Citation: Ding Shuang, Ge Qingfeng, Zhu Xinli. Research Progress in Ketonization of Biomass-derived Carboxylic Acids over Metal Oxides[J]. Acta Chimica Sinica, ;2017, 75(5): 439-447. doi: 10.6023/A17020061 shu

Research Progress in Ketonization of Biomass-derived Carboxylic Acids over Metal Oxides

Collaborative Innovation Center of Chemical Science and Engineering, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, China

Corresponding author: Zhu Xinli, xinlizhu@tju.edu.cn
Received Date: 16 February 2017

Fund Project: the National Natural Science Foundation of China 21676194the National Natural Science Foundation of China 21373148the Ministry of Education of China Program of New Century Excellent Talents in University NCET-12-0407

Figures(5)

With the increasing needs for transportable fuels and the growing concerns on environmental pollution, significant attention has been paid to the conversion of renewable lignocellulosic biomass to liquid fuels. As a major component of bio-oil from biomass depolymerization, organic carboxylic acids make the bio-oil acidic, corrosive and unstable, which are harmful for storage, transportation, and upgrading of bio-oil. Therefore, the removal of carboxylic acids is very important. Ketonization reaction, also called ketonic decarboxylation, converts two moles carboxylic acids to ketone (symmetrical or asymmetrical ketones), carbon dioxide and water, which removes oxygen efficiently and increases the carbon chain length without using hydrogen. In addition, ketones are important chemicals and have been widely used in chemical industry as organic solvent. The mechanism and active site for ketonization are still under debate. Various mechanisms have been proposed for the ketonization, based on different reaction intermediates evolved (i.e., β-keto-acids, ketene, carboxylates and acyl carbonium ions). Ketonization reaction is a surface-structure-sensitive reaction, thus reaction activity depends on surface-structure of the metal oxides (such as crystal surfaces and particle size). The concerted function of oxygen anions (Brønsted bases) and unsaturated metal cations (Lewis acids) is crucial for ketonization. The amphoteric oxides show better catalytic activity than pure acidic or basic oxides. Oxygen vacancy formed on the surface of metal oxides is a key factor for high ketonization activity, which can stabilize the reaction product and reduce the activation energy. This paper reviews the progress in ketonization from the aspects of reaction mechanism, and the effects of surface structure, acidity and basicity, and reducibility of metal oxides on ketonization. The β-keto-acids based mechanism and ketene based mechanism will be discussed in detail to understand how does the C—C coupling happen and the fundamental role of α-H. Finally, the importance of surface structure and properties of metal oxides on the carboxylic acids ketonization reaction is explained.
- carboxylic acid,
- ketonization,
- metal oxides,
- surface-structure and property,
- reaction mechanism
1. [1]
