Ion exchange of different phosphate ions into the zinc–aluminium–chloride layered double hydroxide
Introduction
Significant industrial and academic interests are being paid to the layered double hydroxides (LDH)s, also referred to as anionic clays and hydrotalcite-like compounds, due to their important anionic exchange and intercalation aptitudes which make them potential assets for extremely varied technological applications in various domains such as catalysis, electrochemistry, separation technology, and medicine 1, 2, 3, 4, 5, 6.
Their structure is constituted from positively charged metal hydroxide layers, containing divalent and trivalent cations, of composition [MII1−xMIIIx(OH)2]x+. These layers, which are similar to those in the brucite Mg(OH)2, alternate with charge compensating layers of anions and water, [Xx/mm−·nH2O]x−. LDHs can be represented by the general formula:where, MII=Mg2+, Zn2+, Mn2+, Fe2+, Ni2+, etc.; MIII=Al3+, Cr3+, Fe3+, etc.; and Xm−=Cl−, CO32−, NO3−, etc. 7, 8, 9.
This study forms part of a wider investigation undertaken on the chloride/phosphate ion exchange into the [Zn–Al] LDHs and the study of their stability and physicochemical properties, in particular their ionic conductivity and their thermal behaviour. The phosphate ions are expected to undergo grafting to the layers upon thermal treatment, leading to pillared materials.
In this paper, we report on structural characteristics of the [Zn–Al–Cl] following the exchange of Cl− by a series of phosphate ions with different charges and sizes; namely, the metaphosphate (PO3−), the dihydrogenophosphate (H2PO4−), the hydrogenophosphate (HPO42−), the orthophosphate (PO43−), the pyrophosphate (P2O74−) and the triphosphate (P3O105−), leading to the formation of [Zn–Al–phosphate] intercalated phases. Powder X-ray diffraction (PXRD) and Fourier transform infrared spectroscopy (FT-IR) have allowed a correlation to be made of the structural features of the precursor and the exchanged materials.
Section snippets
Experimental
All experiments were carried out under a stream of N2 in order to avoid, or at least minimise, the contamination by atmospheric CO2. The [Zn–Al–Cl] precursor, with [Zn2+]/[Al3+] ratio equal to 2, was prepared by the method of coprecipitation at constant pH as described elsewhere 10, 11. Exchange reactions were carried out, at room temperature, with 200 mg of the [Zn–Al–Cl] LDH suspended in the phosphate ion-containing solutions 10, 11that were stirred and then centrifuged. The effects of anion
Results and discussion
The PXRD patterns of the [Zn–Al–Cl] precursor and the exchanged phases (Fig. 1) are in good agreement with those found for the hydrotalcite-like compounds [12]. [Zn–Al–phosphate] LDHs present some common features. The layered structure of the material is preserved upon exchange. However, the crystallinity is lowered, as attested to by the broadening of the lines and the decrease in their intensity. In addition, the ion exchange is observed to cause a little broadening of the (110) reflection,
Conclusion
The present study provides very good examples for the ion exchange capabilities of layered double hydroxide materials. XRD and IR revealed that, in all cases, the crystallinity of phosphate-intercalated phases is lower than that of the precursor. Ion exchange was also observed to cause certain disorder in the layers without destruction of the layered structure of the material. Microanalysis of the samples confirmed the total phosphate-chloride ion exchange in all cases. It will be of interest
Acknowledgements
The authors wish to thank the `Comité Mixte Interuniversitaire Franco-Marocain' for the financial support (Integrated Action No. 95/856).
References (24)
- et al.
J. Catal.
(1986) - et al.
Catal. Today
(1991) - et al.
J. Electroanal. Chem.
(1994) - et al.
Mater. Chem. Phys.
(1998) - et al.
Solid State Ionics
(1997) - et al.
J. Solid State Chem.
(1997) - et al.
Spectrochim. Acta A
(1964) - et al.
Spectrochim. Acta
(1993) - et al.
J. Am. Chem. Soc.
(1988) - et al.
Pharma. Acta Helv.
(1974)
Collect. Czech. Chem. Commun.
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