Citation: Rui Hao, Weixiang Guan, Fei Liu, Leilei Zhang, Aiqin Wang. Reaction Mechanism of Cellulose Conversion to Lactic Acid with Lewis Acid Catalysts[J]. Acta Physico-Chimica Sinica, ;2022, 38(10): 220502. doi: 10.3866/PKU.WHXB202205027 shu

Reaction Mechanism of Cellulose Conversion to Lactic Acid with Lewis Acid Catalysts

Rui Hao ¹ ,
Weixiang Guan ^1,, ,
Fei Liu ¹ ,
Leilei Zhang ¹ ,
Aiqin Wang ^{1, 2,,}

1.
CAS Key Laboratory of Science and Technology on Applied Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning Province, China
2.
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning Province, China

Corresponding author: Weixiang Guan, wxguan@dicp.ac.cn Aiqin Wang, aqwang@dicp.ac.cn
Received Date: 12 May 2022
Revised Date: 31 May 2022
Accepted Date: 1 June 2022
Available Online: 7 June 2022
Fund Project: the National Key R&D Program of China 2018YFB1501602National Natural Science Foundation of China 22132006the China Postdoctoral Science Foundation 2021M690149

Because fossil fuels are continuously depleted, valorization of biomass into valuable liquid products and chemicals is of great significance yet it remains challenging. Among many biomass-derived products, lactic acid is one of the most important renewable monomers for preparing the degradable polymer polylactic acid. The use of raw biomass to produce lactic acid through catalytic conversion is an attractive approach. In this work, the catalytic reaction performance and mechanism of different Lewis acids (Y³⁺, Sc³⁺, and Al³⁺) for the production of lactic acid from cellulose were investigated in detail by isotopic nuclear magnetic resonance (NMR) and mass spectrometry. The production of lactic acid from cellulose includes tandem and competing reactions. The order of catalytic activity for the one-pot conversion of cellulose into lactic acid is as follows: Y³⁺ > Al³⁺ > Sc³⁺. The main tandem reactions involve the hydrolysis of cellulose into glucose, the isomerization of glucose into fructose (the order of catalytic activity, the same below: Y³⁺ > Al³⁺, Y³⁺ > Sc³⁺), the cleavage of fructose via a retro-aldol reaction to glyceraldehyde (GLY) and 1, 3-dihydroxyacetone (DHA) (Sc³⁺ > Y³⁺ > Al³⁺), and the conversion of DHA or GLY to the final product lactic acid (Al³⁺ > Y³⁺ > Sc³⁺). It was found that the process of glucose isomerization to fructose was the key step to the final selectivity of the tandem reaction of cellulose conversion to lactic acid, and it was clarified that the production of lactic acid from DHA underwent a keto-enol (K-E) tautomerization process rather than a classical 1, 2-shift process. First, DHA was transformed into GLY via the isomerization process, then the adjacent hydroxyl group of GLY was removed in the form of water to produce an α, β-unsaturated species. After that, the α, β-unsaturated species underwent K-E tautomerization to generate unsaturated aldehyde-ketone intermediates. Meanwhile, a molecule of water was added to aldehyde-ketone intermediates to obtain a diol product, the hydrogen atom at the methine position was transferred and the lactic acid was finally obtained through the K-E tautomerization process. The in-depth understanding of the reaction mechanism presented in this work will help to design more selective catalysts for cellulose conversion into value-added oxygen-containing small molecule chemicals.