  Huber, G. W.; Iborra, S.; Corma, A. Chem. Rev. 2006, 106, 4044. doi: 10.1021/cr068360d
2. [2]
  Corma, A.; Iborra, S.; Velty, A. Chem. Rev. 2007, 107, 2411. doi: 10.1021/cr050989d
3. [3]
  Goyal, H. B.; Seal, D.; Saxena, R. C. Renew. Sust. Energ. Rev. 2008, 12, 504. doi: 10.1016/j.rser.2006.07.014
4. [4]
  Tao, J. J.; Chen, S.; Yao, F. Q.; Wang, H. H. Acta Chim. Sinica. 2016, 74, 81 (in Chinese).
5. [5]
  Ou, J. K.; Yang, L.; Xi, X. H. Chin. J. Chem. 2016, 34, 727. doi: 10.1002/cjoc.v34.7
6. [6]
  Dai, N.; Shang, R.; Fu, M. C.; Fu, Y. Chin. J. Chem. 2015, 33, 405. doi: 10.1002/cjoc.v33.4
7. [7]
  Li, J.; Huang, Y. B.; Guo, Q. X.; Fu, Y. Acta Chim. Sinica. 2014, 72, 1223 (in Chinese). doi: 10.3866/PKU.WHXB201405091
8. [8]
  Bertero, M.; Puente, G. D. L.; Sedran, U. Fuel. 2012, 95, 263. doi: 10.1016/j.fuel.2011.08.041
9. [9]
  Ignatchenko, A. V.; Kozliak, E. I. ACS Catal. 2012, 2, 1555. doi: 10.1021/cs3002989
10. [10]
  Nagashima, O.; Sato, S.; Takahashi, R.; Sodesawa, T. J. Mol. Catal. A: Chem. 2005, 227, 231. doi: 10.1016/j.molcata.2004.10.042
11. [11]
  Randery, S. D.; Warren, J. S.; Dooley, K. M. Appl. Catal., A 2002, 226, 265. doi: 10.1016/S0926-860X(01)00912-7
12. [12]
  Hendren, T. S.; Dooley, K. M. Catal. Today 2003, 85, 333. doi: 10.1016/S0920-5861(03)00399-7
13. [13]
  Dooley, K. M.; Bhat, A. K.; Plaisance, C. P.; Roy, A. D. Appl. Catal., A 2007, 320, 122. doi: 10.1016/j.apcata.2007.01.021
14. [14]
  Murkute, A. D.; Jackson, J. E.; Miller, D. J. J. Catal. 2011, 278, 189. doi: 10.1016/j.jcat.2010.12.001
15. [15]
  Ignatchenko, A. V.; Deraddo, J. S.; Marino, V. J.; Mercado, A. Appl. Catal., A 2015, 498, 10. doi: 10.1016/j.apcata.2015.03.017
16. [16]
  Friedel, C. Justus Liebigs Ann. Chem. 1858, 108, 122. doi: 10.1002/(ISSN)1099-0690
17. [17]
  Hu, M.; Zhu, Z. Q.; Xu, Z. H. Chem. Ind. Eng. Prog. 2010, 29, 316 (in Chinese).
18. [18]
  Pestman, R.; Koster, R. M.; Duijne, A. V.; Pieterse, J. A. Z.; Ponec, V. J. Catal. 1997, 168, 265. doi: 10.1006/jcat.1997.1624
19. [19]
  Pham, T. N.; Shi, D.; Resasco, D. E. J. Catal. 2014. 314, 149. doi: 10.1016/j.jcat.2014.04.008
20. [20]
  Pei, Z. F.; Ponec, V. Appl. Surf. Sci. 1996, 103, 171. doi: 10.1016/0169-4332(96)00453-9
21. [21]
  Calaza, F. C.; Chen, T. L.; Mullins, D. R.; Xu, Y.; Overbury, S. H. Catal. Today 2015, 253, 65. doi: 10.1016/j.cattod.2015.03.033
22. [22]
  Lee, Y.; Choi, J. W.; Suh, D. J.; Ha, J. M.; Lee, C. H. Appl. Catal., A 2015, 506, 288. doi: 10.1016/j.apcata.2015.09.008
23. [23]
  Das, J.; Parida, K. React. Kinet. Catal. Lett. 2000, 69, 223. doi: 10.1023/A:1005627228083
24. [24]
  Parida, K.; Das, J. J. Mol. Catal. A: Chem. 2000, 151, 185. doi: 10.1016/S1381-1169(99)00240-X
25. [25]
  Martens, J. A.; Wydoodt, M.; Espeel, P.; Jacobs, P. A. Stud. Surf. Sci. Catal. 1993, 78, 527. doi: 10.1016/S0167-2991(08)63362-5
26. [26]
  Gumidyala, A.; Sooknoi, T.; Crossley, S. J. Catal. 2016, 340, 76. doi: 10.1016/j.jcat.2016.04.017
27. [27]
  Yamada, Y.; Segawa, M.; Sato, F.; Kojima, T.; Sato, S. J. Mol. Catal. A: Chem. 2011, 346, 79. doi: 10.1016/j.molcata.2011.06.011
28. [28]
