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Scalable production of carboxylated cellulose nanofibres using a green and recyclable solvent

Nature Sustainability volume 7, pages 315–325 (2024)Cite this article

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Abstract

Produced from plant renewable resources, cellulose nanofibres are an emerging class of sustainable materials with favourable mechanical properties. Once carboxylated, they can be used even more widely thanks to the possibility of surface chemical modifications. However, the current fabrication processes for carboxylated cellulose nanofibres (C-CNFs) either require harsh reaction conditions or severely impair the high aspect ratio of products, resulting in low yields, environmental impacts and poor practical value. Here we address these limitations by using a hydrated multi-carboxylic acid deep eutectic solvent comprised of only choline chloride, citric acid and water to produce ultrafine and fairly long C-CNFs. The resultant C-CNFs possess fine diameters of ~3.4 nm, high aspect ratios up to 2,500, a high carboxyl content of 1.5 mmol g−1 and a high mass yield of 90.12%. Superior stability of the C-CNFs suspensions even at high concentrations allows for easy storage, transportation, processing and utilization. Moreover, the solvent exhibits a tenfold increase in its reusability, thereby highlighting its recyclability and economic viability. We further show large-scale production of C-CNFs for preparing large-area, high-performance structural materials. These unique advantages open a new avenue to the production of functional C-CNFs at an industry compatible scale.

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Fig. 1: Fabrication mechanism and advantages of this method.
Fig. 2: Morphological features of CNFs and C-CNFs.
Fig. 3: Depictions of the chemical structures of CNFs and C-CNFs.
Fig. 4: Large-scale preparation of C-CNFs and efficient reuse of H-DES.
Fig. 5: Economic efficacy and environmental impact of C-CNFs production.
Fig. 6: Physical and mechanical properties of C-CNF-derived materials.

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Data availability

The data supporting the findings are provided within this article and its Supplementary Information and are available from the corresponding authors on reasonable request.

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Acknowledgements

H.Y. thanks the generous support by the National Science Fund for Distinguished Young Scholars of China (H.Y.; grant number 31925028) and the Fundamental Research Funds for the Central Universities (H.Y.; grant number 2572023CT04). Z.W. and S.L. thank China Scholarship Council for the financial support for PhD study.

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Author notes

  1. These authors contributed equally: Xiaochao Shi, Zengbin Wang.

Authors and Affiliations

  1. Key Laboratory of Bio-based Material Science and Technology of Ministry of Education, Northeast Forestry University, Harbin, China

    Xiaochao Shi, Qinqin Xia, Yongzhuang Liu, Wenshuai Chen & Haipeng Yu

  2. Sustainable Materials and Chemistry, Department of Wood Technology and Wood-based Composites, University of Göttingen, Göttingen, Germany

    Zengbin Wang, Siyuan Liu & Kai Zhang

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Contributions

H.Y. and K.Z. conceived the concept. X.S. and Z.W. performed most of the experiments. X.S., Z.W., H.Y. and K.Z. co-wrote the paper. S.L., Q.X., Y.L., W.C. and K.Z. participated in analysis of the results. All authors contributed to the general discussion and reviewing of the paper.

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Correspondence to Haipeng Yu or Kai Zhang.

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Nature Sustainability thanks Haishun Du, Zhiqiang Fang, Akira Isogai, Junyong Zhu and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–46, Tables 1–6 and Movies 1–4.

Reporting Summary

Supplementary Video 1

Pilot-scale production of C-CNFs.

Supplementary Video 2

Suspension of C-CNFs with high solids content.

Supplementary Video 3

Fabrication of a large-area C-CNF film.

Supplementary Video 4

The recyclability and reusability of C-CNFs products.

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Shi, X., Wang, Z., Liu, S. et al. Scalable production of carboxylated cellulose nanofibres using a green and recyclable solvent. Nat Sustain 7, 315–325 (2024). https://doi.org/10.1038/s41893-024-01267-0

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