酸性体系V催化木质素β-O-4模型物C-C键高选择性切断

doi:10.6023/A17050199

化学学报 ›› 2017, Vol. 75 ›› Issue (8): 788-793.DOI: 10.6023/A17050199 上一篇下一篇

研究通讯

酸性体系V催化木质素β-O-4模型物C-C键高选择性切断

刘新鑫, 严龙, 傅尧

安徽省生物质洁净能源重点实验室化学与材料科学学院中国科学技术大学 230026

投稿日期:2017-05-08 发布日期:2017-06-15
通讯作者: 傅尧,E-mail:fuyao@ustc.edu.cn E-mail:fuyao@ustc.edu.cn
基金资助:
项目受国家自然科学基金（Nos.21325208，21272050，21402181，21572212）、合肥物质科学技术中心方向项目培育基金（No.2014FXCX006）、中国科学院项目基金（Nos.KFJ-EW-STS-051，XDB20000000，YZ201563）、高等学校博士学科点科研专项基金（No.20123402130008）、中央高校基础研究经费（Nos.WK2060190025，WK2060190040）、安徽省科技攻关计划（No.1604a0702027）及教育部长江学者和创新团队发展计划资助.

Lignin C-C Bond's Cleavage by Vanadium Catalyzed with High Selectivity in Acid Environment

Liu Xinxin, Yan Long, Fu Yao

Anhui Province Key Laboratory of Biomass Clean Energy, School of Chemistry and Materials Science, University of Science and Technology of China, Hefei 230026

Received:2017-05-08 Published:2017-06-15
Contact: 10.6023/A17050199 E-mail:fuyao@ustc.edu.cn
Supported by:
Project supported by the National Natural Science Foundation of China (Nos.21325208,21272050,21402181,21572212),the Index Program Directive Foundation of Hefei Centre for Physical Science and Technology (No.2014FXCX006),the Science Foundation of the Chinese Academy of Sciences (Nos.KFJ-EW-STS-051,XDB20000000,YZ201563),the Specialized Research Fund for the Doctoral Program of Higher Education (No.20123402130008),the Fundamental Research Funds for the Central Universities (Nos.WK2060190025,WK2060190040),the Key Technologies R&D Program of Anhui Province (No.1604a0702027) and the Program for Changjiang Scholars and Innovative Research Team in University of the Ministry of Education of China.

文章分享

1. 酸性体系V催化木质素β-O-4模型物C-C键高选择性切断.PDF(743KB)

摘要/Abstract

研究了酸性体系下NH₄VO₃催化木质素模型物2-（苯氧基）-1-苯乙酮（1a）的C-C键氧化切断过程.通过优选反应溶剂，在温和条件下（100℃，101 kPa O₂）于DMSO-HOAc（V：V=3：1）溶剂中高选择性地得到了苯甲酸和苯酚（产率分别为82.1%和88.1%），并通过对反应过程的监测和催化剂的研究提出了该反应可能的反应路径.反应过程存在两条可能的途径，一是1a先发生C-O键断裂生成苯酚和2-羟基苯乙酮，再催化2-羟基苯乙酮C-C键氧化断裂生成苯甲酸；二是1a直接发生C-C键氧化断裂生成苯甲酸和苯酚.同时，催化剂表征结果表明，+5价钒氧离子是催化活性物种.钒催化剂在反应过程中通过+4和+5价循环完成催化过程.

