language	English
Pages (from-to)	936-940
Number of pages	5
Journal	Sustainable Energy & Fuels
Volume	2
Issue number	5
Early online date	6 Mar 2018
DOIs	https://doi.org/10.1039/C8SE00045J https://doi.org/10.1039/c8se00045j
Publication status	Published - 6 Mar 2018

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© The Royal Society of Chemistry 2018. This is an author-produced version of the published paper. Uploaded in accordance with the publisher’s self-archiving policy. Further copying may not be permitted; contact the publisher for details

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RSC Sustainable & Fuels - Just Accepted - Mechanistic Understanding of Salt-Assisted Autocatalytic Hydrolysis of Cellulose
© The Royal Society of Chemistry 2018. This is an author-produced version of the published paper. Uploaded in accordance with the publisher’s self-archiving policy. Further copying may not be permitted; contact the publisher for details
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abstract = " Depolymerisation of cellulose is a critical step for biomass-based bio-refining processes to produce valuable chemicals. Herein, we propose the mechanism of the promoting effect of NaCl on the cellulose hydrolysis process based on a systematic kinetic study involving variable temperature studies and the use of deuterated agents. It has been found that the presence of NaCl simultaneously enhances the generation of acidic products from cellulose decomposition and pushes the generated protons to the surface of cellulose, dramatically increasing surface acidity and facilitating the autocatalytic hydrolysis of cellulose. Cl - disrupted the intermolecular hydrogen bonding of cellulose, especially in the first surface layer. Thus, the solid cellulose chains were peeled off layer-by-layer, leading to an accelerated hydrolysis of cellulose by the adsorbed protons. Without the need for traditional acidic catalysts, this autocatalytic depolymerisation of cellulose in water, assisted by salt provides a practically viable route to the enhanced conversion of biomass to chemicals. ",

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AU - Gao, Yang

AU - Li, Tianzong

AU - Hu, Changwei

AU - Clark, James H.

N1 - © The Royal Society of Chemistry 2018. This is an author-produced version of the published paper. Uploaded in accordance with the publisher’s self-archiving policy. Further copying may not be permitted; contact the publisher for details

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AB - Depolymerisation of cellulose is a critical step for biomass-based bio-refining processes to produce valuable chemicals. Herein, we propose the mechanism of the promoting effect of NaCl on the cellulose hydrolysis process based on a systematic kinetic study involving variable temperature studies and the use of deuterated agents. It has been found that the presence of NaCl simultaneously enhances the generation of acidic products from cellulose decomposition and pushes the generated protons to the surface of cellulose, dramatically increasing surface acidity and facilitating the autocatalytic hydrolysis of cellulose. Cl - disrupted the intermolecular hydrogen bonding of cellulose, especially in the first surface layer. Thus, the solid cellulose chains were peeled off layer-by-layer, leading to an accelerated hydrolysis of cellulose by the adsorbed protons. Without the need for traditional acidic catalysts, this autocatalytic depolymerisation of cellulose in water, assisted by salt provides a practically viable route to the enhanced conversion of biomass to chemicals.

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Mechanistic understanding of salt-assisted autocatalytic hydrolysis of cellulose

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