Citation: ZHU Qing, LIANG Li-Ping, JIA Zhi-Qi, GAO Chun-Guang, ZHAO Yong-Xiang. Polyoxotungstate-Modified Zirconia Aerogel as a Solid Catalyst for Tetrahydrofuran Polymerization[J]. Acta Physico-Chimica Sinica, ;2011, 27(02): 491-498. doi: 10.3866/PKU.WHXB20110212 shu

Polyoxotungstate-Modified Zirconia Aerogel as a Solid Catalyst for Tetrahydrofuran Polymerization

1.
1. School of Chemistry and Chemical Engineering, Engineering Research Center for Fine Chemicals of Ministry of Education, Shanxi University, Taiyuan 030006, P. R. China;
2. School of Materials Science and Engineering, Taiyuan University of Science and Technology, Taiyuan 030024, P. R. China

Received Date: 10 August 2010
Available Online: 24 December 2010
Fund Project: 山西省科技攻关计划项目(20090321059) (20090321059)山西省发改委产业技术开发项目(2009164)资助 (2009164)

Catalysts with different loadings (mass fractions from 5% to 45%) of tungstophosphoric acid (TPA) on zirconia were prepared by suspending zirconia aerogel in an ethanol solution of TPA, removing the solvent via evaporation, drying and then calcining the powder at 750 °C. These catalysts were characterized by N₂ adsorption, X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, FTIR spectroscopy of adsorbed Pyridine (Py-IR), and temperature programmed desorption of NH₃ (NH₃-TPD). The catalytic performances of these materials were examined for the polymerization of tetrahydrofuran (THF). The experimental results indicated that the strong interaction between TPA and zirconia retarded both the crystallization of zirconia and the destruction of the Keggin-unit of TPA. In these materials, the major tungsten species were found to be zirconia-anchored heteropolytungstates (with distorted intact and/or partially fragmented Keggin-units) and Zr-containing pseudo-heteropolyanions produced by the chemical bonding of Zr⁴⁺ with the WO_x fragments from TPA decomposition as well as some amount of WO₃. The catalysts showed both Brönsted and Lewis acidity, and the catalyst with 20% TPA loading had the highest total acidity and catalytic activity because of the monolayer coverage of the active species. Under the reaction conditions of 40 °C for 20 h, the most active catalyst, 20TPZ-750, gave a high polymer yield of 30.9%±2%. During recycling for 6 times, no obvious activity loss was observed.
- Zirconia aerogel,
- Tungstophosphoric acid,
- Polyoxotungstate,
- Tetrahydrofuran,
- Polymerization
1. [1]
  