关键词: 木质素, 解聚, C-C键切断, 钒催化, 氧化

Lignin is a potential resources of aromatic compound that can be obtained from renewable biomass. There are many ongoing research efforts to utilize lignin as a sustainable alternative to petroleum derived aromatic compounds. Because of the complex three-dimensional structure, the depolymerization of lignin into monomer molecule became a core challenge for the utilization of lignin. The β-O-4 structure is the most abundant linkage in lignin. Owing to its abundance, the β-O-4 structure has been representatively studied in many aspects of scientific research on lignin degradation. Among the different reported strategies for the cleavage of β-O-4 ether bonds, C-C bond cleavage is one of the most important approaches to depolymerizing lignin. In this study, we accomplished the oxidative C-C bond cleavage of the β-O-4 structure by the catalysis of NH₄VO₃ using the pre-oxidized 2-phenoxy-1-phenylethanone (1a) as a model compound of lignin. In the DMSO-HOAc solvent system, benzoic acid and phenol were produced in a moderate condition, the yeild of benzoic acid and phenol were 82.1% and 88.1%, respectively. The reaction process was investigated via ¹H NMR and X-ray photoelectron spectra (XPS) characterizations and the possible reaction pathway was further proposed. As the results shown, two possible reaction routes existed in this catalytic system. Pathway one:the 2-hydroxyacetophenone and phenol formed after the C-O bond cleavage of 1a in the acidic system, then, the intermediate 2-hydroxyacetophenone was converted to benzoic via the cleavage of C-C bond. Pathway two:benzoic acid and phenol yielded by the C-C bond of 1a cleaved directly over the catalyst. In addition, the catalyst characterization results confirmed that the oxovanadium(V) directly catalyzed the depolymerization of the β-O-4 structure and generated oxovanadium(IV), then oxovanadium(IV) was oxidized by O₂ and finish the catalytic cycle. All reactions were carried out by the following general procedure. This reaction was carried out in glass tube and heated by oil bath. 0.5 mmol of 1a was added into 2 mL of DMSO-HOAc (V:V=3:1) with 30 mol% NH₄VO₃ (17.5 mg) under an oxygen atmosphere (101 kPa, in balloon). The reactor was heated to 100℃ with a powerful stirring. After 8 h, the reaction was cooled to room temperature, then 5 mL of ethyl acetate was added into the mixtures. Ash black precipitate was removed by filtration and the liquid mixture was detected by GC.

Key words: lignin, depolymerization, C-C bond cleavage, V-catalyzed reaction, oxidation reaction

引用此文

刘新鑫, 严龙, 傅尧. 酸性体系V催化木质素β-O-4模型物C-C键高选择性切断[J]. 化学学报, 2017, 75(8): 788-793.

Liu Xinxin, Yan Long, Fu Yao. Lignin C-C Bond's Cleavage by Vanadium Catalyzed with High Selectivity in Acid Environment[J]. Acta Chim. Sinica, 2017, 75(8): 788-793.

