Citation: LIANG Li-Ping, ZHU Qing, ZHAO Yong-Xiang, LIU Dian-Sheng. Effects of Heat Treatment on the Structure and Properties of the Tungstophosphoric Acid-Modified Zirconia Aerogel Solid Acids[J]. Acta Physico-Chimica Sinica, ;2011, 27(08): 1933-1940. doi: 10.3866/PKU.WHXB20110829 shu

Effects of Heat Treatment on the Structure and Properties of the Tungstophosphoric Acid-Modified Zirconia Aerogel Solid Acids

1.
1. Engineering Research Center for Fine Chemicals of Ministry of Education, School of Chemistry and Chemical Engineering, 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: 30 January 2011
Available Online: 24 June 2011
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)

Based on detailed experimental results, the effects of heat treatment on the structure, acidity, and catalytic performance of the 12-tungstophosphoric acid (TPA) modified zirconia aerogel (ZA) (TPZA) solid acids were investigated. TPZA samples, with TPA mass fraction of 25% and heat-treated at 120- 750 °C, were characterized by N₂ physical adsorption, X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, FTIR spectroscopy of adsorbed pyridine (Py-FTIR), and temperature programmed desorption of NH₃ (NH₃-TPD). And they were used as catalysts in the polymerization of tetrahydrofuran (THF). The results show that, although the heat treatment might greatly influence both the surface density and type of tungsten species, the TPZA materials with the TPA loading of 25% could acquire suitable Brönsted and Lewis acidity and accordingly acceptable catalytic activities over the wide temperature ranges of 120-300 °C and 550-750 °C. In the TPZA samples treated at 120-300 °C, the presence of Brönsted acid sites can be associated with the presence of highly dispersed and somewhat distorted but intact Keggin-anions, whereas the Brönsted acid sites in the samples treated at 550-750 °C might originate from the zirconia-anchored, highly polymerized tungstate surface species. Moreover, all the samples show obvious Lewis acidity, which is associated with the presence of coordinatively unsaturated Zr⁴⁺ and phosphorous oxide produced by the decomposition of TPA.
- Zirconia aerogel,
- Tungstophosphoric acid,
- Polytungstate,
- Tetrahydrofuran,
- Polymerization
References
1. [1]
  
