Deep Eutectic Solvents for Efficient Fractionation of Lignocellulose to Produce Uncondensed Lignin and High-Quality Cellulose

Miao, Guohua; Li, Haichao; Zhu, Yutong; Chen, Sheng; Lu, Fachuang; Ralph, John; Xu, Feng

doi:10.1021/acssuschemeng.4c09673

Deep Eutectic Solvents for Efficient Fractionation of Lignocellulose to Produce Uncondensed Lignin and High-Quality Cellulose

Journal Article · Mon Jan 27 00:00:00 EST 2025 · ACS Sustainable Chemistry & Engineering

DOI:https://doi.org/10.1021/acssuschemeng.4c09673· OSTI ID:2539828

Miao, Guohua ^[1]; Li, Haichao ^[1]; Zhu, Yutong ^[1]; ^[1]; Lu, Fachuang ^[2]; ^[2]; Xu, Feng ^[1]

Beijing Forestry University (China)
University of Wisconsin, Madison, WI (United States)

Simultaneously inhibiting lignin condensation and cellulose degradation remains a major challenge for achieving holistic valorization of lignocellulose. Here, we developed a deep eutectic solvent (DES), composed of l-cysteine (Cys) and lactic acid (LA), to fractionate both uncondensed lignin and high-quality cellulose from eucalyptus wood by leveraging the unique properties of Cys, i.e., highly nucleophilic groups (–SH) and hydrogen bond acceptor/donor groups (–NH₂ and –COOH). The nucleophilic –SH in Cys effectively quenches the benzylic carbocations (C_α⁺ ions, formed at the benzylic sites of lignin) that lead to lignin condensation. This enables the high yield of uncondensed lignin (81%) with high retention of β–O–4 bonds (up to 90%). The separated uncondensed lignin is further depolymerized to prepare monophenols in a satisfactory 43% yield, equivalent to 73% of the theoretical yield. Moreover, the –NH₂ and –COOH groups in Cys form extensive hydrogen bonds with the hydroxyl groups in cellulose, thus decreasing the interaction energy of DES on cellulose. As a result, the cellulose achieves an astonishing 99% retention and maintains a high degree of polymerization of 1160. The obtained high-quality cellulose is further conversed into cellulose nanofibers for strong and transparent films. Furthermore, this study provides new insights into the efficient separation of uncondensed lignin and high-quality cellulose from lignocellulose by a novel DES system.

View Accepted Manuscript (DOE)

Research Organization:: Great Lakes Bioenergy Research Center (GLBRC), Madison, WI (United States)

Sponsoring Organization:: National Science Foundation of China; USDOE Office of Science (SC), Biological and Environmental Research (BER)

Grant/Contract Number:: SC0018409

OSTI ID:: 2539828

Journal Information:: ACS Sustainable Chemistry & Engineering, Journal Name: ACS Sustainable Chemistry & Engineering Journal Issue: 5 Vol. 13; ISSN 2168-0485

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Deep Eutectic Solvents for Efficient Fractionation of Lignocellulose to Produce Uncondensed Lignin and High-Quality Cellulose

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