导出引用 EndNote|Reference Manager|ProCite|BibTeX|RefWorks

分享此文

参考文献

[1] Corma, A.; Iborra, S.; Velty, A. Chem. Rev. 2007, 107, 2411.
[2] (a) Delidovich, I.; Hausoul, P. J. C.; Deng, L.; Pfuzenreuter, R.; Rose, M.; Palkovits, R. Chem. Rev. 2016, 116, 1540.
(b) Yang, Z.; Fu, Y.; Guo, Q. X. Chin. J. Org. Chem. 2015, 35, 273(in Chinese). (杨珍, 傅尧, 郭庆祥, 有机化学, 2016, 35, 273.)
[3] (a) Ragauskas, A. J.; Williams, C. K.; Davison, B. H.; Britovsek, G.; Cairney, J.; Eckert, C. A.; Hallett, J. P.; Leak, D. J.; Liotta, C. L.; Mielenz, J. R.; Murphy, R.; Templer, R.; Tschaplinski. T. Science 2006, 311, 484.
(b) Regalbuto, J. R. Science 2009, 325, 822.
(c) Holm, M. S.; Saravanamurugan, S.; Taarning, E. Science 2010, 328, 602.
(d) Luo, C.; Wang, S.; Liu, H. Angew. Chem., Int. Ed. 2007, 46, 7636.
(e) Wang, H. J.; Zhao, Y.; Wang, C.; Fu, Y.; Guo, Q. X. Acta Chim. Sinica 2009, 67, 893(in Chinese). (王华静, 赵岩, 王晨, 傅尧, 郭庆祥, 化学学报, 2009, 67, 893.)
[4] (a) Xu, C. P.; Arancon, R. A. D.; Labidi, J.; Luque, R. Chem. Soc. Rev. 2014, 43, 7485.
(b) Upton, B. M.; Kasko, A. M. Chem. Rev. 2016, 116, 2275.
(c) Li, C. Z.; Zhao, X. C.; Wang, A. Q.; Huber, G. W.; Zhang, T. Chem. Rev. 2015, 115, 11559.
(d) Deng, W. P.; Zhang, H. X.; Xue, L. Q.; Zhang, Q. H.; Wang, Y. Chin. J. Catal. 2015, 36, 1440.
[5] (a) Zaheer, M.; Kempe, R. ACS Catal. 2015, 5, 1675.
(b) Zeng, W. P.; Li, X. H.; Du, J.; Li, J. M.; Zhang, P.; Hu, C. W.; Meng, X. G. Acta Chim. Sinica 2010, 68, 27(in Chinese). (曾伟鹏, 李小红, 杜娟, 李建梅, 张平, 胡常伟, 孟祥光, 化学学报, 2010, 68, 27.)
[6] (a) Sergeev, A. G.; Hartwig, J. F. Science 2011, 332, 439.
(b) Sergeev, A. G.; Webb, J. D.; Hartwig, J. F. J. Am. Chem. Soc. 2012, 134, 20226.
[7] (a) Zhou, C. H.; Xia, X.; Lin, C. X.; Tong, D. S.; Berltramini, J. Chem. Soc. Rev. 2011, 40, 5588.
(b) Wang, W. L.; Wang, J. Y.; Dong, X. Z.; Chen, P. Chem. Bull. 2016, 79, 731(in Chinese). (王唯黎, 王景芸, 董晓哲, 陈平, 化学通报, 2016, 79, 731.)
[8] Shiramizu, M.; Toste, F. D. Angew. Chem., Int. Ed. 2012, 51, 8082.
[9] Zakzeski, J.; Bruijnincx, P. C. A.; Jongerius, A. L.; Weckhuysen, B. M. Chem. Rev. 2010, 110, 3552.
[10] Alonso, D. M.; Wettstein, S.; G. Dumesic, J. A. Chem. Soc. Rev. 2012, 41, 8075.
[11] (a) Zhang, H. F.; Yang, J. Y.; Wu, J. X.; Mao, H. F.; Sun, X. L. Chin. J. Org. Chem. 2016, 36, 1266(in Chinese). (张海峰, 杨军艳, 吴建新, 毛海舫, 孙小玲, 有机化学, 2016, 36, 1266.)
(b) Ouyang, X. P.; Yang, Y.; Zhu, G. D.; Qiu, X. Q. Chin. Chem. Lett. 2015, 26, 980.
[12] (a) He, J.; Zhao, C.; Lercher, J. A. J. Am. Chem. Soc. 2012, 134, 20768.
