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The oxidation state and microstructural environment of transition metals (V, Co, and Ni) in magnetite: an XAFS study

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Abstract

Transition metal-substituted magnetite minerals have attracted increasing attention for their wide application in industry and environmental protection. In this study, the valence and atomic environment of some substituting metals in magnetites (Fe3−x M x O4, M = V, Co, and Ni) were investigated using X-ray absorption fine structure spectroscopy. The results deduced from X-ray absorption near-edge structure spectroscopy indicated that the valences of V, Co, and Ni in Fe3−x M x O4 were +3, +2, and +2, respectively. The valences did not change as the substitution extent increased. Extended X-ray absorption fine structure spectroscopy suggested that the substituting cations occupied octahedral sites in the magnetite structure. The M–O and M–M/Fe distances were consistent with the Feoct–O and Feoct–Fe distances, respectively, in the magnetite (Fe3O4) structure. The occupancy of the substituting cations was assessed by crystal-field theory. We also considered the relationship between the chemical environment of substituting cations and their effects on the physicochemical properties of magnetite, including thermal stability, surface properties, and catalytic reactivity.

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Acknowledgments

We gratefully acknowledge Beijing Synchrotron Radiation Facility (BSRF) for providing us the beam time for the XAFS measurement. We gratefully acknowledge the National Natural Science Foundation of China (Grant Nos. 41172045 and 41302026) and Natural Science Foundation of Guangdong Province, China (Grant No. S2012010009598) for financial support. This is contribution No. IS-1990 from GIG CAS.

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Authors and Affiliations

  1. Key Laboratory of Mineralogy and Metallogeny, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences and Guangdong Provincial Key Laboratory of Mineral Physics and Materials, Guangzhou, 510640, China

    Xiaoliang Liang, Zisen He, Wei Tan, Peng Liu, Jianxi Zhu & Hongping He

  2. University of Chinese Academy of Sciences, Beijing, 100049, China

    Zisen He, Wei Tan & Peng Liu

  3. Institute of High Energy Physics, Chinese Academy of Sciences, Beijing, 100049, China

    Jing Zhang

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  1. Xiaoliang Liang
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  2. Zisen He
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  4. Peng Liu
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Correspondence to Hongping He.

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Liang, X., He, Z., Tan, W. et al. The oxidation state and microstructural environment of transition metals (V, Co, and Ni) in magnetite: an XAFS study. Phys Chem Minerals 42, 373–383 (2015). https://doi.org/10.1007/s00269-014-0727-4

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