乙醇胺电氧化合成甘氨酸的研究

doi:10.6023/cjoc202502009

摘要/Abstract

本研究旨在通过电化学方法氧化乙醇胺(MEA)合成甘氨酸(Gly). 对电解槽结构对反应效果的影响进行了研究, 发现无隔膜电解槽在提高Gly收率、Gly选择性、MEA转化率和电流效率等方面的效果优于隔膜电解槽. 通过一系列实验设计, 发现无隔膜电解槽电解效果高于隔膜电解槽的主要原因为阴极Pb发生了部分Pb(Ⅱ)溶出现象. 溶出的Pb(Ⅱ)迁移至阳极, 在阳极表面氧化生成PbO₂并附着于阳极表面, PbO₂与Pt协同催化氧化乙醇胺提高了甘氨酸的收率. 借助电化学原位红外光谱研究揭示了C—OH在Pt-PbO₂电极表面具有较强吸附, 且Pt-PbO₂可促进乙醇胺中的C—OH电氧化为C=O和COOH. 最后通过优化电解质种类和浓度、乙醇胺浓度等条件, 以90.54%的高收率获得甘氨酸, 甘氨酸选择性和乙醇胺转化率均超过90%. 重复性实验证明该电解法具有较好的重复性. 通过调节溶液pH、过滤、减压蒸馏、洗涤、干燥一系列操作得到Gly固体, Gly分离效率为88%.

关键词: 乙醇胺电氧化, 甘氨酸, 电解槽结构筛选, 电氧化机理, 电解条件优化

The aim of this study was to synthesize glycine (Gly) by electrooxidation of ethanolamine (MEA). The influence of electrolyzer structure on the reaction was studied. Comparing the results of membrane-free and membrane electrolyzers revealed that the membrane-free electrolyzer performed better Gly yield, Gly selectivity, MEA conversion, and current efficiency. Through a series of experiments, it was found that the main reason for the higher performance of membrane-free electrolyzer was the occurrence of dissolving part of Pb(II) species from the cathode Pb surface. The dissolved Pb(II) migrated to the anode, oxidized and attached on the surface of the anode to generate PbO₂, The synergistic effect of PbO₂ and Pt promoted the oxidation of MEA and the yield of glycine. Electrochemical in-situ infrared spectroscopy study was applied to investigate the effect of Pt-PbO₂ and revealed that the adsorbtion of C—OH, the oxidatin of C—OH and C=O bond were promoted on Pt-PbO₂ electrode. Finally, by optimizing the electrolyte type and concentration, ethanolamine concentration, and current density, glycine was obtained in a high yield of 90.54%, along with a glycine selectivity and an ethanolamine conversion of more than 90%. The electrooxidation reaction is repeatable, and 88% MEA can be collected from the electrolyte.

Key words: ethanolamine electrooxidation, glycine, electrolytic cell structure screening, electrooxidation mechanism, optimal electrolysis conditions

引用此文

李颖, 胡硕真, 方卫, 肖星, 张新胜. 乙醇胺电氧化合成甘氨酸的研究[J]. 有机化学, 2025, 45(10): 3873-3884.

Ying Li, Shuozhen Hu, Wei Fang, Xing Xiao, Xinsheng Zhang. Study on Synthesis of Glycine by Electrooxidation of Ethanolamine[J]. Chinese Journal of Organic Chemistry, 2025, 45(10): 3873-3884.

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图/表 15

图1. 电解槽类型对Gly收率、Gly选择性、MEA转化率和法拉第效率的影响

Figure 1. Influence of electrolyzer type on Gly yield, Gly selectivity, MEA conversion, and Faraday efficiency

图2. 阴阳极交换前后Gly的含量对比

Figure 2. Comparison of glycine content before and after exchanging the anode-cathode

图式1. 乙醇胺电氧化反应路径

Scheme 1. Reaction pathways of electro-oxidation of ethanolamine

图3. (a)铅作为阴极时无隔膜电解前后铂阳极的对比图; (b)无隔膜电解前的Pt电极的SEM图和(c)无隔膜电解后的Pt电极的SEM图; (d)无隔膜电解前后的Pt电极的XRD分析图

Figure 3. (a) Comparison diagram of the Pt anode before and after undivided electrolysis with lead as the cathode; (b) SEM image of the Pt electrode before undivided electrolysis and (c) SEM image of the Pt electrode after undivided electrolysis; (d) XRD patterns of the Pt electrode before and after undivided electrolysis