(b) Song, Q.; Wang, F.; Cai, J. Y.; Wang, Y. H.; Zhang, J. J.; Yu, W. Q.; Xu, J. Energy Environ. Sci. 2013, 6, 994;
(c) Wang, X.; Rinaldi, R. ChemSusChem 2012, 5, 1455.
(d) Sturgeon, M. R.; O'Brien, M. R.; Ciesielski, P. N.; Katahira, R.; Kruger, J. S.; Chmely, S. C.; Hamlin, J.; Lawrence, K.; Hunsinger, G. B.; Foust, T. D.; Baldwin, R. M.; Biddy, M. J.; Beckham, G. T. Green Chem. 2014, 16, 824.
(e) Song, Q.; Cai, J. Y.; Zhang, J. J.; Yu, W. Q.; Wang, F.; Xu, J. Chin. J. Catal. 2013, 34, 651.
[13] Ren, Y. L.; Yan, M. J.; Wang, J. J.; Zhang, Z. C.; Yao, K. S. Angew. Chem., Int. Ed. 2013, 52, 12674.
[14] Harm, R. G.; Markovits, I.-I. E.; Drees, M.; Mult, H. C.; Herrmann, W. A.; Cokoja, M.; Kuhn, F.-E. ChemSusChem 2014, 7, 429.
[15] Nichols, J. M.; Bishop, L. M.; Bergman, R. G.; Ellman, J. A. J. Am. Chem. Soc. 2010, 132, 12554.
[16] (a) Zhou, X. Y.; Mitra, J.; Rauchfuss, T. B. ChemSusChem 2014, 7, 1623.
(b) Yan, L.; Pang, H.; Huang, Y. B.; Fu, Y. Acta Chim. Sinica 2014, 72, 1005(in Chinese). (严龙, 庞欢, 黄耀兵, 傅尧, 化学学报, 2014, 72, 1005.)
[17] (a) Guo, H. W.; Zhang, B.; Li, C. Z.; Peng, C.; Dai, T.; Xie, H. B.; Wang, A. Q.; Zhang, T. ChemSusChem 2016, 9, 3220.
(b) Heather, J.; Parker, H. J.; Chuck, C. J.; Woodman, T.; Jones, M. D. Catal. Today 2016, 269, 40.
(c) Xiao, Y. W.; Xiu, Y. L. Chin. J. Chem. 2011, 22, 733.
[18] (a) Hanson, S. K.; Baker, R. T.; Gordon, J. C.; Scott, B. L.; Thorn, D. L. Inorg. Chem. 2010, 49, 5611.
(b) Hanson, S. K.; Wu, R.; Silks, L. A. P. Angew. Chem., Int. Ed. 2012, 51, 3410.
(c) Zhang, G.; Scott, B. L.; Wu, R. L.; Silks, L. A. P.; Hanson, S. K. Inorg. Chem. 2012, 51, 7354.
(d) Sedai, B.; Urrutia, C. D.; Baker, R. T.; Wu, R. L.; Silks, L. A. P.; Hanson, S. K. ACS. Catal. 2013, 3, 3111.
(e) Diaz-Urrutia, C.; Sedai, B.; Leckett, K. C.; Baker, R. T.; Hanson, S. ACS Sustanable Chem. Eng. 2016, 4, 6244.
[19] (a) Ma, Y. Y.; Du, Z. T.; Liu, J. X.; Xia, F.; Xu, J. Green Chem. 2015, 17, 4968.
(b) Ma, Y. Y.; Du, Z. T.; Xia, F.; Ma, J. P.; Gao, J.; Xu, J. RSC Adv. 2016, 6, 110229.
[20] (a) Gazi, S.; Ng, W. K. H.; Ganguly, R.; Moeljadi, A. M. P.; Soo, H. S. Chem. Sci. 2015, 6, 7130.
(b) Mottweiler, J.; Puche, M.; Rauber, C.; Schmidt, T.; Concepcion, P.; Corma, A.; Bolm, C. ChemSusChem 2015, 8, 1206.
[21] (a) Mottweiler, J.; Rinesch, T.; Besson, C.; Buendia, J.; Bolm, C. Green Chem. 2015, 17, 5001.
(b) Stein, T V.; Hartog, T. D.; Buendia, J.; Stoychev, S.; Mottweiler, J.; Bolm, C.; Klankermayer, J.; Leitner, W. Angew. Chem., Int. Ed. 2015, 54, 5859.
(c) Deng, W. P.; Zhang, H. X.; Wu, X. J.; Li, R. S.; Zhang, Q. H.; Wang, Y. Green Chem. 2015, 17, 5009.
