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Multi-catalytic active site biochar-based catalysts for glucose isomerized to fructose: Experiments and density functional theory study

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Abstract

This work provides an innovative method for preparing different isomerization catalysts by impregnating different proportions of MgCl2 and AlCl3 and combining different K compounds on cellulose-derived biochar, followed by pyrolysis. Results show MgO and Al(OH)3 existing in 4Mg-1Al-C catalyst can obtain better catalytic effect on glucose isomerization than the singe of Al presenting in 0Mg-1Al-C catalyst. Moreover, the synergism effects of the multi-catalytic active sites such as β-, γ-Al(OH)3, KCl, MgO, and K4H2(CO3)3 in Mg-Al-KHCO3-C catalyst can further lead to an increase in glucose isomerization, compared to the 4Mg-1Al-C catalyst. The X-ray diffraction results present that the value of O/Al in Mg-Al-KHCO3-C catalyst is as high as 13.38, which provides many unsaturated acidic catalysis sites and benefits the glucose isomerization. Simultaneously, the TPD results reveal that the main active sites (MgO, Al(OH)3, and K4H2(CO3)3) in Mg-Al-KHCO3-C catalyst can provide weakly acidic and basic sites and avoid strongly acidic and basic sites to excessively attack the glucose. Based on the DFT analysis, the results indicate that the MgO has a great effect on the ring-opening reaction to form acyclic glucose, while Al(OH)3+ has a great effect on promoting acyclic glucose hydrogen transfer isomerized to form fructose. Compared to other carbon-based metal catalysts, the prepared Mg-Al-KHCO3-C has excellent catalytic performance, which gives a higher fructose yield (38.7%) and selectivity (87.72%) and glucose conversion (44.12%) at 100 °C in 30 min. In this study, we develop a highly efficient Mg-Al-K-biochar catalyst for glucose isomerization and provide an efficient method for cellulose valorization.

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Funding

This work was sponsored by the National Natural Science Foundation of China (grant no. 22268007); Natural Science Foundation of Guangxi Province, China (grant no. 2021GXNSFDA196006); Guangxi Science and Technology Major Pro-gram (Guike AA22117013); Innovation Project of Guangxi Graduate Education (grant no. YCBZ2023020). AJR efforts were supported by the University of Tennessee, Knoxville.

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Authors and Affiliations

  1. Guangxi Key Laboratory of Clean Pulp & Papermaking and Pollution Control, College of Light Industry and Food Engineering, Guangxi University, Nanning, 530004, People’s Republic of China

    Xiheng Kang, Zi You, Yongheng Huang, Jian Peng & Xueping Song

  2. Jiangsu Co-Innovation Center of Efficient Processing and Utilization of Forest Resources, College of Chemical Engineering, Nanjing Forestry University, Nanjing, 210037, China

    Junhua Zhang

  3. Department of Chemical and Biomolecular Engineering, University of Tennessee, Knoxville, TN, USA

    Arthur J. Ragauskas

  4. Joint Institute for Biological Sciences, Biosciences Division, Oak Ridge National Laboratory, Oak Ridge, TN, USA

    Arthur J. Ragauskas

  5. Center for Renewable Carbon, Department of Forestry, Wildlife and Fisheries, The University of Tennessee, Knoxville, TN, 37996, USA

    Arthur J. Ragauskas

  6. School of Mechanical, Medical and Process Engineering, Centre for Agriculture and the Bioeconomy, Queensland University of Technology, Brisbane, QLD, 4000, Australia

    Zhanying Zhang

  7. Center for Agriculture and the Bioeconomy Faculty of Science, Queensland University of Technology, Brisbane, QLD, 4000, Australia

    Zhanying Zhang

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  1. Xiheng Kang
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Contributions

Xiheng Kang: Conceptualization, data curation, investigation, methodology, project administration, DFT, Multiwfn, supervision, validation, visualization, writing (original draft), writing—review and editing. Zi You: Methodology, validation, visualization. Yongheng Huang: Resource. Jian Peng: Software. Junhua Zhang: Methodology. Arthur J. Ragauskas: Formal analysis, funding acquisition, writing—review and editing. Zhanying Zhang: Methodology. Xueping Song: Methodology, project administration, supervision, validation, visualization, writing (original draft), writing—review and editing.

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Kang, X., You, Z., Huang, Y. et al. Multi-catalytic active site biochar-based catalysts for glucose isomerized to fructose: Experiments and density functional theory study. Adv Compos Hybrid Mater 7, 54 (2024). https://doi.org/10.1007/s42114-024-00861-2

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