- Cellulose,
- Glucose,
- Fructose,
- Lactic acid,
- Lewis acid,
- Keto-enol tautomerization
1. [1]
  Pang, X.; Zhuang, X.; Tang, Z.; Chen, X. Biotechnol. J. 2010, 5 (11), 1125. doi: 10.1002/biot.201000135 doi: 10.1002/biot.201000135
2. [2]
  Ilyas, R. A.; Sapuan, S. M.; Harussani, M. M.; Hakimi, M.; Haziq, M. Z. M.; Atikah, M. S. N.; Asyraf, M. R. M.; Ishak, M. R.; Razman, M. R.; Nurazzi, N. M.; et al. Polymers (Basel) 2021, 13 (8), 1326. doi: 10.3390/polym13081326 doi: 10.3390/polym13081326
3. [3]
  Zhang, J.; Lu, F.; Yu, W.; Lu, R.; Xu, J. Chin. J. Catal. 2016, 37 (1), 177. doi: 10.1016/S1872-2067(15)60976-7 doi: 10.1016/S1872-2067(15)60976-7
4. [4]
  Wang, F. -F.; Liu, J.; Li, H.; Liu, C. -L.; Yang, R. -Z.; Dong, W. -S. Green Chem. 2015, 17 (4), 2455. doi: 10.1039/c4gc02131b doi: 10.1039/c4gc02131b
5. [5]
  Marianou, A. A.; Michailof, C. C.; Ipsakis, D.; Triantafyllidis, K.; Lappas, A. A. Green Chem. 2019, 21 (22), 6161. doi: 10.1039/c9gc02622c doi: 10.1039/c9gc02622c
6. [6]
  Alves de Oliveira, R.; Komesu, A.; Vaz Rossell, C. E.; Maciel Filho, R. Biochem. Eng. J. 2018, 133, 219. doi: 10.1016/j.bej.2018.03.003 doi: 10.1016/j.bej.2018.03.003
7. [7]
  Dusselier, M.; Van Wouwe, P.; Dewaele, A.; Makshina, E.; Sels, B. F. Energy Environ. Sci. 2013, 6 (5), 1415. doi: 10.1039/c3ee00069a doi: 10.1039/c3ee00069a
8. [8]
  Wang, Y.; Deng, W.; Wang, B.; Zhang, Q.; Wan, X.; Tang, Z.; Wang, Y.; Zhu, C.; Cao, Z.; Wang, G.; et al. Nat. Commun. 2013, 4, 2141. doi: 10.1038/ncomms3141 doi: 10.1038/ncomms3141
9. [9]
  Yang, M.; Qi, H.; Liu, F.; Ren, Y.; Pan, X.; Zhang, L.; Liu, X.; Wang, H.; Pang, J.; Zheng, M.; et al. Joule 2019, 3 (8), 1937. doi: 10.1016/j.joule.2019.05.020 doi: 10.1016/j.joule.2019.05.020
10. [10]
  Zhou, H.; Jing, Y.; Wang, Y. Acta Phys. -Chim. Sin. 2022, 38, 2203016
11. [11]
  Li, D.; Ni, W.; Hou, Z. Chin. J. Catal. 2017, 38 (11), 1784. doi: 10.1016/S1872-2067(17)62908-5 doi: 10.1016/S1872-2067(17)62908-5
12. [12]
  Ye, J.; Chen, C.; Zheng, Y.; Zhou, D.; Liu, Y.; Chen, D.; Ni, L.; Xu, G.; Wang, F. Appl. Catal. A: Gen. 2021, 619, 118133. doi: 10.1016/j.apcata.2021.118133 doi: 10.1016/j.apcata.2021.118133
13. [13]
  Chambon, F.; Rataboul, F.; Pinel, C.; Cabiac, A.; Guillon, E.; Essayem, N. Appl. Catal. B: Environ. 2011, 105 (1–2), 171. doi: 10.1016/j.apcatb.2011.04.009 doi: 10.1016/j.apcatb.2011.04.009
14. [14]
  Nguyen, V. C.; Dandach, A.; Vu, T. T. H.; Fongarland, P.; Essayem, N. Mol. Catal. 2019, 476, 110518. doi: 10.1016/j.mcat.2019.110518 doi: 10.1016/j.mcat.2019.110518
15. [15]
  Shi, N.; Liu, Q.; He, X.; Cen, H.; Ju, R.; Zhang, Y.; Ma, L. Bioresour. Technol. Rep. 2019, 5, 66. doi: 10.1016/j.biteb.2018.12.005 doi: 10.1016/j.biteb.2018.12.005
16. [16]
  Xia, M.; Shen, Z.; Xiao, S.; Peng, B. -Y.; Gu, M.; Dong, W.; Zhang, Y. Appl. Catal. A: Gen. 2019, 583, 117126. doi: 10.1016/j.apcata.2019.117126 doi: 10.1016/j.apcata.2019.117126
17. [17]
  Wang, F. -F.; Liu, C. -L.; Dong, W. -S. Green Chem. 2013, 15 (8), 2091. doi: 10.1039/c3gc40836a doi: 10.1039/c3gc40836a
18. [18]
