Near-zero-coordinate thallium(I). The crystal structures of hydrated and dehydrated zeolite A fully exchanged with thallium hydroxide

Firor, Roger L.; Seff, Karl

doi:10.1021/ja00454a023

Cited by 42 publications

(52 citation statements)

References 6 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…They can be the precursors for the formation of various hydroxide or oxide clusters which may evolve further upon heating and/or vacuum dehydration. This has been seen when Tl + , 46 Cd 2+ , 47 and Pb 2+ 48-50 were exchanged into zeolite A (LTA), Cd 2+ into zeolite Y (FAU), 38 and Co 2+ , 23 Table 7), while those at Ni2′ in crystal 4 are trigonal bipyramidal. The values of x in the Ni 8 O 4 · xH 2 O 8+ clusters (see Table 7) are about 4.0, their maximum possible value, for crystals 1 and 2 which were dehydrated at the lower temperature (623 K).…”

Section: +mentioning

confidence: 97%

Crystal Structures of Vacuum-Dehydrated Ni²⁺-Exchanged Zeolite Y (FAU, Si/Al = 1.69) Containing Three-Coordinate Ni²⁺, Ni₈O₄·xH₂O⁸⁺, x ≤ 4, Clusters with Near Cubic Ni₄O₄ Cores, and H⁺

Kim¹,

Jung²,

Heo³

et al. 2009

J. Phys. Chem. C

Self Cite

View full text Add to dashboard Cite

Five single crystals of vacuum-dehydrated Ni 2+ -exchanged zeolite Y (Ni-Y) were variously prepared by the exchange of Na-Y or K-Y (Na 71 -or K 71 -Si 121 Al 71 O 384 , Si/Al ) 1.69) with Ni 2+ using flowing aqueous 0.05 M Ni(NO 3 ) 2 at 294 or 353 K, followed by vacuum dehydration at 2.0 × 10 -6 Torr and 623 or 723 K. Their crystal structures and chemical compositions were determined using synchrotron X-radiation and energy dispersive X-ray (EDX) analyses to give Ni n -Y, where 25.3 e n e 34.1 per unit cell:121+z Al 71-z O 384 ]-FAU, where 21.4 e u e 24.2, M ) Na and/or Ca, 3.3 e V e 13.1, 9.5 e w e 21.6, 2 e x e 4, 0.3 e y e 3.2, and 0 e z e 2.5. In each of the five crystal structures (space group Fd3 j m; mean a ) 24.47 Å), Ni 2+ is found at sites I, I′, a second I′, II′, and sometimes II; unexpectedly, Na + and Ca 2+ are found at another site II. Two extra-framework oxygen positions (O e ), one in the sodalite cavity and the other nearby in the supercage, are seen on 3-fold axes in all crystals. They bond to Al 3+ and Ni 2+ ions in the sodalite cavities to form Al(O e H) 4 -and Ni 8 (O e ) 4 · xH 2 O e 8+ clusters with Ni 4 (O e ) 4 cores, and with framework oxygens (O f ) to give trigonal bipyramidal Ni(O f ) 3 (O e ) 2 2+ and trigonal pyramidal Ni(O f ) 3 O e 2+ . At site I (centers of double 6-rings) in the Na-Y crystal that was Ni 2+ -exchanged at 294 K, ∼14 Ni 2+ ions per unit cell each coordinate octahedrally to six framework oxygen atoms. The Ni 2+ ions at the first I′ site are 3-coordinate near planar in all crystals. The Ni 2+ ions at the second I′ site are members of the Ni 4 O 4 cores, tetrahedrally distorted cubes with Ni-O ) 2.199(13) Å and O-Ni-O ) 79.6(9)°in a representative crystal; these Ni 2+ ions are distorted octahedral with three O e 's of the cluster and three O f 's. The Ni 2+ ions at sites II′ and II are 3-, 4-, or 5-coordinate. Al(OH) 4-from framework dealumination centers some sodalite cavities in four of the five crystals; their number increased with both ion-exchange and dehydration temperatures, suggesting that dealumination occurred during both processes. The number of Ni 2+ ions per unit cell increases with Ni 2+ -exchange temperature and is greater with K-Y than with Na-Y, perhaps because the larger K + ions are more loosely held. The leaving cation affects the Ni 2+ distribution over the available sites, perhaps via the level of Ni 2+ -exchange. Both a greater degree of Ni 2+ -exchange and a higher dehydration temperature cause more Ni 8 O 4 · xH 2 O 8+ clusters to form, leaving fewer Ni 2+ ions at sites I and II. As more Ni 8 O 4 · xH 2 O 8+ formed, more H + ions were produced. Some H + and some 3-and 4-coordinate Ni 2+ ions are easily accessible for catalysis.

