Investigation into the effect on structure of oxoanion doping in Na2M(SO4)2·2H2O

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@article{de5507dcc6e64f7b96e966d2a4f1695a,
title = "Investigation into the effect on structure of oxoanion doping in Na2M(SO4)2·2H2O",
abstract = "In this paper an investigation into the effect of transition metal ion and selenate/fluorophosphate doping on the structures of Na2M(SO4)2·2H2O (M=transition metal) materials is reported. In agreement with previous reports, the monoclinic (Kr{\"o}hnkite) structure is adopted for M=Mn, Fe, Co, Cu, while for the smallest first row divalent transition metal ion, M=Ni, the triclinic (Fairfieldite structure) is adopted. On selenate doping there is a changeover in structure from monoclinic to triclinic for M=Fe, Co, Cu, with the larger Fe2+ system requiring the highest level of selenate to complete the changeover. Thus the results suggest that the relative stability of the two structure types is influenced by the relative size of the transition metal: oxoanion group, with the triclinic structure favoured for small transition metals/large oxoanions.The successful synthesis of fluorophosphate doped samples, Na2M(SO4)2−x(PO3F)x·2H2O was also obtained for M=Fe, Co, Cu, with the results showing a changeover in structure from monoclinic to triclinic for M=Co, Cu for very low levels (x=0.1) of fluorophosphate. In the case of M=Fe, the successful synthesis of fluorophosphates samples was achieved for x≤0.3, although no change in cell symmetry was observed. Rather in this particular case, the X-ray diffraction patterns showed evidence for selective peak broadening, attributed to local disorder as a result of the fluorophosphate group disrupting the H-bonding network. Overall the work highlights how isovalent doping can be exploited to alter the structures of Na2M(SO4)2·2H2O systems.",
keywords = "Sodium ion, Sulfate, Selenate, Fluorophosphate, Crystal Structure",
author = "Laura Driscoll and Adrian Wright and Emma Kendrick and Peter Slater",
year = "2016",
month = oct
doi = "10.1016/j.jssc.2016.07.004",
language = "English",
volume = "242",
pages = "103--111",
journal = "Journal of Solid State Chemistry",
issn = "0022-4596",
publisher = "Elsevier",
number = "Part 1",

}

RIS

TY - JOUR

T1 - Investigation into the effect on structure of oxoanion doping in Na2M(SO4)2·2H2O

AU - Driscoll, Laura

AU - Wright, Adrian

AU - Kendrick, Emma

AU - Slater, Peter

PY - 2016/10

Y1 - 2016/10

N2 - In this paper an investigation into the effect of transition metal ion and selenate/fluorophosphate doping on the structures of Na2M(SO4)2·2H2O (M=transition metal) materials is reported. In agreement with previous reports, the monoclinic (Kröhnkite) structure is adopted for M=Mn, Fe, Co, Cu, while for the smallest first row divalent transition metal ion, M=Ni, the triclinic (Fairfieldite structure) is adopted. On selenate doping there is a changeover in structure from monoclinic to triclinic for M=Fe, Co, Cu, with the larger Fe2+ system requiring the highest level of selenate to complete the changeover. Thus the results suggest that the relative stability of the two structure types is influenced by the relative size of the transition metal: oxoanion group, with the triclinic structure favoured for small transition metals/large oxoanions.The successful synthesis of fluorophosphate doped samples, Na2M(SO4)2−x(PO3F)x·2H2O was also obtained for M=Fe, Co, Cu, with the results showing a changeover in structure from monoclinic to triclinic for M=Co, Cu for very low levels (x=0.1) of fluorophosphate. In the case of M=Fe, the successful synthesis of fluorophosphates samples was achieved for x≤0.3, although no change in cell symmetry was observed. Rather in this particular case, the X-ray diffraction patterns showed evidence for selective peak broadening, attributed to local disorder as a result of the fluorophosphate group disrupting the H-bonding network. Overall the work highlights how isovalent doping can be exploited to alter the structures of Na2M(SO4)2·2H2O systems.

AB - In this paper an investigation into the effect of transition metal ion and selenate/fluorophosphate doping on the structures of Na2M(SO4)2·2H2O (M=transition metal) materials is reported. In agreement with previous reports, the monoclinic (Kröhnkite) structure is adopted for M=Mn, Fe, Co, Cu, while for the smallest first row divalent transition metal ion, M=Ni, the triclinic (Fairfieldite structure) is adopted. On selenate doping there is a changeover in structure from monoclinic to triclinic for M=Fe, Co, Cu, with the larger Fe2+ system requiring the highest level of selenate to complete the changeover. Thus the results suggest that the relative stability of the two structure types is influenced by the relative size of the transition metal: oxoanion group, with the triclinic structure favoured for small transition metals/large oxoanions.The successful synthesis of fluorophosphate doped samples, Na2M(SO4)2−x(PO3F)x·2H2O was also obtained for M=Fe, Co, Cu, with the results showing a changeover in structure from monoclinic to triclinic for M=Co, Cu for very low levels (x=0.1) of fluorophosphate. In the case of M=Fe, the successful synthesis of fluorophosphates samples was achieved for x≤0.3, although no change in cell symmetry was observed. Rather in this particular case, the X-ray diffraction patterns showed evidence for selective peak broadening, attributed to local disorder as a result of the fluorophosphate group disrupting the H-bonding network. Overall the work highlights how isovalent doping can be exploited to alter the structures of Na2M(SO4)2·2H2O systems.

KW - Sodium ion

KW - Sulfate

KW - Selenate

KW - Fluorophosphate

KW - Crystal Structure

U2 - 10.1016/j.jssc.2016.07.004

DO - 10.1016/j.jssc.2016.07.004

M3 - Article

VL - 242

SP - 103

EP - 111

JO - Journal of Solid State Chemistry

JF - Journal of Solid State Chemistry

SN - 0022-4596

IS - Part 1

ER -