Abstract
Adsorption isotherms of nitrogen monoxide (NO) and in situ EPR spectra of adsorbed NO on mordenite zeolites (MOR) of different cation types (HM, NaM and CaM) are measured at different temperatures to elucidate the effect of the strong adsorption promoted by the enhancement of potential field in micropore of MOR (micropore filling) as well as the electrostatic interaction in MOR on NO adsorption. The NO molecules adsorb irreversibly and fill up the micropore of MOR at 201 K, above the critical temperature of NO, regardless of the kind of cation species. The NO adsorption takes place even at 273 K. In the adsorption at 273 K, the strength of electrostatic field formed by cation sites affects the adsorptivity and the order of saturation amount of adsorption (V s) corresponds to that of the electrostatic field strength. EPR results show that NO molecules strongly interact with cation sites in MOR and disproponation reaction of NO take place on CaM.
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References
Addison,W.E. and R.M. Barrer, “Sorption and Reactivity of Nitrous Oxide and Nitric Oxide in Crystalline and Amorphous Siliceous Sorbents,” J. Chem. Soc., 1955, 757–769 (1955).
Barrer, R.M., “Specificity in Physical Sorption,” J. Colloid Interface Sci., 21, 415–434 (1966).
Barrer, R.M., Zeolites and Clay Minerals as Sorbents and Molecular Sieves, Ch. 4, Academic Press, London, 1978.
Chao, C.-C. and J.H. Lunsford, “Infrared Studies of the Disproportionation Reaction of Nitric Oxide on Y-Type Zeolites,” J. Amer. Chem. Soc., 93, 71–77 (1971a).
Chao, C.-C. and J.H. Lunsford, “Adsorption of Nitric Oxide on Y-Type Zeolites. A Low-Temperature Infrared Study,” J. Amer. Chem. Soc., 93, 6794–6801 (1971b).
Dinermann, C.E. and G.E. Ewing, “Structure of (NO)2 in the Molecular Crystal. Comment,” J. Chem. Phys., 54, 3660–3661 (1971).
Dulmage,W.J., E.A. Meyers, and W.N. Lipscomp, “The Crystal and Molecular Structure of N2O2,” Acta Cryst., 6, 760–764 (1953).
Everett, D.H. and J.C. Powl, “Adsorption in Slit-like and Cylindrical Micropores in the Henry's Law Region,” J. Chem. Soc. Faraday Trans. I, 72, 619–636 (1976).
Gardner, C.L. and M.A. Weinberger, “Electron Spin Resonance Spectra of Nitric Oxide Adsorbed on Zeolites,” Can. J. Chem., 48, 1317–1322 (1968).
Gregg, S.J. and K.S.W. Sing, Adsorption Surface Area and Porosity, Ch. 4, Academic Press, London, 1982.
Gutsze, A., M. Plato, H. Karge, and F. Witzel, “Characterization of Lewis-Acid Sites in Zeolites by EPR Using the NO Molecule as a Probe,” J. Chem. Soc. Faraday Trans., 92, 2495–2498 (1996).
Kaneko, K., “Anomalous Micropore Filling ofNOon ®-FeOOH Dispersed Activated Carbon Fibers,” Langmuir, 3, 357–363 (1987).
Kaneko, K., “Effect of Temperature on Micropore Filling of Supercritical NO on Fe2O3-Dispersed Activated Carbon Fibers,” Colloids Surf., 37, 115–124 (1989).
Kaneko, K., A.Kobayashi, A. Matsumoto, Y. Hotta, T. Suzuki, and S. Ozeki, “Enhanced Intermolecular Interaction ofNOin Cylindrical Micropores,” Chem. Phys. Lett., 163, 61–64 (1989).
Kasai, P.H., “Electron Spin Resonance Studies of Zeolites,” in Zeolite Chemistry and Catalysis, ACS Monograph 171, J.A. Rabo (Ed.), Ch. 6, American Chemical Society, Washington, 1976.
Kasai, P.H. and R.J. Bishop, Jr., “Electron Spin Resonance Study of Nitric Oxide Adsorption on Linde Type Y Zeolite,” J. Amer. Chem. Soc., 94, 5560–6666 (1972).
Kasai, P.H. and R.M. Gauro, “EPR Study of Nitric Oxide Adsorbed in Na-A Zeolite,” J. Phys. Chem., 86, 4257–4260 (1982).
Kiselev, A.V., “Non-specific and Specific Interactions of Molecules of Different Electronic Structures with Solid Surfaces,” Dis. Faraday Soc., 40, 205–231 (1965).
Lunsford, J.H., “Surface Interactions of NaY and Decationated Y Zeolites with Nitric Oxide as Determined by Electron Paramagnetic Resonance Spectroscopy,” J. Phys. Chem., 72, 4163–4168 (1968).
Meier, W.M. and D.H. Olsen, Atlas of Zeolite Structure Types, 3rd ed., p. 144, Butterworth-Heinemann, Stoneham, 1992.
Rouquerol, F., J. Rouquerol, and K.S.W. Sing, Adsorption by Powders and Porous Solids, Ch. 13, Academic Press, London, 1999.
Smith, A.L. and H.L. Johnston, “The Magnetic Susceptibility of Liquid Nitric Oxide and the Heat of Dissociation of (NO)2,” J. Amer. Chem. Soc., 74, 4696–4698 (1952).
Stoeckli, F., “The Gas-Solid Interface Calculations of Adsorption Potentials in Slot-like Pores of Molecular Dimensions,” Helv. Chim. Acta, 57, 2195–2199 (1974).
Tsutsumi, K. and H. Takahashi, “A Study of the Nature of Active Sites on Zeolites by the Measurement of Heat of Immersion. I. Electrostatic Field of Calcium-Substituted Y Zeolite,” J. Phys. Chem., 74, 2710–2713 (1970).
Tsutsumi, K. and H. Takahashi, “A Study of the Nature of Active Sites on Zeolites by the Measurement of Heat of Immersion. II. Effects of Silica/Alumina Ratio to Electrostatic-Field Strength of Calcium-Exchanged Zeolites,” J. Phys. Chem., 76, 110–172 (1972).
Uytterhoeven, J.B., L.G. Christner, and W.K. Hall, “The Decationated Zeolites,” J. Phys. Chem., 69, 2117–2126 (1965).
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Matsumoto, A., Sano, M., Nishimiya, N. et al. Adsorption Characteristics in Zeolite Nano-Pore Evaluated by use of Nitrogen Monoxide as a Probe Adsorbate. Adsorption 6, 251–257 (2000). https://doi.org/10.1023/A:1008945412770
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DOI: https://doi.org/10.1023/A:1008945412770