  (1) Rafiee, E.; Joshaghani, M.; Tork, F.; Fakhri, A.; Eavani, S. J. Mol. Catal. A-Chem. 2008, 283, 1.
2. [2]
  (2) Guo,Y.; Li, K.; Yu, X.; Clark, J. H. Appl. Catal. B-Environ. 2008, 81, 182.
3. [3]
  (3) Kumbar, S. M.; Shanbhag, G. V.; Lefebvre, F.; Halligudi, S. B. J. Mol. Catal. A-Gen. 2006, 256, 324.
4. [4]
  (4) Bachiller-Baeza, B.; Anderson, J. A. J. Catal. 2004, 228, 225.
5. [5]
  (5) Yadav, G. D.; Pimparkar, K. P. J. Mol. Catal. A-Chem. 2007, 264, 179.
6. [6]
  (6) Obal?, Z.; Do?u, T. Chem. Eng. J. 2008, 138, 548.
7. [7]
  (7) Bhatt, N.; Patel, A. Catal. Lett. 2007, 113 (3-4), 99.
8. [8]
  (8) Bhatt, N.; Patel, A. J. Mol. Catal. A-Chem. 2007, 264, 214.
9. [9]
  (9) Bhatt, N.; Sharma, P.; Patel, A.; Selvam, P. Catal. Commun. 2008, 9, 1545.
10. [10]
  (10) Sharma, P.; Patel, A. Appl. Surf. Sci. 2009, 255, 7635.
11. [11]
  (11) Parida, K. M.; Mallick, S. J. Mol. Catal. A-Chem. 2007, 275, 77.
12. [12]
  (12) Parida, K. M.; Mallick, S.; Pradhan, G. C. J. Mol. Catal. AChem. 2009, 297, 93.
13. [13]
  (13) Devassy, B. M.; Halligudi, S. B. J. Catal. 2005, 236, 313.
14. [14]
  (14) Devassy, B. M.; Lefebvre, F.; Halligudi, S. B. J. Catal. 2005, 231, 1.
15. [15]
  (15) Sawant, D. P.; Vinu, A.; Jacob, N. E.; Lefebvre, F.; Halligudi, S. B. J. Catal. 2005, 235, 341.
16. [16]
  (16) Devassy, B. M.; Halligudi, S. B. J. Mol. Catal. A-Chem. 2006, 253, 8.
17. [17]
  (17) Sunita, G.; Devassy, B. M.; Vinu, A.; Sawant, D. P.; Balasubramanian, V. V.; Halligudi, S. B. Catal. Commun. 2008, 9, 696.
18. [18]
  (18) Lucas, N.; Bordoloi, A.; Amrute, A. P.; Kasinathan, P.; Vinu, A.; Bohringer,W.; Fletcher, J. C. Q.; Halligudi, S. B. Appl. Catal. A-Gen. 2009, 352, 74.
19. [19]
  (19) López-Salinas, E.; Hernández-Cortéz, J. G.; Schifter, I.; Torres- García, E.; Navarrete, J.; Gutiérrez-Carrillo, A.; López, T.; Lottici, P. P.; Bersani, D. Appl. Catal. A-Gen. 2000, 193, 215.
20. [20]
  (20) Liang, L. P.; Dang, S.;Wu, D.; Sun, Y. H. J. Mater. Sci. Technol. 2004, 20, 435.
21. [21]
  (21) Zhao, M.; Jia, Z. Q.; Zhao, L. L.; Sun, Z. J.; Liu, X.W.;Wang, P. F.; Gao, C. G. J. Mol. Catal. 2010, 24, 117. [赵敏, 贾志奇, 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.]
22. [22]
  (22) Wachs, I. E.; Kim, T.; Ross, E. I. Catal. Today 2006, 116, 162.
23. [23]
  (23) Damyanova, S.; Fierro, J. L. G.; Sobrados, I.; Sanz, J. Langmuir 1999, 15, 469.
24. [24]
  (24) Zhu, Q.; Liang, L. P.; Jia, Z. Q.; Gao, C. G.; Zhao, Y. X. Acta Phys. -Chim. Sin. 2011, 27, 491. [朱晴, 梁丽萍, 贾志奇, 高春光, 赵永祥. 物理化学学报, 2011, 27, 491.]
25. [25]
  (25) Onfroy, T.; Clet, G.; Houalla, M. J. Phys. Chem. B 2005, 109, 3345.
26. [26]
  (26) Cortés-Jácome, M. A.; Toledo, J. A.; Angeles-Chavez, C.; Aguilar, M.;Wang, J. A. J. Phys. Chem. B 2005, 109, 22730.
27. [27]
  (27) Lebarbier, V.; Clet, G.; Houalla, M. J. Phys. Chem. B 2006, 110, 13905.
28. [28]
  (28) López, D. E.; Suwannakarn, K.; Bruce, D. A.; odwin J. G. Jr., J. Catal. 2007, 247, 43.
29. [29]
  (29) Reddy, B. M.; Patil, M. K.; Reddy, G. K.; Reddy, B. T.; Rao, K. N. Appl. Catal. A-Gen. 2007, 332, 183.
30. [30]
  (30) Kozhevnikov, I. V. Catalysis by Polyoxometalates (Catalysis for Fine Chemical Synthesis); Chemical Industry Press: Beijing, 2005; pp 17-20; Translated by Tang, P. K., li, X. G.,Wang, S. R. [Kozhevnikov, I. V. 精细化学品的合成: 多酸化合物及其催化. 唐培堃, 李祥高, 王世荣, 译. 北京: 化学工业出版社, 2005: 17-20.]
31. [31]
  (31) Xia, Q. H.; Hidajat, K; Kawi, S. J. Catal. 2002, 205, 318.
1. [1]
  