  (1) Setoyama, T.; Kobayashi, M.; Kabata, Y.; Kawai, T.; Nakanishi, A. Catal. Today 2002, 73, 29.
2. [2]
  (2) Okuhara, T.; Mizuno, N.; Misono, M. Appl. Catal. A: Gen. 2001, 222, 63.
3. [3]
  (3) Rafiee, E.; Joshaghani, M.; Tork, F.; Fakhri, A.; Eavani, S. J. Mol. Catal. A: Chem. 2008, 283, 1.
4. [4]
  (4) Bhatt, N.; Patel, A. J. Mol. Catal. A: Chem. 2007, 264, 214.
5. [5]
  (5) Bhatt, N.; Sharma, P.; Patel, A.; Selvam, P. Catal. Commun. 2008, 9, 1545.
6. [6]
  (6) Sharma, P.; Patel, A. Appl. Surf. Sci. 2009, 255, 7635.
7. [7]
  (7) Mallick, S.; Parida, K. M. Catal. Commun. 2007, 8, 889.
8. [8]
  (8) Parida, K. M.; Mallick, S. J. Mol. Catal. A: Chem. 2007, 275, 7.
9. [9]
  (9) Parida, K. M.; Mallick, S.; Pradhan, G. C. J. Mol. Catal. A: Chem. 2009, 297, 93.
10. [10]
  (10) Rajkumar, T.; Rao, G. R. J. Mol. Catal. A: Chem. 2008, 295, 1.
11. [11]
  (11) Oliveira, C. F.; Dezaneti, L. M.; Garcia, F. A. C.; de Macedo, J. L.; Dias, J. A.; Dias, S. C. L.; Alvim, Kayne S. P. Appl. Catal. A: Gen. 2010, 372, 153.
12. [12]
  (12) Devassy, B. M.; Lefebvre, F.; Halligudi, S. B. J. Catal. 2005, 31, 1.
13. [13]
  (13) Devassy, B. M.; Halligudi, S. B. J. Catal. 2005, 236, 313.
14. [14]
  (14) Devassy, B. M.; Halligudi, S. B. J. Mol. Catal. A: Chem. 2006, 253, 8.
15. [15]
  (15) Sunita, G.; Devassy, B. M.; Vinu, A.; Sawant, D. P.; alasubramanian, V. V.; Halligudi, S. B. Catal. Commun. 2008, 9, 696.
16. [16]
  (16) Lucas, N.; Bordoloi, A.; Amrute, A. P.; Kasinathan, P.; Vinu, A.; ohringer,W.; Fletcher, J. C. Q.; Halligudi, S. B. Appl. Catal. A: Gen. 2009, 352, 74.
17. [17]
  (17) Sawant, D. P.; Vinu, A.; Lefebvre, F.; Halligudi, S. B. J. Mol. Catal. A: Chem. 2007, 262, 98.
18. [18]
  (18) Sawant, D. P.; Vinu, A.; Mirajkar, S. P.; Lefebvre, F.; Ariga, K.; Anandan, S.; Mori, T.; Nishimura, C.; Halligudi, S. B. J. Mol. atal. A: Chem. 2007, 271, 46.
19. [19]
  (19) Sawant, D. P.; Hartmann, M.; Halligudi, S. B. Microporous Mesoporous Mat. 2007, 102, 223.
20. [20]
  (20) Satam, . R.; Parghi, K. D.; Jayaram, R. V. Catal. Commun. 2008, 9, 1071.
21. [21]
  (21) Chai, S. H.;Wang, H. P.; Liang, Y.; Xu, B. Q. Appl. Catal. A: Gen., 2009, 353, 213.
22. [22]
  (22) Liang, L. P.; Dang, S.;Wu, D.; Sun, Y. H. J. Mater. Sci. Technol. 2004, 20, 435.
23. [23]
  (23) Zhao, M.; Jia, Z. Q.; Zhao, L. L.; Sun, Z. J.; Liu, X.W.;Wang, P. F.; Gao, C. G. J. Mol. Catal. (China) 2010, 24, 117.
24. [24]
  [赵敏, 志奇, 赵丽丽, 孙自瑾, 刘新文, 王鹏飞, 高春光, 赵永祥. 分子催化, 2010, 24, 117.]
25. [25]
  (24) Damyanova, S.; Fierro, J. L. G.; Sobrados, I.; Sanz, J. Langmuir 1999, 15, 469.
26. [26]
  (25) López-Salinas, E.; Hernández-Cortéz, J. G.; Schifter, I.; Torres- arcía, E.; Navarrete, J.; Gutiérrez-Carrillo, A.; López, T.; ottici, P. P.; Bersani, D. Appl. Catal. A: Gen. 2000, 193, 215.
27. [27]
  (26) Vu, T. N.; Van Gestel, J.; Gilson, J. P.; Collet, C.; Dath, J. P.; uchet, J. C. J. Catal. 2005, 231, 453.
28. [28]
  (27) Martínez, A.; Prieto, G.; Arribas, M. A.; Concepción, P.; ánchez-Royo, J. F. J. Catal. 2007, 248, 288.
29. [29]
  (28) Lebarbier, V.; Clet, G.; Houalla, M. J. Phys. Chem. B 2006, 110, 3905.
30. [30]
  (29) Chen, S. C.; Lin, F. S.; Chou, J. Y.; Hsu, L. A.; Chu, M. H.; Huang, C. C.; Shao, M. H. Method for preparing polyether olyol and copolymer thereof. US Patent 6313262, 2001-11-06.
31. [31]
  (30) Liao, X. M.; Chu,W.; Li, Y.; Zhou, F. D.; Luo, S. Z. Chinese hem. Lett. 2009, 20, 344.
32. [32]
  (31) Huang, M.; Chu,W.; Liao, X. M.; Dai, X. Y. Chinese Sci. Bull. 2010, 55, 2652.
1. [1]
  Zhengyu Zhou , Huiqin Yao , Youlin Wu , Teng Li , Noritatsu Tsubaki , Zhiliang Jin . Synergistic Effect of Cu-Graphdiyne/Transition Bimetallic Tungstate Formed S-Scheme Heterojunction for Enhanced Photocatalytic Hydrogen Evolution. Acta Physico-Chimica Sinica, 2024, 40(10): 2312010-. doi: 10.3866/PKU.WHXB202312010
2. [2]
  Laiying Zhang , Yinghuan Wu , Yazi Yu , Yecheng Xu , Haojie Zhang , Weitai Wu . Innovation and Practice of Polymer Chemistry Experiment Teaching for Non-Polymer Major Students of Chemistry: Taking the Synthesis, Solution Property, Optical Performance and Application of Thermo-Sensitive Polymers as an Example. University Chemistry, 2024, 39(4): 213-220. doi: 10.3866/PKU.DXHX202310126
3. [3]
  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
4. [4]
  Xiao SANG , Qi LIU , Jianping LANG . Synthesis, structure, and fluorescence properties of Zn(Ⅱ) coordination polymers containing tetra-alkenylpyridine ligands. Chinese Journal of Inorganic Chemistry, 2024, 40(11): 2124-2132. doi: 10.11862/CJIC.20240158