show abstract

Section: +mentioning

confidence: 97%

Crystal Structures of Vacuum-Dehydrated Ni²⁺-Exchanged Zeolite Y (FAU, Si/Al = 1.69) Containing Three-Coordinate Ni²⁺, Ni₈O₄·xH₂O⁸⁺, x ≤ 4, Clusters with Near Cubic Ni₄O₄ Cores, and H⁺

Kim¹,

Jung²,

Heo³

et al. 2009

J. Phys. Chem. C

Self Cite

View full text Add to dashboard Cite

show abstract

“…Also, monopositive cations commonly approach eight-ring oxygens at longer distances than six-ring oxygens in zeolite A. 17 …”

Section: Assignment Of Oxidation States To Indium Cationsmentioning

confidence: 99%

“…Again, such a difference is commonly seen for many cations located in the sodalite unit. 17,18,20,21 Each of the 2.0 and 1.6 indium ions per unit cell at In(2) in crystals 1 and 2 is 2.35(1) and 2.35(2) Å, respectively, from three six-ring oxygens at O(3) (see Table 4). The radii of these indium ions are both ca.…”

Section: Assignment Of Oxidation States To Indium Cationsmentioning

confidence: 99%

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

Self Cite

View full text Add to dashboard Cite

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.

show abstract

“…[28][29][30][31] Ge 136 presents a neutral clathrate. Thallium in the cages alone or with Na is also discovered in the zeolites of Tl 12 (Al 12 Si 12 O 48 ) 35 and Tl 8 Na 4 (Al 12 Si 12 O 48 ). The framework of the fulfilled clathrate-I Ba 8 36.4 ), the Ba1 and Ba2 structures locate in big and small cages, while Ge1, Ge2 and Tl1/Ba3/Ge3 occupy three crystallographic sites in the framework, respectively.…”

Section: Introductionmentioning

confidence: 97%

“…In Ba 8 (Ba 2.4 Tl 7.2 Ge 36.4 ), the Ba1 and Ba2 structures locate in big and small cages, while Ge1, Ge2 and Tl1/Ba3/Ge3 occupy three crystallographic sites in the framework, respectively. Thallium in the cages alone or with Na is also discovered in the zeolites of Tl 12 (Al 12 Si 12 O 48 ) 35 and Tl 8 Na 4 (Al 12 Si 12 O 48 ). 36 To reveal the nature of Tl's location in clathrates-II, we herein report the synthesis and properties of type-II clathrate Cs 8 Na 15 was prepared for comparison (n = 0).…”

Section: Introductionmentioning

confidence: 97%

Structure and properties of type-II clathrate Cs₈Na_16−xTl_xGe₁₃₆

Zhang

et al. 2015

Dalton Trans.

