Lamellar polymer–Li_xMoO₃ nanocomposites via encapsulative precipitation

Abstract

With Li_xMoO₃ (x=0.31–0.40) as a host material, a new family of polymer–molybdenum bronze nanocomposites has been synthesized using an exfoliation/encapsulation methodology. Nanocomposites with poly(ethylene oxide), poly(ethylene glycol), poly(propylene glycol), poly(vinylpyrrolidinone), methyl cellulose, polyacrylamide, and nylon-6 were prepared and characterized by thermal gravimetric analysis (TGA), differential scanning calorimetry (DSC), powder X-ray diffraction, FTIR spectroscopy, UV–VIS spectroscopy, variable-temperature ⁷Li and ¹³C solid-state NMR spectroscopy and magnetic susceptibility measurements. The electrical conductivity of these materials lies in the range from 10^-2 to 10^-7 S cm^-1 , and decreases as the interlayer separation increases. The intercalated polymer imparts both mechanical strength and ease of processing to these materials. The water-soluble polymer–Li_xMoO₃ nanocomposites can be cast into films and other shapes, which may provide opportunities for applications. Factors affecting the intercalation reaction and the structure of nanocomposites, such as variations in the preparation procedure, the polymer molecular mass and the annealing behaviour of the products are discussed.

References

1. (a) Y. Fukushima and S. Inagaki, J. Inclusion Phenom., 1987, 5, 473; (b) Y. Fukushima, A. Okada, M. Kawasumi, T. Kurauchi and O. Kamigaito, Clay Miner., 1988, 23, 27; (c) A. Usuki, M. Kawasumi, Y. Kojima, A. Okada, T. Kurauchi and O. Kamigaito, J. Mater. Res., 1993, 8, 1174; (d) A. Usuki, Y. Kojima, M. Kawasumi, A. Okada, Y. Fukushima, T. Kurauchi and O. Kamigaito, J. Mater. Res., 1993, 8, 1179; (e) Y. Kojima, A. Usuki, M. Kawasumi, A. Okada, Y. Fukushima, T. Kurauchi and O. Kamigaito, J. Mater. Res., 1993, 8, 1185.
2. (a) E. P. Giannelis, Adv. Mater., 1996, 8, 29; (b) R. Krishnamoorti, R. A. Vaia and E. P. Giannelis, Chem. Mater., 1996, 8, 1728; (c) E. P. Giannelis, V. Mehrotra, O. Tse, R. A. Vaia and T.-C. Sung, Mater. Res. Soc. Symp. Proc., 1992, 267, 969; (d) R. A. Vaia, H. Ishii and E. P. Giannelis, Chem. Mater., 1993, 5, 1694; (e) R. A. Vaia, S. Vasudevan, W. Krawiec, L. G. Scanlon and E. P. Giannelis, Adv. Mater., 1995, 7, 154; (f) S. D. Burnside and E. P. Giannelis, Chem. Mater., 1995, 7, 1597; (g) R. A. Vaia, K. D. Jandt, E. J. Kramer and E. P. Giannelis, Macromolecules, 1995, 28, 8080; (h) P. B. Messersmith and E. P. Giannelis, J. Polym. Sci., Part A: Polym. Chem., 1995, 33, 1047; (i) P. B. Messersmith and E. P. Giannelis, Chem. Mater., 1993, 5, 1064; (j) 1994, 6, 1719.
3. (a) M. S. Wang and T. J. Pinnavaia, Chem. Mater., 1994, 6, 468; (b) T. Lan, P. D. Kaviratna and T. J. Pinnavaia, Chem. Mater., 1994, 6, 573; (c) T. Lan and T. J. Pinnavaia, Chem. Mater., 1994, 6, 2216; (d) H. Shi, T. Lan and T. J. Pinnavaia, Chem. Mater., 1996, 8, 1584; (e) Z. Wang, T. Lan and T. J. Pinnavaia, Chem. Mater., 1996, 8, 2200; (f) T. Lan, D. Kaviratna and T. J. Pinnavaia, J. Phys. Chem. Solids, 1996, 57, 1005.
4. (a) E. Ruiz-Hitzky and P. Aranda, Adv. Mater., 1990, 2, 545; (b) P. Aranda and E. Ruiz-Hitzky, Chem. Mater., 1992, 4, 1395.
