skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Crystal structure of a zinc sorption complex of Cd{sup 2+}-exchanged zeolite X containing tetrahedral Cd{sub 4}{sup 2+}({mu}{sub 3}-Zn{sup 0}Cd{sup 2+}Zn{sup 0}){sub 4} clusters

Abstract

The sorption of Zn vapor at 480 C onto fully dehydrated fully Cd{sup 2+}-exchanged zeolite X (Cd{sub 46}Si{sub 100}Al{sub 92}O{sub 384} per unit cell) has been studied at 23 C by single-crystal X-ray diffraction in the cubic space group Fd3 (a{sub 0} = 24.895(3) {angstrom}). In this structure, Cd{sub 46}Si{sub 100}Al{sub 92}O{sub 384}{center_dot}20Zn, Cd{sup 2+} ions are found at five nonequivalent sites, redistributed significantly from 16, 0, 30, 0, 0 in dehydrated Cd{sub 46}-X to 12, 8, 12, 6, 8 (best integers) at sites I, I{prime}, II, III{prime}, and another III{prime} respectively. The 8 Cd{sup 2+} ions at site I{prime} and 8 of the 12 Cd{sup 2+} ions at site II have captured 16 Zn atoms to form two Cd{sub 4}{sup 2+}({mu}{sub 3}-Zn{sup 0}Cd{sup 2+}Zn{sup 0}){sub 4} clusters per unit cell. The remaining four Cd{sup 2+} ions at site II have captured the remaining (about four) Zn atoms. Each Cd{sub 4}{sup 2+}({sub 3}-Zn{sup 0}Cd{sup 2+}Zn{sup 0}){sub 4} cluster has at its center interpenetrating tetrahedra of (Cd{sup 2+}){sub 4} and (Zn{sup 0}){sub 4} in the sodalite unit, with four terminal Cd{sup 2+}-Zn{sup 0} groups extending radially into the supercage from each of the above Zn{sup 0} atoms; Cd{sup 2+} ions andmore » Zn{sup 0} atoms alternate throughout. The central four Zn{sup 0} atoms form a tetrahedral Zn{sub 4}{sup 0} cluster with Zn-Zn = 2.88(4) {angstrom}, somewhat longer than the 2.66 {angstrom} distance in Zn metal, due perhaps to delocalization of bonding density to adjacent Cd{sup 2+} ions. In each Cd{sub 4}{sup 2+}({mu}{sub 3}-Zn{sup 0}Cd{sup 2+}Zn{sup 0}){sub 4} cluster, each sodalite unit Cd{sup 2+} ion has a distorted octahedral environment, 2.566(11) {angstrom} to three framework oxygens at 2.225(8) {angstrom} and axially to two Zn atoms at 2.408(23) {angstrom} and 1.97(5) {angstrom}, respectively. Each sodalite unit Zn atom coordinates tetrahedrally to four Cd{sup 2+} ions; each terminal Zn atom interacts only with one Cd{sup 2+} ion. Surprisingly, no Cd{sup 2+} ions have been reduced by Zn atoms; all Cd{sup 2+} ions are at reasonable bonding distances to framework oxygens, and all Zn atoms are far from framework oxygens. About 12 Cd{sup 2+} ions remained at site I upon Zn sorption; each coordinates octahedrally to six framework oxygens at 2.430(10) {angstrom}. About 6 + 8 = 14 Cd{sup 2+} ions have relocated to two III{prime} sites, 2.46(5) {angstrom} and 2.38(3) {angstrom}, respectively, from framework oxygens.« less

Authors:
;  [1]
  1. Univ. of Hawaii, Honolulu, HI (United States). Dept. of Chemistry
Publication Date:
OSTI Identifier:
682067
Resource Type:
Journal Article
Journal Name:
Journal of Physical Chemistry B: Materials, Surfaces, Interfaces, amp Biophysical
Additional Journal Information:
Journal Volume: 103; Journal Issue: 31; Other Information: PBD: 5 Aug 1999
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; CRYSTAL STRUCTURE; ZINC; VAPOR DEPOSITED COATINGS; ZEOLITES; ELECTRONIC STRUCTURE; CADMIUM

