Metal Structural Environment in Zn<sub>x</sub>Ni<sub>1–x</sub>O Macroscale and Nanoscale Solid Solutions
摘要:
The metal structural environments in macroscale and nanoscale Zn<sub>x</sub>Ni<sub>1–x</sub>O solid solutions were examined using X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS), and X-ray photoelectron spectroscopy (XPS). XRD demonstrates that solid solutions form for both macroscale (bulk) and nanoscale crystallites, and that the lattice parameter increases linearly as the amount of zinc increases, an indication of a homogeneous solid solution. XAS for both the bulk material and the nanoparticles reveals that the zinc atoms are incorporated into the rocksalt lattice and do not form zinc oxide clusters. The X-ray absorption near edge spectroscopy (XANES) of the Zn k-edge region in the solid solution is similar to the Ni k-edge region of NiO, and not the Zn k-edge region of ZnO. XPS confirms that solid solutions are formed; Auger parameters for zinc are consistent with a different geometry than the tetrahedral coordination of wurtzite ZnO. Nanoscaled solid solutions show evidence of a lattice contraction relative to macroscale solutions of the same concentration. While the contraction persists across the entire concentration range, the nanoparticle lattice parameter approaches the bulk Zn<sub>x</sub>Ni<sub>1–x</sub>O value as the concentration of zinc increases to predict ZnO rocksalt lattice parameters that are in agreement with observed ZnO data.
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DOI:
10.1021/jp502866m
年份:
2014
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