5. M. Iwai, H. Shoji, S. Shimazu and T. Uematsu, Chem. Lett., 1993, 403.
6. T. Kyotani, T. Mori and A. Tomita, Chem. Mater., 1994, 6, 2138.
7. J. J. Tunney and C. Detellier, Chem. Mater., 1996, 8, 927.
8. J. C. Hutchison, R. Bissessur and D. F. Shriver, Chem. Mater., 1996, 8, 1597.
9. Y. Kurokawa, H. Yasuda and A. Oya, J. Mater. Sci. Lett., 1996, 15, 1481.
10. (a) M. G. Kanatzidis, L. M. Tonge, T. J. Marks, H. O. Marcy and C. R. Kannewurf, J. Am. Chem. Soc., 1987, 109, 3797; (b) M. G. Kanatzidis, H. O. Marcy, W. J. McCarthy, C. R. Kannewurf and T. J. Marks, Solid State Ionics, 1989, 32/33, 594; (c) M. G. Kanatzidis, C.-G. Wu, H. O. Marcy, D. C. DeGroot, C. R. Kannewurf, A. Kostikas and V. Papaefthymiou, Adv. Mater., 1990, 2, 364; (d) C.-G. Wu, H. O. Marcy, D. C. DeGroot, J. L. Schindler, C. R. Kannewurf, W.-Y. Leung, M. Benz, E. LeGoff and M. G. Kanatzidis, Synth. Met., 1991, 41–43, 797; (e) M. G. Kanatzidis, C.-G. Wu, D. C. DeGroot, J. L. Schindler, M. Benz, E. LeGoff and C. R. Kannewurf, in Chemical Physics of Intercalation II, ed. J. Fisher, NATO ASI Ser., Plenum, 1993, p. 63.
11. (a) Y.-J. Liu, D. C. DeGroot, J. L. Schindler, C. R. Kannewurf and M. G. Kanatzidis, Chem. Mater., 1991, 3, 992; (b) Y.-J. Liu, D. C. DeGroot, J. L. Schindler, C. R. Kannewurf and M. G. Kanatzidis, Adv. Mater., 1993, 5, 369; (c) Y.-J. Liu, J. L. Schindler, D. C. DeGroot, C. R. Kannewurf, W. Hirpo and M. G. Kanatzidis, Chem. Mater., 1996, 8, 525; (d) C.-G. Wu, M. G. Kanatzidis, H. O. Marcy, D. C. DeGroot and C. R. Kannewurf, in Lower-Dimensional Systems and Molecular Electronics, ed. R. M. Metzger, et al., Plenum, New York, 1991, p. 427; (e) Y.-J. Liu, D. C. DeGroot, J. L. Schindler, C. R. Kannewurf and M. G. Kanatzidis, J. Chem. Soc., Chem. Commun., 1993, 593; (f) C.-G. Wu, D. C. DeGroot, H. O. Marcy, J. L. Schindler, C. R. Kannewurf, Y.-J. Liu, W. Hirpo and M. G. Kanatzidis, Chem. Mater., 1996, 8, 1992.
12. G. M. Kloster, J. A. Thomas, P. W. Brazis, C. R. Kannewurf and D. F. Shriver, Chem. Mater., 1996, 8, 2418.
13. F. Leroux, B. E. Koene and L. F. Nazar, J. Electrochem. Soc., 1996, 143, L181.
14. (a) L. F. Nazar, X. T. Yin, D. Zinkweg, Z. Zhang and S. Liblong, Mater. Res. Soc. Symp. Proc., 1991, 210, 417; (b) L. F. Nazar, Z. Zhang and D. Zinkweg, J. Am. Chem. Soc., 1992, 114, 6239; (c) L. F. Nazar, H. Wu and W. P. Power, J. Mater. Chem., 1995, 5, 1985; (d) T. A. Kerr, H. Wu and L. F. Nazar, Chem. Mater., 1996, 8, 2005.
15. R. Bissessur, D. C. DeGroot, J. L. Schindler, C. R. Kannewurf and M. G. Kanatzidis, J. Chem. Soc., Chem. Commun., 1993, 687.
16. G. Cao and T. E. Mallouk, J. Solid State Chem., 1991, 94, 59.
17. J. E. Pillion and M. E. Thompson, Chem. Mater., 1991, 3, 777.
18. A. Clearfield and C. Y. Ortiz-Avila, in ACS Symposium 499: Supramolecular Architecture, ed. T. Bein, American Chemical Society, 1992, p. 178.