5. [5]
  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
6. [6]
  Junjie Zhang , Yue Wang , Qiuhan Wu , Ruquan Shen , Han Liu , Xinhua Duan . Preparation and Selective Separation of Lightweight Magnetic Molecularly Imprinted Polymers for Trace Tetracycline Detection in Milk. University Chemistry, 2024, 39(5): 251-257. doi: 10.3866/PKU.DXHX202311084
7. [7]
  Zizheng LU , Wanyi SU , Qin SHI , Honghui PAN , Chuanqi ZHAO , Chengfeng HUANG , Jinguo PENG . Surface state behavior of W doped BiVO₄ photoanode for ciprofloxacin degradation. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 591-600. doi: 10.11862/CJIC.20230225
8. [8]
  Bo YANG , Gongxuan LÜ , Jiantai MA . Nickel phosphide modified phosphorus doped gallium oxide for visible light photocatalytic water splitting to hydrogen. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 736-750. doi: 10.11862/CJIC.20230346
9. [9]
  .
  南开大学师唯/华北电力大学（保定）刘景维：二维配位聚合物中有序的亲锂冠醚位点用于无枝晶锂沉积
  . CCS Chemistry, 2025, 7(0): -.
10. [10]
  Xiaoning TANG , Shu XIA , Jie LEI , Xingfu YANG , Qiuyang LUO , Junnan LIU , An XUE . Fluorine-doped MnO₂ with oxygen vacancy for stabilizing Zn-ion batteries. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1671-1678. doi: 10.11862/CJIC.20240149
11. [11]
  Zhiquan Zhang , Baker Rhimi , Zheyang Liu , Min Zhou , Guowei Deng , Wei Wei , Liang Mao , Huaming Li , Zhifeng Jiang . Insights into the Development of Copper-based Photocatalysts for CO₂ Conversion. Acta Physico-Chimica Sinica, 2024, 40(12): 2406029-. doi: 10.3866/PKU.WHXB202406029
12. [12]
  Yongzhi LI , Han ZHANG , Gangding WANG , Yanwei SUI , Lei HOU , Yaoyu WANG . A two-dimensional metal-organic framework for the determination of nitrofurantoin and nitrofurazone in aqueous solution. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 245-253. doi: 10.11862/CJIC.20240307
13. [13]
  Caixia Lin , Zhaojiang Shi , Yi Yu , Jianfeng Yan , Keyin Ye , Yaofeng Yuan . Ideological and Political Design for the Electrochemical Synthesis of Benzoxathiazine Dioxide Experiment. University Chemistry, 2024, 39(2): 61-66. doi: 10.3866/PKU.DXHX202309005
14. [14]
  Bing WEI , Jianfan ZHANG , Zhe CHEN . Research progress in fine tuning of bimetallic nanocatalysts for electrocatalytic carbon dioxide reduction. Chinese Journal of Inorganic Chemistry, 2025, 41(3): 425-439. doi: 10.11862/CJIC.20240201
15. [15]
  Yongwei ZHANG , Chuang ZHU , Wenbin WU , Yongyong MA , Heng YANG . Efficient hydrogen evolution reaction activity induced by ZnSe@nitrogen doped porous carbon heterojunction. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 650-660. doi: 10.11862/CJIC.20240386
16. [16]
  Jie ZHAO , Huili ZHANG , Xiaoqing LU , Zhaojie WANG . Theoretical calculations of CO₂ capture and separation by functional groups modified 2D covalent organic framework. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 275-283. doi: 10.11862/CJIC.20240213
17. [17]
  Zhongxin YU , Wei SONG , Yang LIU , Yuxue DING , Fanhao MENG , Shuju WANG , Lixin YOU . Fluorescence sensing on chlortetracycline of a Zn-coordination polymer based on mixed ligands. Chinese Journal of Inorganic Chemistry, 2024, 40(12): 2415-2421. doi: 10.11862/CJIC.20240304
18. [18]
  Linjie ZHU , Xufeng LIU . Electrocatalytic hydrogen evolution performance of tetra-iron complexes with bridging diphosphine ligands. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 321-328. doi: 10.11862/CJIC.20240207
19. [19]
  Wei HE , Jing XI , Tianpei HE , Na CHEN , Quan YUAN . Application of solar-driven inorganic semiconductor-microbe hybrids in carbon dioxide fixation and biomanufacturing. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 35-44. doi: 10.11862/CJIC.20240364
20. [20]
  Jianjun LI , Mingjie REN , Lili ZHANG , Lingling ZENG , Huiling WANG , Xiangwu MENG . UV-assisted degradation of tetracycline hydrochloride by MnFe₂O₄@activated carbon activated persulfate. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1869-1880. doi: 10.11862/CJIC.20240187

Get Citation

PDF

XML

Metrics

PDF Downloads(1146)
Abstract views(2930)
HTML views(54)

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

Polyoxotungstate-Modified Zirconia Aerogel as a Solid Catalyst for Tetrahydrofuran Polymerization

南开大学师唯/华北电力大学（保定）刘景维：二维配位聚合物中有序的亲锂冠醚位点用于无枝晶锂沉积

Metrics

通讯作者: 陈斌, bchen63@163.com