  Sun, C. H.; Chen, Y. S.; Li, J. Inorg. Chem. Ind. 2008, 40, 44 (in Chinese). doi: 10.3969/j.issn.1006-4990.2008.03.015
29. [29]
  Pulido, A.; Oliver-Tomas, B.; Renz, M.; Boronat, M.; Corma, A. Chem Sus Chem 2013, 6, 141. doi: 10.1002/cssc.201200419
30. [30]
  Pham, T. N.; Dachuan, S.; Resasco, D. E. Top. Catal. 2014, 57, 706. doi: 10.1007/s11244-013-0227-7
31. [31]
  Snell, R. W.; Shanks, B. H. ACS Catal. 2013, 3, 783. doi: 10.1021/cs400003n
32. [32]
  Gaertner, C. A.; Serrano-Ruiz, J. C.; Braden, D. J.; Dumesic, J. A. Ind. Eng. Chem. Res. 2010, 49, 6023.
33. [33]
  Gaertner, C. A.; Serrano-Ruiz, J. C.; Braden, D. J.; Dumesic, J. A. J. Catal. 2009, 266, 71. doi: 10.1016/j.jcat.2009.05.015
34. [34]
  Gaertner, C. A.; Serrano-Ruiz, J. C.; Braden, D. J.; Dumesic, J. A. Chem Sus Chem 2009, 2, 1121. doi: 10.1002/cssc.v2:12
35. [35]
  Rajadurai, S. Catal. Rev. 1994, 36, 385. doi: 10.1080/01614949408009466
36. [36]
  Renz, M. Eur. J. Org. Chem. 2005, 2005, 979. doi: 10.1002/(ISSN)1099-0690
37. [37]
  Ning, P. G.; Cao, H. B.; Zhang, Y. Mod. Chem. Ind. 2008, 28, 22 (in Chinese). doi: 10.3321/j.issn:0253-4320.2008.01.006
38. [38]
  Pham, T. N.; Tawan, S.; Steven, P. C.; Resasco, D. E. ACS Catal. 2013, 3, 2456. doi: 10.1021/cs400501h
39. [39]
  Pacchioni, G. ACS Catal. 2014, 4, 2874. doi: 10.1021/cs500791w
40. [40]
  Mekhemer, G. A. H.; Halawy, S. A.; Mohamed, M. A.; Zaki, M. I. J. Catal. 2005, 230, 109. doi: 10.1016/j.jcat.2004.09.030
41. [41]
  Pham, T. N.; Shi, D.; Sooknoi, T.; Resasco, D. E. J. Catal. 2012, 295, 169. doi: 10.1016/j.jcat.2012.08.012
42. [42]
  Idriss, H.; Diagne, C.; Hindermann, J. P.; Kiennemann, A.; Barteau, M. A. J. Catal. 1995, 155, 219. doi: 10.1006/jcat.1995.1205
43. [43]
  Zhang, Y.; Gao, Z. L.; Chen, Y. S.; Li, X. Chin. J. Rare Met. 2010, 34, 574 (in Chinese). doi: 10.3969/j.issn.0258-7076.2010.04.019
44. [44]
  Zhang, Y.; Gao, Z. L.; Chen, Y. S.; Li, X. Inorg. Chem. Ind. 2010, 4, 33 (in Chinese). doi: 10.3969/j.issn.1006-4990.2010.04.011
45. [45]
  Gliński, M.; Zalewski, G.; Burno, E.; Jerzak, A. Appl. Catal., A 2014, 470, 278. doi: 10.1016/j.apcata.2013.10.047
46. [46]
  Zaytseva, Y. A.; Panchenko, V. N.; Simonov, M. N.; Shutilov, A. A.; Zenkovets, G. A.; Renz, M.; Simakova, I. L.; Parmon, V. N. Top. Catal. 2013, 56, 846. doi: 10.1007/s11244-013-0045-y
47. [47]
  Crisci, A. J.; Dou, H.; Prasomsri, T.; Román-Leshkov, Y. ACS Catal. 2014, 4, 4196. doi: 10.1021/cs501018k
48. [48]
  Snell, R. W.; Shanks, B. H. ACS Catal. 2014, 4, 512. doi: 10.1021/cs400851j
49. [49]
  Teterycz, H.; Klimkiewicz, R.; Łaniecki, M. Appl. Catal., A 2003, 249, 313. doi: 10.1016/S0926-860X(03)00231-X
50. [50]
  Kobume, M.; Sato, S.; Takahashi, R. J. Mol. Catal. A: Chem. 2008, 279, 10. doi: 10.1016/j.molcata.2007.09.027
51. [51]
  Wang, W. D.; Lin, P. Y.; Fu, Y. L.; Yu, S. M.; Meng, M.; Zhang, X. P. Chin. J. Chem. 2000, 18, 673.
52. [52]
  Vohs, J. M. Chem. Rev. 2013, 113, 4136. doi: 10.1021/cr300328u
53. [53]
  Stubenrauch, J.; Brosha, E.; Vohs, J. M. Catal. Today 1996, 28, 431. doi: 10.1016/S0920-5861(96)00251-9
54. [54]
  Wang, Z. L.; Feng, X. D. J. Phys. Chem. B 2003, 107, 13563. doi: 10.1021/jp036815m