View full text Add to dashboard Cite

Tl-doped type-II clathrate Cs8Na16-xTlxGe136 was synthesized from its elements. The structure was characterised by single crystal and powder diffraction. Cs8Na16-xTlxGe136 crystallized in the space group Fd3[combining macron]m. The melting point decreased with increasing Tl content at 925.0 °C, 922.8 °C and 915.7 °C for Cs8Na14.76(3)Tl1.24(2)Ge136, Cs8Na9.94(2)Tl6.06(2)Ge136 and Cs8Na8.36(2)Tl7.64(2)Ge136 in Ar atmosphere, respectively. Cs8Na9.94(2)Tl6.06(2)Ge136 exhibited diamagnetism with χ = -3.11 × 10(-3) emu mol(-1) at 1.8 K. The heat capacity of Cs8Na9.94(2)Tl6.06(2)Ge136 presented an Einstein peak at 10 K. The fitted parameters for Cs8Na9.94(2)Tl6.06(2)Ge136 were λ = 0.115(4) J mol(-1) K(-2), β = 0.0289(2) J mol(-1) K(-4), NE = 7.94(4), θE = 56.9(1) K, ND = 152.06(4) and θD = 217(1) K using the equation Cp = Ce + CD + CE from 1.8 K to 10 K. The thermoelectric measurement showed metallic resistivity and a negative Seebeck coefficient, indicating electron-type charge carriers. The electronic structure calculation for Cs8Na10Tl6Ge136 confirmed the nature of the metallic transport behavior with conducting electrons, mainly from the Ge p orbitals.

show abstract

Near-zero-coordinate thallium(I). The crystal structures of hydrated and dehydrated zeolite A fully exchanged with thallium hydroxide

Cited by 42 publications

References 6 publications

Crystal Structures of Vacuum-Dehydrated Ni²⁺-Exchanged Zeolite Y (FAU, Si/Al = 1.69) Containing Three-Coordinate Ni²⁺, Ni₈O₄·xH₂O⁸⁺, x ≤ 4, Clusters with Near Cubic Ni₄O₄ Cores, and H⁺

Crystal Structures of Vacuum-Dehydrated Ni²⁺-Exchanged Zeolite Y (FAU, Si/Al = 1.69) Containing Three-Coordinate Ni²⁺, Ni₈O₄·xH₂O⁸⁺, x ≤ 4, Clusters with Near Cubic Ni₄O₄ Cores, and H⁺

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⁺

Structure and properties of type-II clathrate Cs₈Na_16−xTl_xGe₁₃₆

Contact Info

Product

Resources

About

Near-zero-coordinate thallium(I). The crystal structures of hydrated and dehydrated zeolite A fully exchanged with thallium hydroxide

Cited by 42 publications

References 6 publications

Crystal Structures of Vacuum-Dehydrated Ni2+-Exchanged Zeolite Y (FAU, Si/Al = 1.69) Containing Three-Coordinate Ni2+, Ni8O4·xH2O8+, x ≤ 4, Clusters with Near Cubic Ni4O4 Cores, and H+

Crystal Structures of Vacuum-Dehydrated Ni2+-Exchanged Zeolite Y (FAU, Si/Al = 1.69) Containing Three-Coordinate Ni2+, Ni8O4·xH2O8+, x ≤ 4, Clusters with Near Cubic Ni4O4 Cores, and H+

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+

Structure and properties of type-II clathrate Cs8Na16−xTlxGe136

Contact Info

Product

Resources

About

Crystal Structures of Vacuum-Dehydrated Ni²⁺-Exchanged Zeolite Y (FAU, Si/Al = 1.69) Containing Three-Coordinate Ni²⁺, Ni₈O₄·xH₂O⁸⁺, x ≤ 4, Clusters with Near Cubic Ni₄O₄ Cores, and H⁺

Crystal Structures of Vacuum-Dehydrated Ni²⁺-Exchanged Zeolite Y (FAU, Si/Al = 1.69) Containing Three-Coordinate Ni²⁺, Ni₈O₄·xH₂O⁸⁺, x ≤ 4, Clusters with Near Cubic Ni₄O₄ Cores, and H⁺

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⁺

Structure and properties of type-II clathrate Cs₈Na_16−xTl_xGe₁₃₆