Citation Formats

Zhen, S., and Seff, K. Crystal structure of a zinc sorption complex of Cd{sup 2+}-exchanged zeolite X containing tetrahedral Cd{sub 4}{sup 2+}({mu}{sub 3}-Zn{sup 0}Cd{sup 2+}Zn{sup 0}){sub 4} clusters. United States: N. p., 1999. Web. doi:10.1021/jp991073b.
Zhen, S., & Seff, K. Crystal structure of a zinc sorption complex of Cd{sup 2+}-exchanged zeolite X containing tetrahedral Cd{sub 4}{sup 2+}({mu}{sub 3}-Zn{sup 0}Cd{sup 2+}Zn{sup 0}){sub 4} clusters. United States. doi:10.1021/jp991073b.
Zhen, S., and Seff, K. Thu . "Crystal structure of a zinc sorption complex of Cd{sup 2+}-exchanged zeolite X containing tetrahedral Cd{sub 4}{sup 2+}({mu}{sub 3}-Zn{sup 0}Cd{sup 2+}Zn{sup 0}){sub 4} clusters". United States. doi:10.1021/jp991073b.
@article{osti_682067,
title = {Crystal structure of a zinc sorption complex of Cd{sup 2+}-exchanged zeolite X containing tetrahedral Cd{sub 4}{sup 2+}({mu}{sub 3}-Zn{sup 0}Cd{sup 2+}Zn{sup 0}){sub 4} clusters},
author = {Zhen, S. and Seff, K.},
abstractNote = {The sorption of Zn vapor at 480 C onto fully dehydrated fully Cd{sup 2+}-exchanged zeolite X (Cd{sub 46}Si{sub 100}Al{sub 92}O{sub 384} per unit cell) has been studied at 23 C by single-crystal X-ray diffraction in the cubic space group Fd3 (a{sub 0} = 24.895(3) {angstrom}). In this structure, Cd{sub 46}Si{sub 100}Al{sub 92}O{sub 384}{center_dot}20Zn, Cd{sup 2+} ions are found at five nonequivalent sites, redistributed significantly from 16, 0, 30, 0, 0 in dehydrated Cd{sub 46}-X to 12, 8, 12, 6, 8 (best integers) at sites I, I{prime}, II, III{prime}, and another III{prime} respectively. The 8 Cd{sup 2+} ions at site I{prime} and 8 of the 12 Cd{sup 2+} ions at site II have captured 16 Zn atoms to form two Cd{sub 4}{sup 2+}({mu}{sub 3}-Zn{sup 0}Cd{sup 2+}Zn{sup 0}){sub 4} clusters per unit cell. The remaining four Cd{sup 2+} ions at site II have captured the remaining (about four) Zn atoms. Each Cd{sub 4}{sup 2+}({sub 3}-Zn{sup 0}Cd{sup 2+}Zn{sup 0}){sub 4} cluster has at its center interpenetrating tetrahedra of (Cd{sup 2+}){sub 4} and (Zn{sup 0}){sub 4} in the sodalite unit, with four terminal Cd{sup 2+}-Zn{sup 0} groups extending radially into the supercage from each of the above Zn{sup 0} atoms; Cd{sup 2+} ions and Zn{sup 0} atoms alternate throughout. The central four Zn{sup 0} atoms form a tetrahedral Zn{sub 4}{sup 0} cluster with Zn-Zn = 2.88(4) {angstrom}, somewhat longer than the 2.66 {angstrom} distance in Zn metal, due perhaps to delocalization of bonding density to adjacent Cd{sup 2+} ions. In each Cd{sub 4}{sup 2+}({mu}{sub 3}-Zn{sup 0}Cd{sup 2+}Zn{sup 0}){sub 4} cluster, each sodalite unit Cd{sup 2+} ion has a distorted octahedral environment, 2.566(11) {angstrom} to three framework oxygens at 2.225(8) {angstrom} and axially to two Zn atoms at 2.408(23) {angstrom} and 1.97(5) {angstrom}, respectively. Each sodalite unit Zn atom coordinates tetrahedrally to four Cd{sup 2+} ions; each terminal Zn atom interacts only with one Cd{sup 2+} ion. Surprisingly, no Cd{sup 2+} ions have been reduced by Zn atoms; all Cd{sup 2+} ions are at reasonable bonding distances to framework oxygens, and all Zn atoms are far from framework oxygens. About 12 Cd{sup 2+} ions remained at site I upon Zn sorption; each coordinates octahedrally to six framework oxygens at 2.430(10) {angstrom}. About 6 + 8 = 14 Cd{sup 2+} ions have relocated to two III{prime} sites, 2.46(5) {angstrom} and 2.38(3) {angstrom}, respectively, from framework oxygens.},
doi = {10.1021/jp991073b},
journal = {Journal of Physical Chemistry B: Materials, Surfaces, Interfaces, amp Biophysical},
number = 31,
volume = 103,
place = {United States},
year = {1999},
month = {8}
}