TY - JOUR
T1 - 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+
AU - Heo, Nam Ho
AU - Chun, Chang Woo
AU - Park, Jong Sam
AU - Lim, Woo Taik
AU - Park, Man
AU - Li, Song Lin
AU - Zhou, Ling Ping
AU - Seff, Karl
PY - 2002/5/9
Y1 - 2002/5/9
N2 - 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.
AB - 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.
UR - https://www.scopus.com/pages/publications/0037046752
U2 - 10.1021/jp011839j
DO - 10.1021/jp011839j
M3 - Article
AN - SCOPUS:0037046752
SN - 1520-6106
VL - 106
SP - 4578
EP - 4587
JO - Journal of Physical Chemistry B
JF - Journal of Physical Chemistry B
IS - 18
ER -