(d) Mitchell, L. J.; Moody, C. J. J. Org. Chem. 2014, 79, 11091.
[22] (a) Rahimi, A.; Ulbrich, A.; Coon, J. J.; Stahl, S. S. Nature 2015, 515, 249.
(b) Rahimi, A.; Azarpira, A.; Kim, H.; Ralph, J.; Stahl, S. S. J. Am. Chem. Soc. 2013, 135, 6415.
[23] (a) Patil, N. D.; Yan, N. Catal. Commun. 2016, 84, 155.
(b) Yao, S. G.; Meier, M. S.; Pace Ⅲ, R. B.; Crocker, M. RSC Adv. 2016, 6, 104742.
(c) Mobley, J. K.; Yao, S. G.; Crocker, M.; Meier, M. RSC Adv. 2015, 5, 105136.
(d) Nguyen, J. D.; Matsuura, B. S.; Stepemson, C. R. J. J. Am. Chem. Soc. 2014, 136, 1218.
(e) Luo, J.; Zhang, J. J. Org. Chem. 2016, 81, 9131.
(f) Karakas, D. M.; Bosque, I.; Stephenson, C. R. J. Org. Lett. 2016, 18, 5166.
[24] (a) Wang, M.; Lu, J. M.; Zhang, X. C.; Li, L. H.; Li, Hong. J.; Luo, N. C.; Wang, F. ACS Catal. 2016, 6, 6086.
(b) Wang, M.; Li, L. H.; Lu, J. M.; Li, H. J.; Zhang, X. C.; Liu, H. F.; Luo, N. C.; Wang, F. Green Chem. 2017, 19, 702.
(c) Liu, H. F.; Wang, M.; Li, H. J.; Luo, N. C.; Xu, S. T.; Wang, F. J. Catal. 2017, 346, 170.
[25] (a) Yang, Y. Y.; Fan, H. L.; Song, J. L.; Meng, Q. L.; Zhou, H. C.; Wu, L. Q.; Yang, G. Y.; Han, B. X. Chem. Coummn. 2015, 51, 4028.
(b) Paitil, N. D.; Yan, N. Tetrahedron Lett. 2016, 57, 3024.
[26] (a) Luo, N. C.; Wang, M.; Li, H.; Zhang, J.; Liu, H.; Wang, F. ACS Catal. 2016, 6, 7716.
(b) Zhang, J.; Liu, Y.; Chiba, S.; Loh, T.-P. Chem. Commun. 2013, 49, 11439.
[27] Dakkach, M.; Atlamsani, A.; Sebti, S. C. R. Chim. 2012, 15, 482.
[28] (a) Wang, W. H.; Niu, M.; Hou, Y. C.; Wu, W. Z.; Liu, Z. Y.; Liu, Q. Y.; Ren, S. H.; Marsh, K. N. Green Chem. 2014, 16, 2614.
(b) Niu, M.; Hou, Y.-C.; Ren, S. H.; Wang, W. H.; Zheng, Q. T.; Wu, W. Z. Green Chem. 2015, 17, 335.
(c) Niu, M.; Hou, Y. C.; Ren, S. H.; Wu, W. Z.; Marsh, K. N. Green Chem. 2015, 17, 453.
[29] (a) Custodis, V. B. F.; Karakoulia, S. A.; Triantafyllidis, K. S.; van Bokhoven, J. A. ChemSusChem 2016, 9, 1134.
(b) Shu, R. Y.; Xu, Y.; Zhang, Q.; Ma, L. L.; Wang, T. J. CIESC J. 2016, 67, 4523(in Chinese). (舒日洋, 徐莹, 张琦, 马隆龙, 王铁军, 化工学报, 2016, 67, 4523.)
[30] (a) Shuai, L.; Amiri, M. T.; Questell-Santiago, Y. M.; Heroguel, F.; Li, Y. D.; Kim, H.; Meilan, R.; Chapple, C.; Ralph, J.; Luterbacher, J. Science 2016, 354, 329.
(b) Wang, L.; Meng, Y. Z.; Wang, S. J.; Shang, X. Y.; Li, L.; Hay, A. S. Macromolecules 2004, 37, 3151.
[31] Huang, X. Q.; Li, X. Y.; Zou, M. C.; Song, S.; Tang, C. H.; Yuan, Y. Z.; Jiao, N. J. Am. Chem. Soc. 2014, 136, 14858.
[32] Jiang, Y. Y.; Yan, L.; Zhang, Q.; Fu, Y. ACS Catal. 2016, 6, 4399.

