Electron spin resonance study of nitric oxide adsorption on Linde Type Y zeolites

Kasai, Paul H.; Bishop, R.J.

doi:10.1021/ja00771a005

Cited by 88 publications

(58 citation statements)

References 4 publications

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“…Even though NO has an unpaired electron, it usually exhibits no paramagnetism in the ground state, 30 since the odd electron is localized in a degenerate π* antibonding orbital. Therefore, no ESR signal is observed for gaseous NO molecules.…”

Section: Discussionmentioning

confidence: 99%

“…They are intersected by another eight-membered channel (C) that runs along the a-axis. 1 The chemical formula for clinoptilolite is (Na,K) 6 [Al 6 Si 30 O 72 ]‚24H 2 O. 3 The negative charge of the clinoptilolite framework from tetrahedrally coordinated aluminum is balanced by Na and K. These cations can be exchanged to some extent by transition metal ions.…”

Section: Introductionmentioning

confidence: 99%

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Electron Spin Resonance and Electron Spin Echo Modulation Studies on the Formation and Adsorbate Interactions of Ni(Ι) in Synthetic Clinoptilolite

et al. 1999

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Electron spin resonance (ESR) and electron spin echo modulation (ESEM) spectroscopies were used to study the formation of Ni(Ι) by various reduction methods and various adsorbate interactions of Ni(Ι) in synthetic clinoptilolite, in which Ni(ΙΙ) was ion-exchanged into extraframework sites of clinoptilolite. Thermal reduction by dehydration at 573 K shows a single species assigned to Ni(Ι) ions. Two isolated Ni(Ι) ions are observed after hydrogen reduction at 623 K. Adsorption of methanol on hydrogen-reduced NiNaK-Clino forms a Ni(Ι)-(CD 3 OH) n complex resulting from the interaction of methanol with one of the isolated Ni(Ι) ions. Adsorption of ammonia on hydrogen-reduced NiNaK-Clino produces a prominent Ni(Ι)-(ND 3 ) n complex by interaction with both Ni(Ι) ions. The 13 C hyperfine structure and ESEM analysis parameters after 13 CO adsorption indicate that Ni(Ι) interacts with one CO molecule and forms a Ni(Ι)-(CO) 1 complex. Two Ni-(Ι)-(C 2 D 4 ) n complexes are generated after adsorption of ethylene on dehydrated Ni(II)NaK-Clino and subsequent heating below 623 K. At higher temperature, these species disappear with the concomitant formation of two Ni(Ι)-(C 4 D 8 ) n complexes, indicating ethylene dimerization. 2 D ESEM confirms the coordination of Ni(Ι) with butene. Adsorption of NO on dehydrated Ni(II)NaK-Clino produces two Ni(Ι)-NO + complexes formed by transfer of the odd electron from NO to Ni(ΙΙ) ions. Along with two Ni(Ι)-NO + species, another species assigned to the NO radical is also observed in NiNaK-Clino after NO adsorption on Ni(II)NaKClino and NaK-Clino.

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Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Electron Spin Resonance and Electron Spin Echo Modulation Studies on the Formation and Adsorbate Interactions of Ni(Ι) in Synthetic Clinoptilolite

et al. 1999

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“…Electron spin resonance (ESR) is a well established technique to investigate the structure of the adsorption complexes with NO, in previous studies mainly by measuring the anisotropic g-factors, which are affected by the interaction with the surface. These studies are well documented in the literature [22][23][24][25]. The interaction between surface sites and the adsorbed NO is usually quite weak, however, so that the structure of the adsorption complex is only indirectly revealed by CW (continuous-wave) ESR.…”

Section: Introductionmentioning

confidence: 83%

Structure and dynamics of radicals in zeolite matrices: ESR and theoretical studies

