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One-step conversion of biomass to reduced graphene oxide at room temperature

Nature Sustainability volume 7, pages 1699–1708 (2024)Cite this article

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Abstract

Although graphene and graphene-related two-dimensional materials (GR2Ms) hold much potential for various applications, the current methods for their large-scale production rely heavily on graphite minerals and energy-intensive techniques. Here we report a one-step dehydration–condensation method for the economical and green preparation of GR2Ms on a gram scale from biomass at room temperature under atmospheric pressure using only concentrated sulfuric acid. This protocol has been applied successfully to various types of biomass and carbohydrates, delivering a 33% mass yield of GR2M product. The properties of the product are consistent with those of classical reduced graphene oxide (RGO), with the twist that it does not need to be produced from graphite minerals. The mild reaction conditions substantially reduce the energy input, while providing a facile platform for monitoring the kinetics of RGO nucleation and growth. Compared with conventional methods, a 98% reduction in energy consumption is achieved. Overall, the results of this research pave a new avenue to scalable and sustainable GR2M production.

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Fig. 1: Conversion of biomass into graphene at room temperature and characterization of the D–C RGO.
Fig. 2: Characterization of the D–C RGO derived from biomass.
Fig. 3: Exploration of the reaction mechanism at the molecular level and the proposed pure carbon paradigm.
Fig. 4: Comparison of the D–C method with conventional methods for the preparation of GR2M.
Fig. 5: New understanding of graphene nucleation and growth behaviour in the D–C reaction.

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All of the data needed to evaluate the conclusions in the paper are presented in the paper and/or its Supplementary Information. Source data are provided with this paper.

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Acknowledgements

We thank M.-X. Wang at Tsinghua University most sincerely for fruitful discussions. This work was supported by the National Natural Science Foundation of China (22193020, 22193022 and 22371251, Q.-H.G.), the China Postdoctoral Science Foundation (2022M722734, D.-C.W.), the Tsinghua University Initiative Scientific Research Program (Q.-H.G.), the Postdoctoral Science Preferential Funding of Zhejiang Province (ZJ2022100, D.-C.W.), the Intergovernmental Scientific and Technological Innovation Cooperation Project of Zhejiang Province (2023C04031, D.-C.W.) and the Starry Night Science Fund of the ZJU Shanghai Institute for Advanced Study (SN-ZJU-SIAS-006, Q.-H.G.). H.-Y.Y. acknowledges support from the National Natural Science Foundation of China (42125105). We thank Zhejiang University (ZJU) and the ZJU-Hangzhou Global Scientific and Technological Innovation Center (ZJU-HIC) for their continued support. J.F.S. acknowledges support from Northwestern University. We thank G.-Q. Zhu, L.-N. Wang, X.-F. Yu, Y.-X. Qian, X.-C. Bo, Y. Wu, X. Xiao and S.-T. Han for their helpful discussions on characterization protocols.

Author information

Authors and Affiliations

  1. Stoddart Institute of Molecular Science, Department of Chemistry, Zhejiang University, Hangzhou, China

    Duan-Chao Wang, Jin-Ze Lv, Yang Liu, Sheng-Nan Lei, J. Fraser Stoddart & Qing-Hui Guo

  2. ZJU-Hangzhou Global Scientific and Technological Innovation Center, Hangzhou, China

    Duan-Chao Wang, Sheng-Nan Lei, J. Fraser Stoddart & Qing-Hui Guo

  3. Hangzhou Institute of Technology, Xidian University, Hangzhou, China

    Shenjie Zhong

  4. Department of Industrial Design, Hangzhou City University, Hangzhou, China

    Yuhang Wu

  5. MOE Key Laboratory of Advanced Textile Materials and Manufacturing Technology, Zhejiang Sci-Tech University, Hangzhou, China

    Hou-Yong Yu

  6. MOE Key Laboratory of Organic Optoelectronics and Molecular Engineering, Department of Chemistry, Tsinghua University, Beijing, China

    Liangti Qu

  7. Department of Chemistry, Northwestern University, Evanston, IL, USA

    J. Fraser Stoddart

  8. Center for Regenerative Nanomedicine, Northwestern University, Evanston, IL, USA

    J. Fraser Stoddart

  9. School of Chemistry, University of New South Wales, Sydney, New South Wales, Australia

    J. Fraser Stoddart

  10. MOE Key Laboratory of Bioorganic Phosphorus and Chemical Biology, Department of Chemistry, Tsinghua University, Beijing, China