酸性体系V催化木质素β-O-4模型物C-C键高选择性切断

Lignin C-C Bond's Cleavage by Vanadium Catalyzed with High Selectivity in Acid Environment

PDF

补充材料

可视化

摘要/Abstract

引用此文

分享此文

参考文献

相关文章 15

编辑推荐

相关统计

本文评价

[1]	林航青, 马若茹, 江怡蓝, 许木榕, 林洋彭, 杜克钊. 用于卤素捕获的材料研究进展[J]. 化学学报, 2024, 82(1): 62-74.
[2]	王志强, 苏进展. 磷酸钴修饰Cu₃V₂O₈/ZnO光阳极的动力学特性及光电化学水分解研究[J]. 化学学报, 2024, 82(1): 26-35.
[3]	李萍, 杨琪玉, 曾婧, 张然, 陈秋燕, 闫飞. 氟掺杂对可逆固体氧化物电池性能的影响及相关动力学研究[J]. 化学学报, 2024, 82(1): 36-45.
[4]	高炜洋, 邓伟超, 高扬, 梁仁校, 贾义霞. 吲哚分子间不对称去芳构化氧化Heck反应[J]. 化学学报, 2024, 82(1): 1-4.
[5]	付信朴, 王秀玲, 王伟伟, 司锐, 贾春江. 团簇Au/CeO₂的制备及其催化CO氧化反应构效关系的研究^★[J]. 化学学报, 2023, 81(8): 874-883.
[6]	刘建川, 李翠艳, 刘耀祖, 王钰杰, 方千荣. 高稳定二维联咔唑sp²碳共轭共价有机框架材料用于高效电催化氧还原^★[J]. 化学学报, 2023, 81(8): 884-890.
[7]	徐袁利, 潘辉, 杨义, 左智伟. 连续流条件下蒽-铈协同催化的苄位碳氢键选择性氧化反应^★[J]. 化学学报, 2023, 81(5): 435-440.
[8]	贾洋刚, 陈诗洁, 邵霞, 程婕, 林娜, 方道来, 冒爱琴, 李灿华. 高性能无钴化钙钛矿型高熵氧化物负极材料的制备及储锂性能研究[J]. 化学学报, 2023, 81(5): 486-495.
[9]	张慧颖, 于淑艳, 李从举. 高分子聚合物基碳纳米膜的电催化降解污水性能及机理[J]. 化学学报, 2023, 81(4): 420-430.
[10]	高丰琴, 刘洋, 张引莉, 蒋育澄. 羧基功能化Fe₃O₄固定化酶反应器的构筑及性能研究[J]. 化学学报, 2023, 81(4): 338-344.
[11]	王文涛, 赖欣婷, 闫士全, 朱雷, 姚玉元, 丁黎明. 双功能气凝胶吸附-降解协同处理染料废水[J]. 化学学报, 2023, 81(3): 222-230.
[12]	于璐瑶, 任祯, 杨宇森, 卫敏. 生物基聚酯单体的定向催化制备[J]. 化学学报, 2023, 81(2): 175-190.
[13]	杨娜, 马建中, 石佳博, 郭旭. 层状复合氢氧化物的有机改性方法及应用研究进展[J]. 化学学报, 2023, 81(2): 207-216.
[14]	常婉莹, 谭莹瑛, 吴静怡, 刘英杰, 蔡金海, 赖春艳. 三维结构Li_6.28La₃Zr₂Al_0.24O₁₂增强聚氧化乙烯基固态电解质的性能研究[J]. 化学学报, 2023, 81(12): 1708-1715.
[15]	杨贯文, 伍广朋. 模块化双功能有机硼氮和硼磷催化体系的设计及其催化转化^★[J]. 化学学报, 2023, 81(11): 1551-1565.