Preparation of size-quantized indium phosphide in zeolite cages

Uchida, Hiroyuki; Ogata, Tomoyuki; Yoneyama, Hiroshi

doi:10.1016/0009-2614(90)85311-y

Cited by 24 publications

(43 citation statements)

References 12 publications

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“…However, the In(6)-In(2) distance (2.759(3) and 2.754(5) Å for crystals 1 and 2, respectively) is reasonable, comparable to 2.70 Å, the sum of the atomic radius of In 0 and the ionic radius of In 2+ (1.03 Å). The association of In 0 at In (6) with In(2) supports the rather longer approach distances of In 2+ at In(2) to the six-ring oxygens, due to the reduced cationic character of In 2+ . These reasonable distances between In 0 and In 2+ indicate that clusters such as (In 2 ) 2+ , (In 3 ) 4+ (linear or bent), (In 4 ) 6+ , or (In 5 ) 8+ (four In 2+ ions tetrahedrally arranged in the sodalite unit with an In 0 at their center) exist.…”

Section: Indium Atoms and Clustersmentioning

confidence: 67%

Reaction of Fully Indium-Exchanged Zeolite A with Hydrogen Sulfide. Crystal Structures of Indium-Exchanged Zeolite A Containing In₂S, InSH, Sorbed H₂S, and (In₅)⁷⁺

et al. 2002

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Four single crystals of fully dehydrated, fully indium-exchanged zeolite A (Inca. 10−Si12Al12O48 or Inca. 10-A, colorless) were exposed to 0.5 atm of H2S for 3 h at 298, 373, 423, and 573 K for crystals 1 to 4, respectively. After evacuation at temperature followed by cooling to 294(2) K, the crystals were red, brown, yellow, and yellow, respectively. Their structures were determined by single-crystal X-ray diffraction techniques in the cubic space group Pm3̄m at 294(2) K (a = 12.083(3), 12.076(2), 12.094(2), and 12.094(2) Å; R1 = 0.069, 0.063, 0.065, and 0.060; R2 = 0.062, 0.058, 0.064, and 0.060 for crystals 1 to 4, respectively). The structures differ in the degree of sorption and/or reaction with H2S. Crystal 1 (In9.5H0.5−A(InSH)0.5(H2S)2.5) may be viewed as being an equimolar mixture of two kinds of unit cells with compositions In9−A(H2S)3 and In10H−A(InSH)(H2S)2. Unit cell 1 contains three H2S molecules stabilized as [(In)2(H2S)3]2+ in the large cavity and a tetrahedral (In5) n + cluster in the sodalite unit. Unit cell 2 contains unreacted (In3)2+ and an [(In)2(InSH)(H2S)2]2+ cluster with one InSH and two sorbed H2S molecules, all in its large cavity. Crystal 2 (In8.4H1.2−A(In2S)0.6(H2S)2) may similarly be viewed as being 40% In9−A(H2S)2 and 60% In8H2−A(In2S)(H2S)2. In9−A(H2S)2 has two sorbed H2S molecules in a [(In)2(H2S)2]2+ cluster, whereas In8H2−A(In2S)(H2S)2 has a [(In)2(In2S)(H2S)2]2+ cluster with one In2S and two sorbed H2S molecules in the large cavity. At higher reaction temperatures (423 and 573 K), the product crystals had less InHS and sorbed H2S. All crystals contain tetrahedral (In5) n + where n is likely to be 7. The number of sorbed H2S molecules decreases monotonically with increasing reaction temperature. In2S and InSH molecules were observed only in the large cavities, where more monopositive indium cations were initially available.

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Section: Indium Atoms and Clustersmentioning

confidence: 67%

Reaction of Fully Indium-Exchanged Zeolite A with Hydrogen Sulfide. Crystal Structures of Indium-Exchanged Zeolite A Containing In₂S, InSH, Sorbed H₂S, and (In₅)⁷⁺

et al. 2002

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“…Full-matrix least-squares refinements (SHELXL97) 47 Introducing In(U) as In 0 atoms at a peak (0.125,0.125,0.125) from a difference Fourier function reduced R 1 to 0.46 with resulting occupancies of 22.8(2) and 4.6(5) at In(II) and In(U), respectively. Adding In(I′) isotropically as In 2+ at another peak (0.063,0.063,0.063) found in a subsequent difference function converged with R 1 sharply reduced to 0.063 with resulting occupancies of 25.9(4), 8.0(1), and 32.4(4) at In(II), In(U), and In(I′), respectively. Including In(IIa) isotropically as In 2+ at a peak (0.23,0.23,0.23) found in a difference function based on this model converged and further reduced R 1 to 0.062 with occupancies of 25.0(4), 7.9(1), 31.7(3), and 0.8(2) at In(II), In(U), In(I′), and In(IIa), respectively.…”

Section: Methodsmentioning

confidence: 89%

“…Including In(IIa) isotropically as In 2+ at a peak (0.23,0.23,0.23) found in a difference function based on this model converged and further reduced R 1 to 0.062 with occupancies of 25.0(4), 7.9(1), 31.7(3), and 0.8(2) at In(II), In(U), In(I′), and In(IIa), respectively. All In positions were refined anisotropically in the final cycles of refinement with occupancies fixed at 25,8,32, and 1 at In(II), In(U), In(I′), and In(IIa), respectively. This converged to the final error index R 1 ) 0.058.…”

