Abstract
Hexagonal mesoporous silicate (HMS) molecular sieve containing zirconium species (Zr-HMS) has been synthesized using a neutral template of hexadecylamine with ethanol and water. A disordered channel structure with a uniform diameter of 44.1 Å was confirmed by powder X-ray diffraction after calcination. From N2 adsorption/desorption measurement, it is found that Zr-HMS has a very high surface area of about 910 m2/g (BET) and a mesopore with a size of 21 Å (BJH). According to the X-ray absorption spectroscopy at the Zr K-edge, it is confirmed that Zr atoms are coordinated by six oxygen neighbors with a distance of 2.13 Å, which is shorter than the (Zr—O) bond distance found in ZrO2 or ZrOCl2·8H2O. The 29Si MAS-NMR spectrum for Zr-HMS shows two additional peaks around −94.6 and −107.2 ppm due to the Q3Zr and Q4Zr components, respectively, besides three peaks at −91.1, −101.5, and −111.3 ppm due to the silicate network. The relation between the pore and crystal structures and the local environment around Zr is discussed in detail.
Similar content being viewed by others
References
C.T. Kresge, M.E. Leonowicz, W.J. Roth, J.C. Vartuli, and J.S. Beck, Nature 359, 710 (1992).
J.S. Beck, J.C. Vartuli, W.J. Roth, M.E. Leonowicz, C.T. Kresge, K.D. Schmitt, C.T.-W. Chu, D.H. Olson, E.W. SHEPPARD, S.B. McCullen, J.B. Higgins, and J.L. Schlenker, J. Am. Chem. Soc. 114, 10834 (1992).
Q. Huo, D.I. Margolese, U. Ciesla, P. Feng, T.E. Gier, P. Sieger, R. Leon, P.M. Petroff, F. Sch¨uth, and G.D. Stucky, Nature 368, 317 (1994).
M.J. Hudson and J.A. Knowles, J. Mater. Chem. 6, 89 (1996).
T. Sun and J.Y. Ying, Nature 389, 704 (1997).
C. Saúl, E.H. Jamel, B.P. Aurelio, B.P. Daniel, M.M. Dolores, and A. Pedro, Solid State Science 2, 513 (2000).
U. Ciesla, D. Demuth, R. Leon, P. Petroff, G. Stucky, K. Unger, and F. Schuth, J. Chem. Soc. Commun. 20, 2083 (1995).
F.L. Chen and M.L. Liu, Chem. Commun. 18, 1829 (1999).
R. Mokaya and W. Jones, J. Chem. Soc., Chem. Commun. 981 (1996).
Z. Zhang, Y. Han, F.S. Xiao, S. Qiu, L. Zhu, R. Wang, Y. Yu, Z. Zhang, B. Zou, Y. Wang, H. Sun, D. Zhao, and Y. Wei, J. Am. Chem. Soc. 123, 5014 (2001).
P.T. Tanev, M. Chibwe, and T.J. Pinnavaia, Nature 368, 321 (1994).
D.J. Jones, J.J. Jimenez, A.J. Lopez, P.M. Torres, and P.O. Pastor, Chem. Commun. 431 (1997).
M.L. Occelli, S. Biz, and A. Auroux, Appl. Catal. A 183, 231 (1999).
J.H. Choy, D.K. Kim, J.C. Park, S.N. Choi, and Y.J. Kim, Inorg. Chem. 36, 189 (1997).
A. Mosset and J. Galy, in Synchrotron Radiation in Chemistry and Biology (Springer-Verlag, Berlin, 1988).
J.H. Choy, J.H. Park, and J.B. Yoon, J. Phys. Chem. 102, 5991 (1998).
P.T. Tanev and T.J. Pinnavaia, Science 267, 865 (1995).
J.A. Bearden and A.F. Burr, Rev. Modern Physics. 39, 125 (1967).
M. Nomura and A. Koyama, KEK Internal 93(1) (1993).
B.K. Teo, Basic Principle of EXAFS (Springer-Verlag, Berlin, 1986).
E.A. Stern, M. Newville, B. Ravel, Y. Yacoby, and D. Haskel, Physica B 208/209, 117 (1995).
J.J. Rehr, J. Mustre de leon, S.I. Zabinsky, and R.C. Albers, J. Am. Chem. Soc. 113, 5135 (1991).
P.A. O'day, J.J. Rehr, S.I. Zabinsky, and G.E. Brown Jr., J. Am. Chem. Soc. 116, 2938 (1994).
S.A. Bagshaw, E. Prouzet, and T.J. Pinnavaia, Science 269, 1242 (1995).
A. Tuel and S. Gontier, Chem. Mater. 8, 114 (1996).
E.P. Barrett, L.G. Joyner, and P.P. Halenda, J. Am. Chem. Soc. 73, 373 (1951).
J.B. Yoon, Ph. D. Thesis, Seoul National Univ., Seoul, Aug. 1998.
C.J. Howard, R.J. Hill, and B.E. Reichert, Acta Crystallogr. B44, 116 (1988).
A. Clearfield and P. A. Vaugham, Acta Crystallogr. 9, 555 (1956).
R.D. Shannon, Acta Crystallogr. A32, 751 (1976).
W. Zhang, M. Froba, J. Wang, P.T. Tanev, J. Wong, and T.J. Pinnavaia, J. Am. Chem. Soc. 118, 9164 (1996).
M. Lipsicas, R.H. Raythatha, T.J. Pinnavaia, I.D. Johnson, R.F. Giese Jr., P.M. Costanzo, and J.L. Robert, Nature 309, 604 (1984).
Z.Y. Yuan, S.Q. Liu, T.H. Chen, J.Z. Wang, and H.X. Li, J. Chem. Soc. Commun. 9, 973 (1995).
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Choy, JH., Yoon, JB., Jung, H. et al. Zr K-Edge XAS and 29Si MAS NMR Studies on Hexagonal Mesoporous Zirconium Silicate. Journal of Porous Materials 11, 123–129 (2004). https://doi.org/10.1023/B:JOPO.0000038007.82949.e1
Issue Date:
DOI: https://doi.org/10.1023/B:JOPO.0000038007.82949.e1