19. Y.-J. Liu and M. G. Kanatzidis, Inorg. Chem., 1993, 32, 2989.
20. Y. Ding, D. J. Jones, P. Maireles-Torres and J. Rozière, Chem. Mater., 1995, 7, 562.
21. W. M. R. Divigalpitiya, R. F. Frindt and S. R. Morrison, J. Mater. Res., 1991, 6, 1103.
22. (a) M. G. Kanatzidis, R. Bissessur, D. C. DeGroot, J. L. Schindler and C. R. Kannewurf, Chem. Mater., 1993, 5, 595; (b) R. Bissessur, M. G. Kanatzidis, J. L. Schindler and C. R. Kannewurf, J. Chem. Soc., Chem. Commun., 1993, 1582; (c) R. Bissessur, J. L. Schindler, C. R. Kannewurf and M. G. Kanatzidis, Mol. Cryst. Liq. Cryst., 1993, 245, 249; (d) L. Wang, J. L. Schindler, J. A. Thomas, C. R. Kannewurf and M. G. Kanatzidis, Chem. Mater., 1995, 7, 1753.
23. J. P. Lemmon and M. M. Lerner, Chem. Mater., 1994, 6, 207.
24. E. Ruiz-Hitzky, R. Jimenez, B. Casal, V. Manriquez, A. S. Ana and G. Gonzalez, Adv. Mater., 1993, 5, 738.
25. I. Lagadic, A. Léaustic and R. Clément, J. Chem. Soc., Chem. Commun., 1992, 1396.
26. C. O. Oriakhi and M. M. Lerner, Chem. Mater., 1996, 8, 2016.
27. P. G. Hill, P. J. S. Foot and R. Davis, Synth. Met., 1996, 76, 289.
28. P. B. Messersmith and S. I. Stupp, Chem. Mater., 1995, 7, 454.
29. H.-L. Tsai, J. Heising, J. L. Schindler, C. R. Kannewurf and M. G. Kanatzidis, to be published.
30. N. Margalit, J. Electrochem. Soc., 1974, 121, 1460.
31. J. Desilvestro and O. Haas, J. Electrochem. Soc., 1990, 137, 5C.
32. M. G. Kanatzidis and T. J. Marks, Inorg. Chem., 1987, 26, 783.
33. (a) B. N. Diel, T. Inabe, J. W. Lyding, K. F. Schock Jr., C. R. Kannewurf and T. J. Marks, J. Am. Chem. Soc., 1983, 105, 1551; (b) J. W. Lyding, H. O. Marcy, T. J. Mark and C. R. Kannewurf, IEEE Trans. Instrum. Meas., 1988, 37, 76.
34. D. M. Thomas and E. M. McCarron III, Mater. Res. Bull., 1986, 21, 945.
35. D. M. Moore and R. C. Reynolds Jr., X-Ray Diffraction and the Identification and Analysis of Clay Minerals, Oxford University Press, Oxford and New York, 1989, p. 83.
36. L. Wang and M. G. Kanatzidis, unpublished work.
37. L. Wang and M. G. Kanatzidis, work in progress.
38. S. Colson, J. M. Tarascon, S. Szu and L. C. Klein, Mater. Res. Soc. Symp. Proc., 1991, 210, 405.
39. J. M. Tarascon and S. Colson, Mater. Res. Soc. Symp. Proc., 1989, 135, 421.
40. Y. Matsuda, M. Sato, M. Onoda and K. Nakao, J. Phys. C: Solid State Phys., 1986, 19, 6039.
41. M. Greenblatt, in Low-Dimensional Electronic Properties of Molybdenum Bronzes and Oxides, ed. C. Schlenker, Kluwer Academic, Dordrecht, Boston, London, 1989.
42. L. F. Schneemeyer, F. J. DiSalvo, R. M. Fleming and J. V. Waszczak, J. Solid State Chem., 1984, 54, 358.
43. G. H. Bouchard Jr., J. Perlstein and M. J. Sienko, Inorg. Chem., 1967, 6, 1682.
44. D. C. Johnston, Phys. Rev. Lett., 1984, 52, 2049.
45. C. Julien and G. A. Nazri, Solid State Ionics, 1994, 68, 111.
46. J. O. Besenhard, J. Heydecke, E. Wudy and H. P. Fritz, Solid State Ionics, 1983, 8, 61.