Green synthesis of cellulose formate and its efficient conversion into 5-hydroxymethylfurfural

Chunxiao Gong, Xianzhi Meng, Caidi Jin, Ming Yang, Jianglong Liu, Kuichuan Sheng, Yunqiao Pu, Arthur Ragauskas, Guanya Ji, Ximing Zhang

Research output: Contribution to journalArticlepeer-review

9 Scopus citations

Abstract

5-hydroxymethylfurfural (HMF) production from cellulose is a hot topic, while the rigidity of cellulose limits its efficient conversion into HMF. Cellulose formate has exhibited the great potential for HMF production but it's synthesis via direct formylation of cellulose in formic acid is difficult. Herein, we reported a green synthetic route of cellulose formate and its efficient conversion into HMF. Ball milled cellulose formate (BCF) was synthesized via ball milling followed by formylation in formic acid at 80 °C for 0.5 h. The structure of BCF was thoroughly characterized and BCF was subsequently converted to HMF catalyzed by AlCl3 and HCl in dimethyl sulfoxide (DMSO)-H2O media. Results showed that ball milling of cellulose for 1–1.5 h efficiently deconstructed its crystallinity and degree of polymerization, boosting its further formylation and catalytic conversion. An overall 66.9% HMF yield from cellulose was achieved at 150 °C for 20 min using BCF derived from cellulose ball milled for 1.5 h as the substrate. BCF exhibits high reactivity toward HMF due to its excellent solubility and accessibility in DMSO-H2O media, and the release of formic acid in reaction further facilitates HMF production. BCF synthesized with different ball milling times shows different degrees of substitution of formyl groups, which could serve as an indicator and regulate the HMF production. The green synthesis of cellulose formate creates an efficient pathway for HMF production.

Original languageEnglish
Article number115985
JournalIndustrial Crops and Products
Volume192
DOIs
StatePublished - Feb 2023

Funding

This work was supported by the National Natural Science Foundation of China (No. 22208291 ) and the Zhejiang University K. P. Chao's High Technology Development Foundation (No. 2020QN021 ), and CG acknowledges the support from 2021 International Postdoctoral Exchange Fellowship Program (Talent-Introduction Program, Grants No. YJ20210167 ) and China Postdoctoral Science Foundation ( 2022M712767 ). GJ acknowledges the support from the Natural Science Foundation of the Jiangsu Higher Education Institutions of China ( 20KJB416009 ) and China Postdoctoral Science Foundation ( 2020M671367 ). AJR and ZM wish to acknowledge University of Tennessee for support for their efforts.

FundersFunder number
National Natural Science Foundation of China22208291
Zhejiang University2020QN021

    Keywords

    • 5-hydroxymethylfurfural
    • Ball milled cellulose formate
    • Cellulose
    • Dimethyl sulfoxide

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