  Deng, W.; Wang, P.; Wang, B.; Wang, Y.; Yan, L.; Li, Y.; Zhang, Q.; Cao, Z.; Wang, Y. Green Chem. 2018, 20 (3), 735. doi: 10.1039/c7gc02975f doi: 10.1039/c7gc02975f
19. [19]
  Xu, S.; Wu, Y.; Li, J.; He, T.; Xiao, Y.; Zhou, C.; Hu, C. ACS Sustain. Chem. Eng. 2020, 8 (10), 4244. doi: 10.1021/acssuschemeng.9b07552 doi: 10.1021/acssuschemeng.9b07552
20. [20]
  Roman-Leshkov, Y.; Moliner, M.; Labinger, J. A.; Davis, M. E. Angew. Chem. Int. Ed. 2010, 49 (47), 8954. doi: 10.1002/anie.201004689 doi: 10.1002/anie.201004689
21. [21]
  Cotton, F. A.; Wilkinson, G.; Murillo, C. A.; Bochmann, M. Advanced Inorganic Chemistry, 6th ed.; John Wiley & Sons Inc: New York, NY, USA, 1999.
22. [22]
  Deng, W.; Zhang, Q.; Wang, Y. Catal. Today 2014, 234, 31. doi: 10.1016/j.cattod.2013.12.041 doi: 10.1016/j.cattod.2013.12.041
23. [23]
  Slak, J.; Pomeroy, B.; Kostyniuk, A.; Grilc, M.; Likozar, B. Chem. Eng. J. 2022, 429, 132325. doi: 10.1016/j.cej.2021.132325 doi: 10.1016/j.cej.2021.132325
24. [24]
  Bayu, A.; Karnjanakom, S.; Kusakabe, K.; Abudula, A.; Guan, G. Chin. J. Catal. 2017, 38 (3), 426. doi: 10.1016/S1872-2067(17)62754-2 doi: 10.1016/S1872-2067(17)62754-2
25. [25]
  Liu, M.; Jia, S.; Li, C.; Zhang, A.; Song, C.; Guo, X. Chin. J. Catal. 2014, 35 (5), 723. doi: 10.1016/S1872-2067(14)60071-1 doi: 10.1016/S1872-2067(14)60071-1
1. [1]
  Xiaoning TANG , Junnan LIU , Xingfu YANG , Jie LEI , Qiuyang LUO , Shu XIA , An XUE . Effect of sodium alginate-sodium carboxymethylcellulose gel layer on the stability of Zn anodes. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1452-1460. doi: 10.11862/CJIC.20240191
2. [2]
  Yiling Wu , Peiyao Jin , Shenyue Tian , Ji Zhang . The Star of Sugar Substitutes: An Interview of Erythritol. University Chemistry, 2024, 39(9): 22-27. doi: 10.12461/PKU.DXHX202404034
3. [3]
  Shijie Li , Ke Rong , Xiaoqin Wang , Chuqi Shen , Fang Yang , Qinghong Zhang . Design of Carbon Quantum Dots/CdS/Ta₃N₅ S-Scheme Heterojunction Nanofibers for Efficient Photocatalytic Antibiotic Removal. Acta Physico-Chimica Sinica, 2024, 40(12): 2403005-. doi: 10.3866/PKU.WHXB202403005
4. [4]
  Zhuoming Liang , Ming Chen , Zhiwen Zheng , Kai Chen . Multidimensional Studies on Ketone-Enol Tautomerism of 1,3-Diketones By ¹H NMR. University Chemistry, 2024, 39(7): 361-367. doi: 10.3866/PKU.DXHX202311029
5. [5]
  Jiajun Lu , Zhehui Liao , Tongxiang Cao , Shifa Zhu . Synergistic Brønsted/Lewis acid catalyzed atroposelective synthesis of aryl-β-naphthol. Chinese Chemical Letters, 2025, 36(1): 109842-. doi: 10.1016/j.cclet.2024.109842
6. [6]
  Yixuan Zhu , Qingtong Wang , Jin Li , Lin Chen , Junlong Zhao . Blog of Oxytocin. University Chemistry, 2024, 39(9): 134-140. doi: 10.12461/PKU.DXHX202310090
7. [7]
  Mianfeng Li , Haozhi Wang , Zijun Yang , Zexiang Yin , Yuan Liu , Yingmei Bian , Yang Wang , Xuerong Zheng , Yida Deng . Synergistic enhancement of alkaline hydrogen evolution reaction by role of Ni-Fe LDH introducing frustrated Lewis pairs via vacancy-engineered. Chinese Chemical Letters, 2025, 36(3): 110199-. doi: 10.1016/j.cclet.2024.110199
8. [8]
  Qingying Gao , Tao Luo , Jianyuan Su , Chaofan Yu , Jiazhu Li , Bingfei Yan , Wenzuo Li , Zhen Zhang , Yi Liu . Refinement and Expansion of the Classic Cinnamic Acid Synthesis Experiment. University Chemistry, 2024, 39(5): 243-250. doi: 10.3866/PKU.DXHX202311074