图4. 铅作为阴极时Pt(黑)和Pt-PbO2(红)分别作为阳极时进行隔膜电解的Gly收率(a)、Gly选择性(b)、MEA转化率(c)的对比

Figure 4. Comparison of Gly yield (a), Gly selectivity (b), and MEA conversion (c), in a diaphragm electrolysis, Pt (black) and Pt-PbO2 (red) as anodes with Pb as cathode

图式2. 探讨阴极溶出物对电解效果影响的实验示意图

Scheme 2. Schematic diagram of the experiment to investigate the effect of cathode dissolution on the electrolysis efficiency

Anode	Gly yield/%	Gly selectivity/%	MEA conversion/%	Faraday efficiency/%
Pt	27.02	45.40	59.52	21.62
PbO₂	70.28	78.50	89.54	56.25
Pt-PbO₂	80.99	81.45	99.43	64.81

表1. Pt、PbO2和Pt-PbO2对Gly收率、Gly选择性、MEA转化率和法拉第效率的影响

Table 1. Influence of Pt, PbO2 and Pt-PbO2 on the yield of Gly, selectivity of Gly, MEA conversion, and Faraday efficiency

图5. 电位为1.9~3.0 V时Pt电极(a, b)和Pt-PbO2电极(c, d)在0.3 mol/L MEA＋2.0 mol/L H2SO4溶液中的原位多步阶跃红外光谱图(vs. Ag/AgCl) (图b、d分别为图a、c中对应红框中的放大图)

Figure 5. In-situ multi-step staircase infrared spectroscopy of Pt electrode (a, b) and Pt-PbO2 electrode (c, d) in 0.3 mol/L MEA＋2.0 mol/L H2SO4 solution at the research potential of 1.9~3.0 V (vs. Ag/AgCl) (b and d are the enlarged view of Figures a and c)

图6. 在2.4 V时Pt电极(a)和Pt-PbO2电极(b)在0.3 mol/L MEA＋2.0 mol/L H2SO4溶液中的时间分辨原位红外光谱图(vs. Ag/AgCl)

Figure 6. Time-resolved in situ infrared spectra of Pt electrode (a) and Pt-PbO2 electrode (b) in 0.3 mol/L MEA＋2.0 mol/L H2SO4 solution at 2.4 V (vs. Ag/AgCl)

Acid-base environment	Gly yield/%	Gly selecti- vity/%	MEA con- version/%
Acidic media	79.22	88.61	89.40
Alkaline media	3.09	5.25	58.99

表2. 酸、碱环境对MEA电合成Gly的影响

Table 2. Effect of acid-base environment on MEA electrosynthesis of Gly

图7. 酸种类对MEA转化率、Gly收率和选择性的影响

Figure 7. Effect of acid type on MEA conversion, Gly yield, and selectivity

图8. 硫酸浓度对Gly收率(a)、电流效率、Gly选择性及MEA转化率(b)的影响

Figure 8. Effect of sulfuric acid concentration on the yield of Gly (a), and current efficiency, Gly selectivity, and MEA conversion (b)

图9. 乙醇胺浓度对Gly收率(a)、电流效率、Gly选择性及MEA转化率(b)的影响

Figure 9. Effect of ethanolamine concentration on the yield of Gly (a), current efficiency, Gly selectivity, and MEA conversion (b)

图10. 电流密度对Gly收率(a), Gly选择性、MEA转化率以及电流效率(b)的影响

Figure 10. Effect of current density on the yield of Gly (a), and Gly selectivity, MEA conversion, and current efficiency (b)

Serial number	Gly yield/%	Gly selecti- vity/%	MEA con- version/%	Faraday efficiency/%
1	84.23	88.03	95.69	67.28
2	86.30	90.16	95.73	69.53
3	85.57	88.43	96.77	68.50

表3. 电解反应重复性测试结果

Table 3. Electrolysis reaction repeatability test results.

