Watching Iron Nanoparticles Rust: An in Situ X-ray Absorption Spectroscopic Study
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- 作者：Yali Yao ; Yongfeng Hu ; Robert W. J. Scott
- 刊名：Journal of Physical Chemistry C
- 出版年：2014
- 出版时间：September 25, 2014
- 年：2014
- 卷：118
- 期：38
- 页码：22317-22324
- 全文大小：408K
- ISSN：1932-7455
文摘
Iron nanoparticles and iron oxide nanoparticles are among the most commonly studied nanomaterials because of their applications in fields ranging from catalysis to ferrofluids. However, many synthetic methods give iron nanoparticles with large size distributions, and it is difficult to follow the kinetics of iron nanoparticle oxidation reactions and the relative speciation of iron oxidation states in real time. Herein, we introduce a simple approach of controlling the sizes of Fe@FexOy nanoparticles and a novel method for following Fe@FexOy nanoparticle oxidation in situ in liquid solutions by Fe K- and L-edge X-ray absorption near-edge structure (XANES) spectroscopy. XANES results show that these Fe@FexOy nanoparticles have similar XANES spectra before exposure to air. In situ XANES measurements allow for quantitative oxidation kinetics of different nanoparticle sizes to be followed; results show that the rate of Fe(0) oxidation increases with a decrease in average nanoparticle size. However, the rate of Fe core size depletion was found to be ca. 0.02 nm/min for all the nanoparticle systems studied. This suggests similar oxidation mechanisms are at work for all the particle sizes studied. This work shows that in situ liquid cell XANES can be used to follow oxidation state and coordination environment changes in Fe NP dispersions.