Zirconium and Hafnium Hydrogen Monothiophosphates, H2Zr(PO3S)2 and H2Hf(PO3S)2. Syntheses and Selective Ion-Exchange Properties of Sul
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- 作者：Alexander E. Gash ; Peter K. Dorhout ; and Steven H. Strauss
- 刊名：Inorganic Chemistry
- 出版年：2000
- 出版时间：November 27, 2000
- 年：2000
- 卷：39
- 期：24
- 页码：5538 - 5546
- 全文大小：136K
- 年卷期：v.39,no.24(November 27, 2000)
- ISSN：1520-510X
文摘
The reactions between aqueous solutions of M4+ (M = Zr, Hf) and PO3S3- each result in the precipitation of awhite gel that can be dried to a powder. Elemental analysis results for the white polycrystalline product yield astoichiometry of H2M(PO3S)2. These new compounds are characterized by thermal analysis (DSC, TG-MS),vibrational spectroscopy (FT-IR, FT-Raman), 31P MAS NMR spectroscopy, energy-dispersive spectroscopy (EDS),and powder X-ray diffraction (XRD). On the basis of the characterizations and the results of trialkylamineintercalation experiments, we conclude that the H2M(PO3S)2 compounds have a layered structure that is likelysimilar to that of 
-H2Zr(PO4)2·H2O. The interlayer spacing for both H2M(PO3S)2 compounds, determined byXRD, is ~9.4 Å. Our characterization results suggest that the sulfur atom of each PO3S3- group is preferentiallypointed into the interlayer region of the compound and is protonated. Two of the many potentially interestingproperties of H2Zr(PO3S)2, its ion-exchange capacity and selectivity, are investigated. H2Zr(PO3S)2 is demonstratedto be an effective and recyclable ion-exchange material for both Zn2+(aq) and Cd2+(aq). Mass balance experimentsindicate that the removal of Cd2+(aq) and Zn2+(aq) ions by solid H2Zr(PO3S)2 occurs by an ion-exchange process.Ion exchange results in the formation of the new compounds H0.2Cd0.9Zr(PO3S)2 and H0.50Zn0.75Zr(PO3S)2. Theextraction of metal ions is monitored by XRD, vibrational spectroscopy, and elemental analysis. H2Zr(PO3S)2reversibly intercalates Zn2+(aq) ions through three complete cycles of intercalation and deintercalation withoutany loss of ion-exchange capacity.
-H2Zr(PO4)2·H2O. The interlayer spacing for both H2M(PO3S)2 compounds, determined byXRD, is ~9.4 Å. Our characterization results suggest that the sulfur atom of each PO3S3- group is preferentiallypointed into the interlayer region of the compound and is protonated. Two of the many potentially interestingproperties of H2Zr(PO3S)2, its ion-exchange capacity and selectivity, are investigated. H2Zr(PO3S)2 is demonstratedto be an effective and recyclable ion-exchange material for both Zn2+(aq) and Cd2+(aq). Mass balance experimentsindicate that the removal of Cd2+(aq) and Zn2+(aq) ions by solid H2Zr(PO3S)2 occurs by an ion-exchange process.Ion exchange results in the formation of the new compounds H0.2Cd0.9Zr(PO3S)2 and H0.50Zn0.75Zr(PO3S)2. Theextraction of metal ions is monitored by XRD, vibrational spectroscopy, and elemental analysis. H2Zr(PO3S)2reversibly intercalates Zn2+(aq) ions through three complete cycles of intercalation and deintercalation withoutany loss of ion-exchange capacity.