55. [55]
  Snell, R. W.; Shanks, B. H. Appl. Catal., A 2013, 451, 86. doi: 10.1016/j.apcata.2012.08.043
56. [56]
  Sun, J.; Gao, L. Acta Chim. Sinica 2002, 60, 1524 (in Chinese). doi: 10.3321/j.issn:0567-7351.2002.08.030
57. [57]
  Kim, K. S.; Barteau, M. A. J. Catal. 1990, 125, 353. doi: 10.1016/0021-9517(90)90309-8
58. [58]
  Ojamäe, L.; Aulin, C.; Pedersen, H.; Käll, P. O. J. Colloid Interface Sci. 2006, 296, 71. doi: 10.1016/j.jcis.2005.08.037
59. [59]
  Glinski, M.; Kijenski, J.; Jakubowski, A. Appl. Catal., A 1995, 128, 209. doi: 10.1016/0926-860X(95)00082-8
60. [60]
  Hasan, M. A.; Zaki, M. I.; Pasupulety, L. Appl. Catal., A 2003, 243, 81. doi: 10.1016/S0926-860X(02)00539-2
61. [61]
  Panchenko, V. N.; Zaytseva, Y. A.; Simonov, M. N.; Simakova, I. L.; Paukshtis, E. A. J. Mol. Catal. A: Chem. 2014, 388, 133.
62. [62]
  Tosoni, S.; Pacchioni, G. J. Catal. 2016, 344, 465. doi: 10.1016/j.jcat.2016.10.002
1. [1]
  Aili Feng , Xin Lu , Peng Liu , Dongju Zhang . Computational Chemistry Study of Acid-Catalyzed Esterification Reactions between Carboxylic Acids and Alcohols. University Chemistry, 2025, 40(3): 92-99. doi: 10.12461/PKU.DXHX202405072
2. [2]
  Ronghao Zhao , Yifan Liang , Mengyao Shi , Rongxiu Zhu , Dongju Zhang . Investigation into the Mechanism and Migratory Aptitude of Typical Pinacol Rearrangement Reactions: A Research-Oriented Computational Chemistry Experiment. University Chemistry, 2024, 39(4): 305-313. doi: 10.3866/PKU.DXHX202309101
3. [3]
  Peng YUE , Liyao SHI , Jinglei CUI , Huirong ZHANG , Yanxia GUO . Effects of Ce and Mn promoters on the selective oxidation of ammonia over V₂O₅/TiO₂ catalyst. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 293-307. doi: 10.11862/CJIC.20240210
4. [4]
  Jiajie Li , Xiaocong Ma , Jufang Zheng , Qiang Wan , Xiaoshun Zhou , Yahao Wang . Recent Advances in In-Situ Raman Spectroscopy for Investigating Electrocatalytic Organic Reaction Mechanisms. University Chemistry, 2025, 40(4): 261-276. doi: 10.12461/PKU.DXHX202406117
5. [5]
  Mingyang Men , Jinghua Wu , Gaozhan Liu , Jing Zhang , Nini Zhang , Xiayin Yao . 液相法制备硫化物固体电解质及其在全固态锂电池中的应用. Acta Physico-Chimica Sinica, 2025, 41(1): 2309019-. doi: 10.3866/PKU.WHXB202309019
6. [6]
  Wentao Lin , Wenfeng Wang , Yaofeng Yuan , Chunfa Xu . Concerted Nucleophilic Aromatic Substitution Reactions. University Chemistry, 2024, 39(6): 226-230. doi: 10.3866/PKU.DXHX202310095
7. [7]
  Hongting Yan , Aili Feng , Rongxiu Zhu , Lei Liu , Dongju Zhang . Reexamination of the Iodine-Catalyzed Chlorination Reaction of Chlorobenzene Using Computational Chemistry Methods. University Chemistry, 2025, 40(3): 16-22. doi: 10.12461/PKU.DXHX202403010
8. [8]
  Guowen Xing , Guangjian Liu , Le Chang . Five Types of Reactions of Carbonyl Oxonium Intermediates in University Organic Chemistry Teaching. University Chemistry, 2025, 40(4): 282-290. doi: 10.12461/PKU.DXHX202407058
9. [9]
  Ling Fan , Meili Pang , Yeyun Zhang , Yanmei Wang , Zhenfeng Shang . Quantum Chemistry Calculation Research on the Diels-Alder Reaction of Anthracene and Maleic Anhydride: Introduction to a Computational Chemistry Experiment. University Chemistry, 2024, 39(4): 133-139. doi: 10.3866/PKU.DXHX202309024