参考文献 48

[1]	Li, Z.; Wang, S.; Sun, K.; Li, H.; Lu, X. SAGE Open 2022, 12, 2.
[2]	Deng, J. S.; Peng, S. P.; Wang, L.; Bi, Y. L.; Yao, J.; Wang, Q. J. Changjiang Riverine and Estuarine Hydro-morphodynamic Processes: In the Context of Anthropocene Era, Springer, Singapore, 2021, p. 374.
[3]	Xu, K.; Yang, M.; Yang, J.; Butina, N.; Cai, Y.; Zhang, H.; Wang, Y. Front. Environ. Sci. 2024, 12, DOI: 10.3389/fenvs.2024.1421990.
[4]	Guo, H.; Niu, D.-F.; Hu, S.-Z. J. Electrochem. 2021, 27, 498 (in Chinese).
	(郭浩, 钮东方, 胡硕真, 电化学, 2021, 27, 498.) doi: 10.13208/j.electrochem.201203
[5]	Wang, Z.-H.; Ma, C.; Fang, P.; Xu, H.-C.; Mei, T.-S. Acta Chim. Sinica 2022, 80, 1115 (in Chinese).
	(王振华, 马聪, 方萍, 徐海超, 梅天胜, 化学学报, 2022, 80, 1115.) doi: 10.6023/A22060260
[6]	Budnikova, Y. H.; Dolengovski, E. L.; Tarasov, M. V.; Gryaznova, T. V. Solid State Electrochem. 2023, 28, 659.
[7]	Horn, E. J.; Rosen, B. R.; Baran, P. S. ACS Cent. Sci. 2016, 2, 302.
[8]	Yuan, Y.; Lei, A. Nat. Commun. 2020, 11, 802.
[9]	Yunus, R.; Abdusweli, K.; Luo, S.-W.; Ablikim, A. Acta Chim. Sinica 2024, 82, 843 (in Chinese).
	(热孜古丽•玉努斯, 卡迪尔亚•阿布都外力, 罗时玮, 阿布都热西提•阿布力克木, 化学学报, 2024, 82, 843.)
[10]	Nurmaimaiti, K.; Wang, C.; Luo, S.-W.; Ablikim, A. Acta Chim. Sinica 2023, 81, 582 (in Chinese).
	(坎比努尔•努尔买买提, 王超, 罗时玮, 阿布都热西提•阿布力克木, 化学学报, 2023, 81, 582.)
[11]	Meléndez-Hevia, E.; de Paz-Lugo, P.; Sánchez, G. Funct. Foods 2021, 76, 104318.
[12]	Cao, C.; Xie, J.; Hou, L.; Zhao, J.; Chen, F.; Xiao, Q.; Zhao, M.; Fan, M. Food Res. Int. 2017, 99, 444.
[13]	Razak, M. A.; Begum, P. S.; Viswanath, B. D.; Rajagopal, S. Oxid. Med. Cell. Longevity 2017, 1716701.
[14]	Li, J.; Yao, Y. N. China Feed Addit. 2010, (9), 26 (in Chinese).
	(李娟, 姚玉妮, 中国饲料添加剂, 2010, (9), 26.)
[15]	Ke, K.; Zhang, Z. W.; Kang, H. F.; Fang, R. J.; Kong, X. F. Feed Res. 2017 (10), 20 (in Chinese).
	(柯轲, 张紫微, 康会芳, 方热军, 孔祥峰, 饲料研究, 2017 (10), 20.)
[16]	Schäfer, H. J. C. R. Chim. 2011, 14, 745.
[17]	Katritzky, A. R.; Denisko, O. V.; Rakhmankulov, D. L.; Rajappa, S.; Voronkov, M. V.; Todorchenko, A. T.; Akhmetova, R. G.; Sha- gidullin, R. R. J. Chem. Sci. 2003, 115, 543.
[18]	Qian, Y. B.; Yang, L. M. Anhui Agric. Sci. 2009, 37, 5828 (in Chinese).
	(钱益斌, 杨利民, 安徽农业科学, 2009, 37, 5828.)
[19]	Rimola, A.; Sodupe, M.; Ugliengo, P. Phys. Chem. Chem. Phys. 2010, 12, 5285.
[20]	Cheng, M. L.; Shi, J. G.; Zhang, Y.; Yuan, L. H.; Yuan, L. H.; Shen, X. N. Sino-global Energy 2022, 27, 70 (in Chinese).
	(程明立, 史建公, 张毅, 苑志伟, 袁立焕, 沈小宁, 中外能源, 2022, 27, 70.)
[21]	Huang, P.; Li, Y. Z.; Zhang, Q. S. Chem. Res. 2004, 15, 77 (in Chinese).
	(黄平, 李云政, 张青山, 化学研究, 2004, 15, 77.)
[22]	Zhu, Z.-H.; Li, Y.; He, C.-H.; Yu, S. C.; Xu, P. R. Petrochem. Technol. 2005, 34, 279 (in Chinese).
	(朱志华, 李燕, 赫崇衡, 于筛成, 徐佩若, 石油化工, 2005, 34, 279.)
[23]	Ohrui, H.; Misawa, T.; Meguro, H. J. Org. Chem. 1985, 50, 3007.