Section: Methodsmentioning

confidence: 99%

Spatially Ordered Quantum Dot Array of Indium Nanoclusters in Fully Indium-Exchanged Zeolite X

et al. 2003

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A spatially ordered quantum dot array of cationic indium nanoclusters has been synthesized in a single crystal of zeolite X. A single crystal of fully dehydrated and fully indium-exchanged zeolite X (ca. In 87 Si 100 Al 92 O 384 , In 87 -X) was exposed to 0.5 atm of H 2 S for 12 h at 673 K. After it was evacuated at temperature and cooled to 294 K, the crystal structure of the product (ca. In 66 Si 100 Al 92 O 384 , In 66 -X, a ) 24.942(4) Å) was determined by single crystal X-ray diffraction techniques in the cubic space group Fd3 hm. It was refined with all measured reflections to the final error index R 1 ) 0.058 for the 754 reflections with F o > 4σ(F o ). X-ray photoelectron spectroscopy experiments confirmed the existence of both atomic and cationic indiums inside the single crystal. The 66 indium atoms or ions per unit cell were found at four crystallographically distinct positions, all on 3-fold axes. Eight In atoms at the sodalite unit centers and 32 In ca.2+ ions nearby (In ca.2+ -In 0 ) 2.683(1) Å), both filling their crystallographic sites, form eight (In 5 ) n+ (n ) 7 satisfies Lewis's rule) per unit cell, one per sodalite cavity. Each (In 5 ) n+ quantum dot (diameter ca. 7.0 Å) is held in place by 12 strong electrostatic interactions with six ring oxygens (In ca.2+ -O(3) ) 2.170(7) Å). These quantum dots are arranged in the diamond structure with intercluster distances of ca. 10.8 Å. This crystal (cross-section ca. 0.15 mm) contains ca. 300 Tera (10 12 ) ordered dots of (In 5 ) n+ . Another 25 In + ions per unit cell were located at a 32-fold site in the supercage, and a single In 2+ ion was found nearby. Treatment with H 2 S has allowed In + ions to disproportionate to give full occupancy at the (In 5 ) n+ site.

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“…Conventional aqueous ion exchange using In(NO 3 ) 3 has been used to introduce the In 3+ into the ammonium forms of ZSM-5 [15,16] and mordenite [17]. This could not be extended to zeolites with higher Al contents because of the loss of crystallinity that occurs at the low pH values required to keep In 3+ in solution [18,19].…”

Section: Vapor Phase Ion Exchange (Vpie)mentioning

confidence: 99%

Using InCl vapor to ion exchange indium into zeolite Na–X. II: A single crystal structure containing (In8Cl8)16+, In57+–Cl−–In57+, and In+

Sen

Kim

Kang

et al. 2013

Microporous and Mesoporous Materials

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Preparation of size-quantized indium phosphide in zeolite cages

Cited by 24 publications

References 12 publications

Reaction of Fully Indium-Exchanged Zeolite A with Hydrogen Sulfide. Crystal Structures of Indium-Exchanged Zeolite A Containing In₂S, InSH, Sorbed H₂S, and (In₅)⁷⁺

Reaction of Fully Indium-Exchanged Zeolite A with Hydrogen Sulfide. Crystal Structures of Indium-Exchanged Zeolite A Containing In₂S, InSH, Sorbed H₂S, and (In₅)⁷⁺

Spatially Ordered Quantum Dot Array of Indium Nanoclusters in Fully Indium-Exchanged Zeolite X

Using InCl vapor to ion exchange indium into zeolite Na–X. II: A single crystal structure containing (In8Cl8)16+, In57+–Cl−–In57+, and In+

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Preparation of size-quantized indium phosphide in zeolite cages

Cited by 24 publications

References 12 publications

Reaction of Fully Indium-Exchanged Zeolite A with Hydrogen Sulfide. Crystal Structures of Indium-Exchanged Zeolite A Containing In2S, InSH, Sorbed H2S, and (In5)7+

Reaction of Fully Indium-Exchanged Zeolite A with Hydrogen Sulfide. Crystal Structures of Indium-Exchanged Zeolite A Containing In2S, InSH, Sorbed H2S, and (In5)7+

Spatially Ordered Quantum Dot Array of Indium Nanoclusters in Fully Indium-Exchanged Zeolite X

Using InCl vapor to ion exchange indium into zeolite Na–X. II: A single crystal structure containing (In8Cl8)16+, In57+–Cl−–In57+, and In+

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Reaction of Fully Indium-Exchanged Zeolite A with Hydrogen Sulfide. Crystal Structures of Indium-Exchanged Zeolite A Containing In₂S, InSH, Sorbed H₂S, and (In₅)⁷⁺

Reaction of Fully Indium-Exchanged Zeolite A with Hydrogen Sulfide. Crystal Structures of Indium-Exchanged Zeolite A Containing In₂S, InSH, Sorbed H₂S, and (In₅)⁷⁺