Ag Ion-Exchange Reactions of Cu2P3I2 and Cu2P1.8As1.2I2

Jayasekera, Buddhimathie; Brock, Stephanie L.

doi:10.1557/proc-755-dd6.12

Cited by 2 publications

(3 citation statements)

References 7 publications

(5 reference statements)

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“…The residual pellet has a similar pattern to that for the crystals, along with peaks corresponding to CuI. Energy dispersive spectroscopy (EDS) on single crystals imaged in the scanning electron microscope (SEM) indicated the presence of Cu, P, As, and I, [15] thus implying that the compound is a quaternary phase. Quantification of As incorporation in crystals of 20 %, 35 %, 40 %, 45 %, and 55 % As samples was achieved by inductively coupled plasma-mass spectrometry (ICP-MS) and the data are presented in Table 1.…”

Section: Resultsmentioning

confidence: 83%

Structure–Property Correlations in Solid Solutions of (CuI)₈P_12−xAs_x, 2.4≤x≤6.6

Jayasekera

Brock

et al. 2005

Chemistry A European J

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A series of P/As mixed pnicogen phases of composition (CuI)(8)P(12-x)As(x), in which x = 2.4, 4.2, 4.8, 5.4, and 6.6, have been synthesized and characterized by X-ray single crystal and powder diffraction, solid-state NMR spectroscopy, thermal gravimetric analysis, and impedance spectroscopy. These materials are isostructural to (CuI)(8)P(12) and consist of neutral, tubular P/As mixed pnicogen chains associated with Cu(I) and I(-) ions. The As is distributed throughout the pnicogen chains; however, the "roof" sites of the [P8] cage show preferred occupation by As relative to the other sites. Accordingly, the change in cell volume is not a linear function of the As incorporation. Solid-state (31)P NMR spectroscopy of the 40 % As incorporated sample are consistent with the X-ray structural model, with extensive broadening due to (31)P-(75)As coupling and site disorder, and a change in the chemical shifts of the resonances due to the As substitution into the lattice. The degree of copper ion site disorder, probed by single-crystal X-ray diffraction, increases with increasing As content. Although very little change is observed in the copper ionic conductivity of polycrystalline samples, which ranges from 1.8-5.1 x 10(-6) S cm(-1) for (CuI)(8)P(12-x)As(x), x = 0, 4.2, 5.4; a single crystal (x = 4.8) measured along the needle axis has a conductivity of 1.7 x 10(-3) S cm(-1) at 128 degrees C. This represents an order of magnitude improvement in conductivity over (CuI)(8)P(12) at the same temperature.

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Section: Resultsmentioning

confidence: 83%

Structure–Property Correlations in Solid Solutions of (CuI)₈P_12−xAs_x, 2.4≤x≤6.6

Jayasekera

Brock

et al. 2005

Chemistry A European J

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“…However, Möller and Jeitschko reported that addition of KCN permitted facile exchange of Cu + by Ag + in Cu 2 P 3 I 2 without silver deposition, and proposed that the reaction proceeds according to eq 1 . Our attempts to employ excess KCN with Cu 2 P 1.8 As 1.2 I 2 did produce a material with Ag incorporation, according to energy dispersive spectroscopy (EDS), but it was X-ray amorphous …”

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confidence: 90%

“…The approach described herein is based on the results from Ag + ion-exchange reactions performed on Cu 2 P 1.8 As 1.2 I 2 to prepare the corresponding Ag analogue . Reactions in aqueous solutions with AgNO 3 invariably produced elemental silver as a byproduct, along with Ag 2 P 1.8 As 1.2 I 2 .…”

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Liberation of Pnicogen Chains from Cu₂P_1.8As_1.2I₂: Synthesis and Characterization of a New Allotrope of P−As

2004

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Removal of CuI from Cu(2)P(1.8)As(1.2)I(2) results in a novel P--As allotrope. Although the product is X-ray amorphous, lattice fringes are observed in the transmission electron micrographs with spacings reflecting the diameter of the linear pnicogen polymer in Cu(2)P(1.8)As(1.2)I(2), suggesting the pnicogen chains remain intact upon loss of CuI. The straight needles present in Cu(2)P(1.8)As(1.2)I(2) appear to be kinked in the P--As phase due to lattice mismatch between the liberated polymers, ultrasonic treatment, or a combination of these effects. This new P--As modification is semiconducting with a band gap of 1.05 eV.

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Ag Ion-Exchange Reactions of Cu₂P₃I₂ and Cu₂P_1.8As_1.2I₂

Cited by 2 publications

References 7 publications

Structure–Property Correlations in Solid Solutions of (CuI)₈P_12−xAs_x, 2.4≤x≤6.6

Structure–Property Correlations in Solid Solutions of (CuI)₈P_12−xAs_x, 2.4≤x≤6.6

Liberation of Pnicogen Chains from Cu₂P_1.8As_1.2I₂: Synthesis and Characterization of a New Allotrope of P−As

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Ag Ion-Exchange Reactions of Cu2P3I2 and Cu2P1.8As1.2I2

Cited by 2 publications

References 7 publications

Structure–Property Correlations in Solid Solutions of (CuI)8P12−xAsx, 2.4≤x≤6.6

Structure–Property Correlations in Solid Solutions of (CuI)8P12−xAsx, 2.4≤x≤6.6

Liberation of Pnicogen Chains from Cu2P1.8As1.2I2: Synthesis and Characterization of a New Allotrope of P−As

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Ag Ion-Exchange Reactions of Cu₂P₃I₂ and Cu₂P_1.8As_1.2I₂

Structure–Property Correlations in Solid Solutions of (CuI)₈P_12−xAs_x, 2.4≤x≤6.6

Structure–Property Correlations in Solid Solutions of (CuI)₈P_12−xAs_x, 2.4≤x≤6.6

Liberation of Pnicogen Chains from Cu₂P_1.8As_1.2I₂: Synthesis and Characterization of a New Allotrope of P−As