DRIFTS and Raman Investigation of N 2 and O 2 Adsorption on Zeolites at Ambient Temperature

Abstract

Diffuse reflectance infrared fourier transform spectroscopy (DRIFTS) and Raman spectroscopy were used to examine N₂ and O₂ adsorption on cation-exchanged (K, Na, Sr, Ca, and Li) low silica X (LSX) zeolites. IR and Raman absorption bands were observed for the molecular vibration of adsorbed N₂ and O₂ at room temperature and atmospheric pressure. The intensity (in Kubelka-Munk units) of the IR band increased with N₂ pressure and mirrored the adsorption isotherm for N₂. Both O₂ and N₂ displayed a similar dependence of the molecular vibrational frequency on cation charge density, which suggests that both gases are interacting directly with the cations. The vibrational frequencies for adsorbed N₂ and O₂ were more sensitive to the cation charge density than to framework Al content. Infrared studies of N₂ and O₂ on mixed cation forms of LSX show that N₂ interaction was localized near individual cations within the sorption cavity of the zeolite. Thus, adsorbed N₂ can be used to probe accessibility of specific cations within the zeolite framework. The spectroscopic data are consistent with the theory that the stronger interaction of N₂ over O₂ is caused by the stronger influence of the electric field with the larger quadrupole of N₂.

Keywords

DRIFTS Raman Zeolites Nitrogen Oxygen Adsorption Infrared

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References

Coe

C. G.

, in Gas Separation Technology, Vansant

E. F.

and DeWolfs

, Eds. (Elsevier, Amsterdam, 1990), p. 149.

Meier

W. M.

and Olson

D. H.

, Atlas of Zeolite Structure Types (Butterworth-Heinemann, London, 1992).

Little

L. H.

, Infrared Spectra of Adsorbed Species (Academic Press, London, 1966).

Coe

C. G.

Parris

G. E.

and Srinivsan

, and Auvil

S. R.

, in New Developments in Zeolite Science Technology, Murakami

and Iljima

, and Ward

J. W.

, Eds. (Kodansha Ltd., Tokyo, 1986), p. 1033.

Parris

G. E.

, unpublished results (1981).

Bose

and Forster

, and Frede

, Chem. Phys. Lett. 138, 401 (1987).

de Lara

Cohen E.

and Delaval

, J. Chem. Soc. Faraday Trans. 2, 74, 790 (1978).

Barrachin

and de Lara

Cohen E.

, J. Chem. Soc. Faraday Trans. 2, 82, 1953 (1986).

de Lara

Cohen E.

, Molec. Phys. 66, 479 (1989).

10.

Soussen-Jacob

and Tsakiris

, and de Lara

Cohen E.

, J. Chem. Phys. 91, 2649 (1989).

11.

de Lara

Cohen E.

and Kahn

, in Guidelines for Mastering the Properties of Molecular Sieves, Bartomeuf

and Deovame

E. G

, and Holderich

, Eds. (Plenum Press, New York, 1990), p. 169.

12.

Koubi

Blain

and de Lara

Cohen E

, and Loelareq

, Chem. Phys. Lett. 217, 544 (1994).

13.

Wakabayashi

Kondo

and Domen

, and Hirose

, Cat. Lett. 21, 257 (1993).

14.

Wakabayashi

Kondo

and Domen

, and Hirose

, J. Phys. Chem. 97, 10761 (1993).

15.

Wakabayashi

Kondo

and Domen

, and Hirose

, Macroporous Materials 2, 35 (1993).

16.

Saperstein

D. D.

and Rein

A. J.

, J. Phys. Chem. 81, 2134 (1977).

17.

Griffiths

P. R.

and de Haseth

J. A.

, Fourier Transform Infrared Spectroscopy (John Wiley & Sons, New York, 1986), p. 536.

18.

Wang

H. P.

and Garland

B. A

, and Eyring

E. M.

, Appl. Spectrosc. 44, 347 (1991).

19.

Muller

J. A.

and Conner

W. C.

, J. Phys. Chem. 97, 1451 (1993).

20.

Johnson

S. A.

Rinkus

R. M.

and Diebold

T. C

, and Maroni

V. A.

, Appl. Spectrosc. 42, 1369 (1988).

21.

Khodakov

A. Y.

Kustov

L. M.

and Kaansky

V. B

, and Williams

, J. Chem. Soc. Faraday Trans. 88, 3251 (1992).

22.

Khodakov

A. Y.

Kustov

L. M.

and Kaansky

V. B

, and Williams

, J. Chem. Soc. Faraday Trans. 89, 1393 (1993).

23.

Fuller

M. P.

and Griffiths

P. R.

, Anal. Chem. 50, 1906 (1978).

24.

Fuller

M. P.

and Griffiths

P. R.

, Appl. Spectrosc. 34, 533 (1980).

25.

Kuhl

G. H.

, Zeolites 7, 451 (1987).

26.

Ward

J. W.

and Habgood

H. W.

, J. Phys. Chem. 70, 1178 (1966).

27.

Olinger

J. M.

and Griffiths

P. R.

, Appl. Spectrosc. 47, 687 (1993).

28.

ISA Instrument Corporation, private communication.

29.

Dutta

P. K.

and Zaykoski

R. E.

, Zeolites 8, 179 (1988).

30.

Nicolet Instrument Corporation, private communication.

31.

Angell

C. L.

and Schaffer

P. C.

, J. Phys. Chem. 70, 1413 (1966).

32.

Smith

J. V.

, Molecular Sieve Zeolites, Adv. Chem. Series 101 (American Chemical Society, Washington, D.C., 1971), p. 171.

33.

Forano

Slade

R. C. T.

Anderson

Krogh E.

and Anderson

Krogh I. G

, and Prince

, J. Solid State Chem. 82, 95 (1989).

34.

Shepelev

Y. F.

and Anderson

A. A

, and Smolin

Y. I.

, Zeolites 10, 61 (1990).

35.

Cheng

, unpublished results (1993).

36.

Barrer

R. M.

, J. Coll. Interface Sci. 21, 415 (1966).