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Nat Commun. 2017 Feb 22;8:14459. doi: 10.1038/ncomms14459.

Enhanced oxidation resistance of active nanostructures via dynamic size effect.

Liu Y1,2, Yang F1, Zhang Y1,2, Xiao J1, Yu L1, Liu Q1,2, Ning Y1, Zhou Z1,2, Chen H1,2, Huang W1,2, Liu P3, Bao X1.

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State Key Laboratory of Catalysis, CAS Center for Excellence in Nanoscience, Collaborative Innovation Center of Chemistry for Energy Materials, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Zhongshan Road 457, Dalian 116023, China.
University of Chinese Academy of Sciences, Beijing 100049, China.
Chemistry Department, Brookhaven National Laboratory, Upton, New York 11973, USA.


A major challenge limiting the practical applications of nanomaterials is that the activities of nanostructures (NSs) increase with reduced size, often sacrificing their stability in the chemical environment. Under oxidative conditions, NSs with smaller sizes and higher defect densities are commonly expected to oxidize more easily, since high-concentration defects can facilitate oxidation by enhancing the reactivity with O2 and providing a fast channel for oxygen incorporation. Here, using FeO NSs as an example, we show to the contrary, that reducing the size of active NSs can drastically increase their oxidation resistance. A maximum oxidation resistance is found for FeO NSs with dimensions below 3.2 nm. Rather than being determined by the structure or electronic properties of active sites, the enhanced oxidation resistance originates from the size-dependent structural dynamics of FeO NSs in O2. We find this dynamic size effect to govern the chemical properties of active NSs.

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