Incorporation of A2Q into HgQ and dimensional reduction to A2Hg3Q4 and A2Hg6Q7 (A = K, Rb, Cs; Q = S, Se).: Access of Li ions in A2Hg6Q7 through topotactic ion-exchange

被引:99
作者
Axtell, EA
Park, Y
Chondroudis, K
Kanatzidis, MG [1 ]
机构
[1] Michigan State Univ, Dept Chem, E Lansing, MI 48824 USA
[2] Michigan State Univ, Ctr Fundamental Mat Res, E Lansing, MI 48824 USA
关键词
D O I
10.1021/ja9713486
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The synthesis of the one-dimensional K(2)Hg(3)Q(4) (Q = S, Se) and Cs2Hg3Se4 and the three-dimensional A(2)Hg(6)S(7) (A = K, Rb, Cs), and A(2)Hg(6)Se(7) (A = Rb, Cs) in reactive A(2)Q(x) fluxes is reported. Pale yellow, hexagonal plates of K2Hg3S4 crystallize in space group Pbcn, with a = 10.561(5) Angstrom, b = 6.534(3) Angstrom, and c = 13.706(2) Angstrom, V = 945.8(7) Angstrom(3), d(calc) = 5.68 g/cm(3), and final R = 5.7%, R-W = 6.3%. Red, hexagonal plates of K2Hg3Se4 crystallize in space group Pbcn, with a = 10.820(2) Angstrom, b = 6.783(1) Angstrom, and c = 14.042(2) Angstrom, V = 1030.6(5) Angstrom(3), d(calc) = 6.42 g/cm(3), and final R = 7.7%, R-W = 8.4%. Orange yellow, hexagonal plates of Cs2Hg3Se4 crystallize in space group Pbcn, with a = 12.047(4) Angstrom, b = 6.465(2) Angstrom, and c = 14.771(6) Angstrom, V = 1150.4(7) Angstrom(3), d(calc) = 6.83 g/cm(3), and final R = 5.5%, R, = 6.2%. Black needles of K2Hg6S7 crystallize in space group <P(4)over bar 2(1)m>, with a = 13.805(8) Angstrom and c = 4.080(3) Angstrom, V = 778(1) Angstrom(3), d(calc) = 6.43 g/cm(3), and final R = 3.1%, R-W = 3.6%. Black needles of Rb2Hg6S7 crystallize in space group P4(2)nm, with a = 13.9221(8) Angstrom and c = 4.1204(2) Angstrom, V = 798.6(1) Angstrom(3), d(calc) = 6.65 g/cm(3), and final R = 4.3%, R-W = 5.0%. Black needles of Cs2Hg6S7 crystallize in space group P4(2)nm, with a = 13.958(4) Angstrom and c = 4.159(2) Angstrom, V = 810.2(8) Angstrom(3), d(calc) = 6.94 g/cm(3), and final R = 4.3%, R-W = 4.4%. Black needles of Cs2Hg6Se7 crystallize in space group P4(2)nm, with a = 14.505(7) Angstrom and c = 4.308(2) Angstrom, V = 906(1) Angstrom(3), d(calc) = 7.41 g/cm(3), and final R 3.6%, R-W = 4.0%. The A(2)Hg(3)Q(4) compounds contain linear chains. The A(2)Hg(6)Q(7) compounds display noncentrosymmetric frameworks with Af cations residing in tunnels formed by both tetrahedral and linear Hg atoms. K2Hg6S7, Rb2Hg6S7, Cs2Hg6S7, Rb2Hg6Se7, and Cs2Hg6Se7 display room-temperature bandgaps of 1.51, 1.55, 1.61, 1.13, and 1.17 eV, respectively. Bandgap engineering through S/Se solid solutions of the type Rb2Hg6Se7-xSx and Cs2Hg6Se7-xSx is possible in these materials. All A(2)Hg(6)Q(7) melt congruently, with melting points of 556 +/- 10 degrees C, except for Rb2Hg6Se7 which degrades. Rb2Hg6S7 can undergo ion exchange reactions with LiI to give Li1.8Rb0.2Hg6S7.
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页码:124 / 136
页数:13
相关论文
共 49 条
[1]  
ALONSOVANTE N, 1987, J AM CHEM SOC, V109, P3251
[2]   K2CD2S3 VS CDS - CAN THE PROPERTIES OF QUANTUM-SIZED CDQ SEMICONDUCTORS BE EMULATED BY BULK ALKALI-METAL TERNARY A/CD/Q PHASES (Q = CHALCOGEN) [J].
AXTELL, EA ;
LIAO, JH ;
PIKRAMENOU, Z ;
PARK, YB ;
KANATZIDIS, MG .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1993, 115 (25) :12191-12192
[3]   Dimensional reduction in II-VI materials: A(2)Cd(3)Q(4) (A=K, Q=S, Se, Te; A=Rb, Q=S, Se), novel ternary low-dimensional cadmium chalcogenides produced by incorporation of A(2)Q in CdQ [J].
Axtell, EA ;
Liao, JH ;
Pikramenou, Z ;
Kanatzidis, MG .
CHEMISTRY-A EUROPEAN JOURNAL, 1996, 2 (06) :656-666
[4]  
AXTELL EA, 1995, THESIS MICHIGAN STAT
[5]   TETRAHEDRAL HGS4 AND LINEAR HGS2 COORDINATION IN THE CRYSTAL-STRUCTURE OF NA2HG3S4(H2O)2 [J].
BANDA, RMH ;
CRAIG, D ;
DANCE, IG ;
SCUDDER, M .
POLYHEDRON, 1991, 10 (01) :41-45
[6]  
BISCHER O, 1982, SUPERCONDUTIVITY TER, V2
[7]  
BISCHER O, 1985, SUPERCONDUTIVITY TER, V1
[8]  
CHEVREL R, 1981, SUPERCONDUCTOR MATER, pCH10
[9]   TRANSITION-METAL SULFIDE CATALYSIS - RELATION OF THE SYNERGIC SYSTEMS TO THE PERIODIC TRENDS IN HYDRODESULFURIZATION [J].
CHIANELLI, RR ;
PECORARO, TA ;
HALBERT, TR ;
PAN, WH ;
STIEFEL, EI .
JOURNAL OF CATALYSIS, 1984, 86 (01) :226-230
[10]  
CHONDROUDIS K, UNPUB