  (1) Rafiee, E.; Joshaghani, M.; Tork, F.; Fakhri, A.; Eavani, S. J. Mol. Catal. A-Chem. 2008, 283, 1.
2. [2]
  (2) Guo,Y.; Li, K.; Yu, X.; Clark, J. H. Appl. Catal. B-Environ. 2008, 81, 182.
3. [3]
  (3) Kumbar, S. M.; Shanbhag, G. V.; Lefebvre, F.; Halligudi, S. B. J. Mol. Catal. A-Gen. 2006, 256, 324.
4. [4]
  (4) Bachiller-Baeza, B.; Anderson, J. A. J. Catal. 2004, 228, 225.
5. [5]
  (5) Yadav, G. D.; Pimparkar, K. P. J. Mol. Catal. A-Chem. 2007, 264, 179.
6. [6]
  (6) Obal?, Z.; Do?u, T. Chem. Eng. J. 2008, 138, 548.
7. [7]
  (7) Bhatt, N.; Patel, A. Catal. Lett. 2007, 113 (3-4), 99.
8. [8]
  (8) Bhatt, N.; Patel, A. J. Mol. Catal. A-Chem. 2007, 264, 214.
9. [9]
  (9) Bhatt, N.; Sharma, P.; Patel, A.; Selvam, P. Catal. Commun. 2008, 9, 1545.
10. [10]
  (10) Sharma, P.; Patel, A. Appl. Surf. Sci. 2009, 255, 7635.
11. [11]
  (11) Parida, K. M.; Mallick, S. J. Mol. Catal. A-Chem. 2007, 275, 77.
12. [12]
  (12) Parida, K. M.; Mallick, S.; Pradhan, G. C. J. Mol. Catal. AChem. 2009, 297, 93.
13. [13]
  (13) Devassy, B. M.; Halligudi, S. B. J. Catal. 2005, 236, 313.
14. [14]
  (14) Devassy, B. M.; Lefebvre, F.; Halligudi, S. B. J. Catal. 2005, 231, 1.
15. [15]
  (15) Sawant, D. P.; Vinu, A.; Jacob, N. E.; Lefebvre, F.; Halligudi, S. B. J. Catal. 2005, 235, 341.
16. [16]
  (16) Devassy, B. M.; Halligudi, S. B. J. Mol. Catal. A-Chem. 2006, 253, 8.
17. [17]
  (17) Sunita, G.; Devassy, B. M.; Vinu, A.; Sawant, D. P.; Balasubramanian, V. V.; Halligudi, S. B. Catal. Commun. 2008, 9, 696.
18. [18]
  (18) Lucas, N.; Bordoloi, A.; Amrute, A. P.; Kasinathan, P.; Vinu, A.; Bohringer,W.; Fletcher, J. C. Q.; Halligudi, S. B. Appl. Catal. A-Gen. 2009, 352, 74.
19. [19]
  (19) López-Salinas, E.; Hernández-Cortéz, J. G.; Schifter, I.; Torres- García, E.; Navarrete, J.; Gutiérrez-Carrillo, A.; López, T.; Lottici, P. P.; Bersani, D. Appl. Catal. A-Gen. 2000, 193, 215.
20. [20]
  (20) Liang, L. P.; Dang, S.;Wu, D.; Sun, Y. H. J. Mater. Sci. Technol. 2004, 20, 435.
21. [21]
  (21) Zhao, M.; Jia, Z. Q.; Zhao, L. L.; Sun, Z. J.; Liu, X.W.;Wang, P. F.; Gao, C. G. J. Mol. Catal. 2010, 24, 117. [赵敏, 贾志奇, 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.]
22. [22]
  (22) Wachs, I. E.; Kim, T.; Ross, E. I. Catal. Today 2006, 116, 162.
23. [23]
  (23) Damyanova, S.; Fierro, J. L. G.; Sobrados, I.; Sanz, J. Langmuir 1999, 15, 469.
24. [24]
  (24) Zhu, Q.; Liang, L. P.; Jia, Z. Q.; Gao, C. G.; Zhao, Y. X. Acta Phys. -Chim. Sin. 2011, 27, 491. [朱晴, 梁丽萍, 贾志奇, 高春光, 赵永祥. 物理化学学报, 2011, 27, 491.]
25. [25]
  (25) Onfroy, T.; Clet, G.; Houalla, M. J. Phys. Chem. B 2005, 109, 3345.
26. [26]
  (26) Cortés-Jácome, M. A.; Toledo, J. A.; Angeles-Chavez, C.; Aguilar, M.;Wang, J. A. J. Phys. Chem. B 2005, 109, 22730.
27. [27]
  (27) Lebarbier, V.; Clet, G.; Houalla, M. J. Phys. Chem. B 2006, 110, 13905.
28. [28]
  (28) López, D. E.; Suwannakarn, K.; Bruce, D. A.; odwin J. G. Jr., J. Catal. 2007, 247, 43.
29. [29]
  (29) Reddy, B. M.; Patil, M. K.; Reddy, G. K.; Reddy, B. T.; Rao, K. N. Appl. Catal. A-Gen. 2007, 332, 183.
30. [30]
  (30) Kozhevnikov, I. V. Catalysis by Polyoxometalates (Catalysis for Fine Chemical Synthesis); Chemical Industry Press: Beijing, 2005; pp 17-20; Translated by Tang, P. K., li, X. G.,Wang, S. R. [Kozhevnikov, I. V. 精细化学品的合成: 多酸化合物及其催化. 唐培堃, 李祥高, 王世荣, 译. 北京: 化学工业出版社, 2005: 17-20.]
31. [31]
  (31) Xia, Q. H.; Hidajat, K; Kawi, S. J. Catal. 2002, 205, 318.
1. [1]
  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
2. [2]
  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
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]
  Yi DING , Peiyu LIAO , Jianhua JIA , Mingliang TONG . Structure and photoluminescence modulation of silver(Ⅰ)-tetra(pyridin-4-yl)ethene metal-organic frameworks by substituted benzoates. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 141-148. doi: 10.11862/CJIC.20240393
17. [17]
  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
18. [18]
  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
19. [19]
  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
20. [20]
  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

Get Citation

PDF

XML

Metrics

PDF Downloads(973)
Abstract views(2504)
HTML views(15)

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

Effects of Heat Treatment on the Structure and Properties of the Tungstophosphoric Acid-Modified Zirconia Aerogel Solid Acids

References

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