Syntheses of Hafnium-Zirconium Silicate Solid Solutions and a Simple Method to Efficiently Evaluate the Homogeneity of Zr and Hf Distribution


Solid solutions of the microporous mixed tetrahedra-octahedra framework with the structures AV-3 Na2+z[(Zr1-xHfx)-Si3O9(Cl, OH)(z)]center dot H2O (x = 0, 0.33, 0.67, and 1), AV-13 Na2+z[(Zr1-xHfx)Si3O9Clz]center dot 2.5H(2)O (x = 0, 0.33, and 1), and AV-14 Na-2[(Zr1-xHfx]Si4O11]center dot 2H(2)O (x = 0, 0.33, and 1) have been prepared under hydrothermal conditions. This was the first time that the hydrothermal synthesis of Hf-AV-3 was reported. Wadeite K-2[(Zr1-xHfx)Si3O9] (x = 0, 0.33, 0.67, and 1) has been prepared using high-temperature phase transformation. The desired phase and phase purity were studied by powder X-ray diffraction, scanning electron microscopy, and energy dispersive X-ray spectrometry. The framework substitution of Zr by Hf has been investigated by Si-29 magic-angle spinning (MAS) nuclear magnetic resonance (NMR) and Raman spectroscopy. In the selected region, Raman shifts depend on the hafnium content in these samples. Si-29 MAS NMR is a unique technique, which provides clear evidence for the framework substitution of Zr by Hf. Therefore, the hafnium content is able to be estimated from Raman shifts of bands in the selected region and the intensity of the Si-29 MAS NMR signals. Si-29 MAS NMR spectroscopy is also proposed to be an efficient technique to evaluate the homogeneity of Zr and Hf distribution in the hafnium-zirconium silicate solid solution.



subject category

Chemistry, Physical; Nanoscience & Nanotechnology; Materials Science, Multidisciplinary


Lin, Z

our authors


This work was supported by the project CICECO-Aveiro Institute of Materials, UIDB/50011/2020 and UIDP/50011/2020, financed by national funds through the Portuguese Foundation for Science and Technology/MCTES.

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