10. [10]
  Jiabo Huang , Quanxin Li , Zhongyan Cao , Li Dang , Shaofei Ni . Elucidating the Mechanism of Beckmann Rearrangement Reaction Using Quantum Chemical Calculations. University Chemistry, 2025, 40(3): 153-159. doi: 10.12461/PKU.DXHX202405172
11. [11]
  Qian Huang , Zhaowei Li , Jianing Zhao , Ao Yu . Quantum Chemical Calculations Reveal the Details Below the Experimental Phenomenon. University Chemistry, 2024, 39(3): 395-400. doi: 10.3866/PKU.DXHX202309018
12. [12]
  Yong Wang , Yingying Zhao , Boshun Wan . Analysis of Organic Questions in the 37th Chinese Chemistry Olympiad (Preliminary). University Chemistry, 2024, 39(11): 406-416. doi: 10.12461/PKU.DXHX202403009
13. [13]
  Zihan Lin , Wanzhen Lin , Fa-Jie Chen . Electrochemical Modifications of Native Peptides. University Chemistry, 2025, 40(3): 318-327. doi: 10.12461/PKU.DXHX202406089
14. [14]
  Xiaoling LUO , Pintian ZOU , Xiaoyan WANG , Zheng LIU , Xiangfei KONG , Qun TANG , Sheng WANG . Synthesis, crystal structures, and properties of lanthanide metal-organic frameworks based on 2, 5-dibromoterephthalic acid ligand. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1143-1150. doi: 10.11862/CJIC.20230271
15. [15]
  Liyang ZHANG , Dongdong YANG , Ning LI , Yuanyu YANG , Qi MA . Crystal structures, luminescent properties and Hirshfeld surface analyses of three cadmium(Ⅱ) complexes based on 2-(3-(pyridin-2-yl)-1H-pyrazol-1-yl)benzoate. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1943-1952. doi: 10.11862/CJIC.20240079
16. [16]
  Lina Guo , Ruizhe Li , Chuang Sun , Xiaoli Luo , Yiqiu Shi , Hong Yuan , Shuxin Ouyang , Tierui Zhang . 层状双金属氢氧化物的层间阴离子对衍生的Ni-Al₂O₃催化剂光热催化CO₂甲烷化反应的影响. Acta Physico-Chimica Sinica, 2025, 41(1): 2309002-. doi: 10.3866/PKU.WHXB202309002
17. [17]
  Xueyu Lin , Ruiqi Wang , Wujie Dong , Fuqiang Huang . 高性能双金属氧化物负极的理性设计及储锂特性. Acta Physico-Chimica Sinica, 2025, 41(3): 2311005-. doi: 10.3866/PKU.WHXB202311005
18. [18]
  Endong YANG , Haoze TIAN , Ke ZHANG , Yongbing LOU . Efficient oxygen evolution reaction of CuCo₂O₄/NiFe-layered bimetallic hydroxide core-shell nanoflower sphere arrays. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 930-940. doi: 10.11862/CJIC.20230369
19. [19]
  Yingchun ZHANG , Yiwei SHI , Ruijie YANG , Xin WANG , Zhiguo SONG , Min WANG . Dual ligands manganese complexes based on benzene sulfonic acid and 2, 2′-bipyridine: Structure and catalytic properties and mechanism in Mannich reaction. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1501-1510. doi: 10.11862/CJIC.20240078
20. [20]
  Chuanming GUO , Kaiyang ZHANG , Yun WU , Rui YAO , Qiang ZHAO , Jinping LI , Guang LIU . Performance of MnO₂-0.39IrO_x composite oxides for water oxidation reaction in acidic media. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1135-1142. doi: 10.11862/CJIC.20230459

Get Citation

PDF

XML

Metrics

PDF Downloads(34)
Abstract views(2291)
HTML views(539)

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