[24]	Li, X.; Zhang, W.; Zhao, G.; He, R. Y.; Han, M.; Yang, R. J.; Wu, N.; Gong, W. Z. Pesticide 2019, 58, 788 (in Chinese).
	(李鑫, 张伟, 赵广, 赫瑞元, 韩萌, 杨仁俊, 毋楠, 龚文照, 农药, 2019, 58, 788.)
[25]	Meng, X. Z.; Zhang, Y. Q.; Li, Z. X.; Wang, H.; Zhang, S. J. Ind. Eng. Chem. Res. 2019, 58, 8506.
[26]	Chi, S.; Rochelle, G. T. Ind. Eng. Chem. Res. 2002, 41, 4178.
[27]	Duan, Z. K.; Yang, Y. Q.; Liu, W. Y.; Xiong, Y.; Li, G. L. Fine Chem. 2000, 17, 345 (in Chinese).
	(段正康, 杨运泉, 刘文英, 熊鹰, 李国龙, 精细化工, 2000, 17, 345.)
[28]	Lu, Z. G. Ph. D. Dissertation, Zhejiang University, Hangzhou, 2003 (in Chinese).
	(卢祖国, 博士论文, 浙江大学, 杭州, 2003.)
[29]	Li, L.; Wan, C.; Wang, S.; Li, X.; Sun, Y.; Xie, Y. Nano Lett. 2024, 24, 2392. doi: 10.1021/acs.nanolett.3c05064 pmid: 38334492
[30]	Cheng, Y. Y.; Liu, S. Q.; Jiao, J. P.; Zhou, M.; Wang, Y. Y.; Xing, X. Q.; Chen, Z. J.; Sun, X. F.; Zhu, Q. G.; Qian, Q. L.; Wang, C. Y.; Liu, H. Z.; Liu, Z. M.; Kang, X. C.; Han, B. X. J. Am. Chem. Soc. 2024, 146, 5678.
[31]	Huynh, T. T.; Huynh, Q.; Nguyen, A. Q. K.; Pham, H. Q. Adv. Sustainable Syst. 2025, DOI: https://doi.org/10.1002/adsu.202400995.
[32]	Song, H.; Qiu, X.; Li, X.; Li, F.; Zhu, W.; Chen, L. J. Power Sources 2007, 168, 50.
[33]	Zhang, K.; Yang, W.; Ma, C.; Wang, Y.; Sun, C.; Chen, Y.; Duchesne, P.; Zhou, J.; Wang, J.; Hu, Y.; Banis, M. N.; Zhang, P.; Li, F.; Li, J.; Chen, L. NPG Asia Mater. 2015,7, e153.
[34]	Flórez-Montaño, J.; García, G.; Guillén-Villafuerte, O.; Rodríguez, J. L.; Planes, G. A.; Pastor, E. Electrochim. Acta 2016, 209, 121.
[35]	Bianchini, C.; Shen, P. K. Chem. Rev. 2009, 109, 4183. doi: 10.1021/cr9000995 pmid: 19606907
[36]	Lee, Y. W.; Kim, M.; Kim, Y.; Kang, S. W.; Lee, J.-H.; Han, S. W. J. Phys. Chem. 2010, 114, 7689.
[37]	Onoe, J.; Kawai, T. J. Chem. Soc., Chem. Commun. 1987, 1480.
[38]	Xu, J.; Gao, M.-X.; Ma, J.-P.; Gao, J.; Fan, X.-M.; Miao, H.CN 202111542769, 2023.
[39]	Halpern, J. General Chemistry: An Atoms First Approach, Howard University, Washington, D. C., 2024, Chapter 17.4.
[40]	Zeng, Y. Z. M.S. Thesis, Fuzhou University, Fuzhou, 2015 (in Chinese).
	(曾燕真, 硕士论文, 福州大学, 福州, 2015.)
[41]	Niedbała, J.; Budniok, A.; Matyja, P. Thin Solid Films 1994, 237, 148.
[42]	Sun, H.; Du, M.; Guo, F.; Gao, S.; Yue, F.; Yang, J. IOP Conf. Ser.: Earth Environ. Sci. 2019, 300, 052036.
[43]	Łuczak, T. J. Appl. Electrochem. 2007, 37, 653.
[44]	Bełtowska-Brzezinska, M.; Zmaczyńska, A.; Łuczak, T. Electrocatalysis 2016, 7, 79.
[45]	Dong, R.; Liu, Y.; Wang, X.; Huang, J. J. Chem. Eng. Data 2011, 56, 3890.
[46]	Sadegh Alvad, B.; Khorshidi, N. Y.; Azad Mehr, A.; Sillanpää, M. Chemosphere 2021, 263, 128064.
[47]	Kazmierczak, Ł.; Janik, I.; Wolszczak, M.; Światła-Wojcik, D. J. Phys. Chem. B 2021, 125, 9564.
[48]	Levanov, A. V.; Isaikina, O. Y. Ind. Eng. Chem. Res. 2020, 59, 14278.