    Qing-Hui Guo

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Contributions

D.-C.W., J.F.S. and Q.-H.G. conceived the study; D.-C.W., J.F.S. and Q.-H.G. designed the experiments; D.-C.W. conducted the experiments and characterizations, analysed the data; D.-C.W., J.-Z.L., Y.L., S.-N.L. and Q.-H.G. conducted the NMR and ESI-MS analyses and proposed the mechanism; D.-C.W. and S.Z. contributed to the XPS studies; J.-Z.L., Y.W. and Q.-H.G. independently performed the replications and validated the experiments; all of the authors contributed to the data analysis; D.-C.W., H.-Y.Y., L.Q., J.F.S. and Q.-H.G. wrote the draft paper with input from all authors.

Corresponding authors

Correspondence to J. Fraser Stoddart or Qing-Hui Guo.

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Competing interests

D.-C.W. and Q.-H.G. have filed two patent applications (Chinese Patent application number 202210494990.3 and US Patent application number US18138020) based on this work, which have been lodged with the ZJU-Hangzhou Global Scientific and Technological Innovation Center. The other authors declare no competing interests.

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Extended data

Extended Data Fig. 1 Several features in D-C RGO growth.

a, AFM Images of zoomed-in view of nuclei 1 and 5 in Fig. 5a in the main text. The white arrows point to wrinkles, which were formed as a result of internal stress. b, The RGO microcrystals observed in the AFM images polymerize towards the center of the nuclei and grow into a new layer. c, Irregular edges. d, HRTEM Images and SAED pattern of grain boundary after the combination of the D-C RGO. The similar results were obtained in three independent experiments.

Extended Data Fig. 2 A set of evidence for layer-by-layer growth of D-C RGO.

An AFM image of a growing D-C RGO nucleus. Statistics on the mean length of each layer in the layer-by-layer, the bottom-up growth rate fitting R2 is 0.989. The error bars are presented as the mean ± s.d. (n = 5). The similar results were obtained in three independent experiments.

Source data

Extended Data Fig. 3 AFM Images of nucleation and growth for D-C-ginger-RGO.

a, The nucleation process. b, Ribbon-like growth mode. c, Large area of D-C RGO and exfoliated few-layer RGO. The similar results were obtained in three independent experiments.

Extended Data Fig. 4 AFM Images of nucleation and growth for D-C-straw-RGO.

a, The nucleation process. b, Ribbon-like growth mode. c, Large area of D-C RGO and exfoliated few-layer RGO. The similar results were obtained in three independent experiments.

Extended Data Fig. 5 AFM Images of nucleation and growth for D-C-cellulose-RGO.

a, The nucleation process. b, Ribbon-like growth mode. c, Large area of D-C RGO and exfoliated few-layer RGO. The similar results were obtained in three independent experiments.

Extended Data Fig. 6 AFM Images of nucleation and growth for D-C-glucose-RGO.

a, The nucleation process. b, Ribbon-like growth mode. c, Large area of D-C RGO and exfoliated few-layer RGO. The similar results were obtained in three independent experiments.

Supplementary information

Supplementary Information

Supplementary text, characterizations, Figs. 1–72 and Tables 1–5.

Reporting Summary

Supplementary Video 1

Experimental procedure for the one-step preparation of D–C RGO at room temperature.

Source data

Source Data Fig. 1

Statistical source data for Fig. 1.

Source Data Fig. 2

Statistical source data for Fig. 2.

Source Data Fig. 3

Statistical source data for Fig. 3.

Source Data Fig. 4

Statistical source data for Fig. 4.

Source Data Fig. 5

Statistical source data for Fig. 5.

Source Data Extended Data Fig. 2

Statistical source data for Extended Data Fig. 2.

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Wang, DC., Lv, JZ., Zhong, S. et al. One-step conversion of biomass to reduced graphene oxide at room temperature. Nat Sustain 7, 1699–1708 (2024). https://doi.org/10.1038/s41893-024-01480-x

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