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
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