9. [9]
  Yuhang Jiang , Weijie Liu , Jiaqi Cai , Jiayue Chen , Yanping Ren , Pingping Wu , Liulin Yang . A Journey into the Science and Art of Sugar: “Dispersion of Light and Optical Rotation of Matter” Science Popularization Experiment. University Chemistry, 2024, 39(9): 288-294. doi: 10.12461/PKU.DXHX202401054
10. [10]
  Runze Liu , Yankai Bian , Weili Dai . Qualitative and quantitative analysis of Brønsted and Lewis acid sites in zeolites: A combined probe-assisted 1H MAS NMR and NH3-TPD investigation. Chinese Journal of Structural Chemistry, 2024, 43(4): 100250-100250. doi: 10.1016/j.cjsc.2024.100250
11. [11]
  Zhao Lu , Hu Lv , Qinzhuang Liu , Zhongliao Wang . Modulating NH₂ Lewis Basicity in CTF-NH₂ through Donor-Acceptor Groups for Optimizing Photocatalytic Water Splitting. Acta Physico-Chimica Sinica, 2024, 40(12): 2405005-. doi: 10.3866/PKU.WHXB202405005
12. [12]
  Yiping HUANG , Liqin TANG , Yufan JI , Cheng CHEN , Shuangtao LI , Jingjing HUANG , Xuechao GAO , Xuehong GU . Hollow fiber NaA zeolite membrane for deep dehydration of ethanol solvent by vapor permeation. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 225-234. doi: 10.11862/CJIC.20240224
13. [13]
  Meijin Li , Xirong Fu , Xue Zheng , Yuhan Liu , Bao Li . The Marvel of NAD⁺: Nicotinamide Adenine Dinucleotide. University Chemistry, 2024, 39(9): 35-39. doi: 10.12461/PKU.DXHX202401027
14. [14]
  Keying Qu , Jie Li , Ziqiu Lai , Kai Chen . Unveiling the Mystery of Chirality from Tartaric Acid. University Chemistry, 2024, 39(9): 369-378. doi: 10.12461/PKU.DXHX202310091
15. [15]
  Ran Yu , Chen Hu , Ruili Guo , Ruonan Liu , Lixing Xia , Cenyu Yang , Jianglan Shui . 杂多酸H₃PW₁₂O₄₀高效催化MgH₂储氢. Acta Physico-Chimica Sinica, 2025, 41(1): 2308032-. doi: 10.3866/PKU.WHXB202308032
16. [16]
  Yukun Xing , Xiaoyu Xie , Fangfang Chen . A Sunlit Gift: Vitamin D. University Chemistry, 2024, 39(9): 28-34. doi: 10.12461/PKU.DXHX202402006
17. [17]
  Juan WANG , Zhongqiu WANG , Qin SHANG , Guohong WANG , Jinmao LI . NiS and Pt as dual co-catalysts for the enhanced photocatalytic H₂ production activity of BaTiO₃ nanofibers. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1719-1730. doi: 10.11862/CJIC.20240102
18. [18]
  Zijian Zhao , Yanxin Shi , Shicheng Li , Wenhong Ruan , Fang Zhu , Jijun Jiang . A New Exploration of the Preparation of Polyacrylic Acid by Free Radical Polymerization Based on the Concept of Green Chemistry. University Chemistry, 2024, 39(5): 315-324. doi: 10.3866/PKU.DXHX202311094
19. [19]
  Ping Song , Nan Zhang , Jie Wang , Rui Yan , Zhiqiang Wang , Yingxue Jin . Experimental Teaching Design on Synthesis and Antitumor Activity Study of Cu-Pyropheophorbide-a Methyl Ester. University Chemistry, 2024, 39(6): 278-286. doi: 10.3866/PKU.DXHX202310087
20. [20]
  Jiahe LIU , Gan TANG , Kai CHEN , Mingda ZHANG . Effect of low-temperature electrolyte additives on low-temperature performance of lithium cobaltate batteries. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 719-728. doi: 10.11862/CJIC.20250023

Get Citation

PDF

XML

Metrics

PDF Downloads(18)
Abstract views(541)
HTML views(98)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142