Inorganic Electrides Formed by Alkali Metal Addition to Pure Silica Zeolites

Wernette, Daryl P.; Ichimura, Atsushi; Urbin, and Stephanie A.; Dye, James

doi:10.1021/cm020906z

Cited by 34 publications

(59 citation statements)

References 44 publications

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“…[40] The oxidizing power of PP 3 C + with respect to the electron-donor AlO 4 H site can be characterized by the PP 3 oxidation potential in solution. The E ox value of 1.78 V versus SCE explains the hole transfer from PP 3 C + to AlO 4 H. [41] A recent publication devoted to the photoionization of PP 3 in Li-MFI demonstrates the main implication of 27 Al, 29 Si and 7 Li nuclei in the spin distribution of electrons and holes in the zeolite framework. [22] The most striking feature of the hole is the intense color due to the prominent absorption bands in the visible range of the PP 3 ···AlO 4 HC + entity.…”

Section: Wwwchemphyschemorgmentioning

confidence: 96%

Effects of Spatial Constraints and Brønsted Acid Site Locations on para‐Terphenyl Ionization and Charge Transfer in Zeolites

et al. 2011

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The locations of Brønsted acid sites (BAS) in the channels of medium-pore zeolites have a significant effect on the spontaneous ionization of para-terphenyl (PP(3)) insofar as spatial constraints determine the stability of transition states and charge-transfer complexes relevant to charge separation. The ionization rates and ionization yield values demonstrate that a strong synergy exists between the H(+) polarization energy and spatial constraints imposed by the channel topology. Spectroscopic and modeling results show that PP(3) incorporation, charge separation, charge transfer and charge recombination differ dramatically among zeolites with respect to channel structure (H-FER, H-MFI, H-MOR) and BAS density in the channel. Compartmentalization of ejected electrons away from the initial site of ionization decreases dramatically the propensity for charge recombination. The main mode of PP(3)(.+) decay is hole transfer to form AlO(4)H(.+) ⋅⋅⋅PP(3) charge-transfer complexes characterized by intense absorption in the visible range. According to the nonadiabatic electron-transfer theory, the small reorganization energy in constrained channels explains the slow hole-transfer rate.

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Section: Wwwchemphyschemorgmentioning

confidence: 96%

Effects of Spatial Constraints and Brønsted Acid Site Locations on para‐Terphenyl Ionization and Charge Transfer in Zeolites

et al. 2011

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“…Diffuse optical reflectance spectra were collected by the Dye group for the alkali metal loaded zeolite samples and converted to apparent absorbance with the Kubelka±Munk function. [7,8] The characteristic near-IR peak at 1400 nm for Cs loaded ITQ-4 sample has been observed. Our first-principles calculation shows that this peak may contribute to the transition between bands that mainly originate from the occupied and unoccupied Cs 6s orbitals.…”

Section: Evidence For Ionization Of Cs and Delocalization Of Electronsmentioning

confidence: 91%

“…[7,8] They have tested various alkali metals and zeolites, but we will only concern the typical cesium-loaded zeoite ITQ-4 example here. ITQ-4 has a unit cell with formula Si 32 O 64 and has sinusoidal open channels with diameters of about 6.4 ä.…”

Section: Synthesis and Structurementioning

confidence: 99%

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Inorganic Electrides

Li¹,

Yang²,

Hou³

et al. 2004

Chemistry A European J

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Inorganic electrides are a novel kind of ionic compounds in which the anions are electrons confined in a complex array of cavities or channels and the cations are nanoscale arrays of alkali metal ions that provide charge balance. In electrides the donated electron behaves like a low-density correlated electron gas, whereby the dimensionality of the electron gas and its electronic and magnetic properties are determined by the topology of the cavities in the host matrix. Unlike traditional electrides, in which alkali cations are encapsulated within an organic cage, inorganic electrides are thermally stable. The current inorganic electrides based on alkali metal loaded zeolites can be designed as useful reduced-dimensionality materials. Inorganic electrides are powerful reducing agents, and they are able to reduce small aromatic molecules to the radical anions within the channels of the zeolite.

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“…[58][59][60] In these cases, the clusters of strongly reducing metals become ionized to afford metal cations and as well as electrons that flow quite freely inside the zeolite pores (electrides). [58] While vapor deposition of calcium on glass produces a metallic mirror surface that becomes immediately oxidized upon exposure to the atmosphere, such a mirror was not observed when calcium was deposited on [RuA C H T U N G T R E N N U N G (bpy) 3 ]@NaY and [RuA C H T U N G T R E N N U N G (bpy) 3 ]@CsY, which suggests that the sublimed calcium atoms have been adsorbed in the zeolite pores.…”

mentioning

confidence: 99%

Electrochemiluminescent Cells Based on Zeolite‐Encapsulated Host–Guest Systems: Encapsulated Ruthenium Tris‐bipyridyl

Álvaro

Cabeza

Fabuel

et al. 2007

Chemistry A European J

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An electrochemiluminescent cell has been developed that has an active layer consisting of ruthenium tris-bipyridyl encapsulated inside zeolite Y supercages. Operation of the cell requires the addition of polyethylene glycol as the solid electrolyte. The cell, which exhibits electrical conductivity behavior typical of a semiconductor, has an optimum operating voltage of 3 V. Ion exchange of sodium by cesium and vapor deposition of calcium metal inside the zeolite pores enhance the electrochemiluminescent efficiency of the cell by a factor of 4.

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Inorganic Electrides Formed by Alkali Metal Addition to Pure Silica Zeolites

Cited by 34 publications

References 44 publications

Effects of Spatial Constraints and Brønsted Acid Site Locations on para‐Terphenyl Ionization and Charge Transfer in Zeolites

Effects of Spatial Constraints and Brønsted Acid Site Locations on para‐Terphenyl Ionization and Charge Transfer in Zeolites

Inorganic Electrides

Electrochemiluminescent Cells Based on Zeolite‐Encapsulated Host–Guest Systems: Encapsulated Ruthenium Tris‐bipyridyl

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