et al. 2003

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Amine radical cations of the type R3N "+ and [R3NCH2] "+, R = CH3, C2H5, C3H7, and nitric oxide, NO, have been used to probe the bonding to the surface and the dynamics of the radicals trapped in the confined space of cages or channels in the zeolite. Regular continuous-wave electron spin resonance (ESR) was employed to study the internal motion of the cation radicals formed by ~/-irradiation of amines and related ammonium ions, introduced during the synthesis of the zeolites A1-offretite, SAPO-37, SAPO-42 and AIPO4-5. The ESR spectra of [(CH3)3NCH2] " § radical cation in several studied systems changed reversibly with temperature, indicating dynamical effects. Free rotation about the >N-CH 2 bond of the [(CH3)3NCH2] "+ species was found to occur in the temperature range of 110 to 300 K, while the rotation about the >N-CH 3 bonds was hindered. The observations contima the theoretical prediction on the basis of density functional theory calculations, which indicate that the corresponding barriers ate of the order of 0.3 and 7 kJ/mol, respectively. The radical cations of the type R3N "+ with R = C:H 5, C3H 7 were found to undergo a different type of dynamics, involving a two-jump process of the methylene hydrogens next to the nitrogen. A cage or channel size effect on the stability and molecular dynamics was inferred in some cases. Pulsed ESR was employed to study the (NO)2 triplet-state dimers in Na-A type zeolite, with the purpose to resolve the interaction with surface groups, and to elucidate the role of the zeolite on stabilizing the triplet rather than the usual singlet state. Measurements performed at 5 K gave rise to Fourier transform spectra that were assigned to the dimer species interacting with one or more '3Na nuclei, with approximative parameters A(23Na) = (4.6, 4.6, 8.2) MHz and Q(Z3Na) = (-0.3, -0.3, 0.6) MHz for the hyperfine and nuclear quadrupote coupling tensors, respectively. The values are of similar magnitude as those determined for the NO---Na + complex. The stability of the triplet-state structure was attributed to an unusual geometric structure imposed by the zeolite matrix, with the N-O bonds along a line as in [O-N---Na+---N-O], which according to UHF ab initio calculations has a triplet ground state. 286W. Liu et al.

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“…Naccache et al [36,37] and Kasai et al [38][39][40] reported that Ni(II) and Cu(II) in Y zeolite were reduced by NO to form Ni(I)-NO+ and Cu(I)-NO+, and that the resulting complexes were stabilized within the zeolite cavities [36,39]. The ESR line at g ii = 2.33 and gl = 2.17 after NO adsorption onto Ni(II) in Y zeolite was assigned to Ni(I)-NO + [37].…”

Section: Coordination and Valence State Of Co In Dehydrated Co-zsm-5 mentioning

confidence: 99%

Electron spin resonance and optical spectroscopic studies of Co-ZSM-5 with nitric oxide

et al. 2000

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The reaction of nitric oxide with ZSM-5 zeolite ion-exchanged by Co(II) (Co-ZSM-5) has been studied by electron spin resonance (ESR), Fourier transform infrared (FTIR) and diffuse reflectance ultraviolet-visible spectroscopy. When dehydrated Co-ZSM-5 reacts at room temperature with nitric oxide, the ESR spectrum of Co(II) at g = 5.5, which is only observable below 45 K, is greatly reduced and a new 59 Co hyperfine octet forms at g,,g = 2.11. The overall Co(II) ESR intensity decreases by about 50% which suggests formation of some diamagnetic cobalt complex. Mononitrosyl cobalt complexes such as Co(I)-NO or less probably Co(III)-(NO) -are suggested as possible precursors of a dintrosyl cobalt complex. The octet indicates hyperfine interaction with "Co and is associated with a cobalt dinitrosyl complex. FTIR bands at 1813 and 1896 cm -' confirm a dinitrosyl species and a broad band from 1600-1800 cm -' is tentatively interpreted as a mononitrosyl species. The visible spectrum for dehydrated Co-ZSM-5 shows a tetrahedral Co(II) band from 500-700 nm with three components which disappears after NO adsorption at room temperature. We suggest that Co(0)-(NO)2 + forms after NO adsorption onto Co(II)-ZSM-5 zeolite on the basis of ESR and ultraviolet-visible spectroscopy.

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Electron spin resonance study of nitric oxide adsorption on Linde Type Y zeolites

Cited by 88 publications

References 4 publications

Electron Spin Resonance and Electron Spin Echo Modulation Studies on the Formation and Adsorbate Interactions of Ni(Ι) in Synthetic Clinoptilolite

Electron Spin Resonance and Electron Spin Echo Modulation Studies on the Formation and Adsorbate Interactions of Ni(Ι) in Synthetic Clinoptilolite

Structure and dynamics of radicals in zeolite matrices: ESR and theoretical studies

Electron spin resonance and optical spectroscopic studies of Co-ZSM-5 with nitric oxide

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