Abstract
Bipyramidal Au microcrystallites have been synthesized by thermalizing a Au-organic complex in the presence of Ag(I) ions, the latter acting as a shape-directing agent. With a highly corrugated morphology leading to strain-induced non-face-centered cubic (non-FCC) Au phases, the non-FCC portion can be tuned by varying the Ag/Au ratio, as verified by diffraction measurements. For a Ag/Au ratio of 0.34, the non-FCC Au portion was as high as 85%. X-ray microdiffraction and electron diffraction measurements reveal that the non-FCC contribution comes primarily from bipyramids, while other microcrystallites, namely, tetrahexahedrons and hexagrams, host non-FCC phases only at the edges and, to an even lesser extent, at the corners. When used as a catalyst for p-nitrophenol reduction, the non-FCC microcrystallites exhibit a significantly enhanced activity compared to FCC Au, which shows only negligible activity. These results are in accordance with trends in the values of two descriptors of reactivity calculated from first principles: The effective coordination number is found to decrease and the d-band center is found to increase in energy going from the FCC to the non-FCC phases of Au. Our findings contradict the general notion that Au is catalytically active only in nanodimensions and is otherwise inert; in this system, its activity arises from the non-FCC phases.
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Acknowledgements
The authors thank Prof. C. N. R. Rao for his constant encouragement. We thank Mr. B. N. Rao for his assistance in profile fitting. G. M. thanks CSIR, India, for a fellowship. S. N. acknowledges funding from the Sheikh Saqr Laboratory of ICMS, JNCASR.
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Mettela, G., Mammen, N., Joardar, J. et al. Non-FCC rich Au crystallites exhibiting unusual catalytic activity. Nano Res. 10, 2271–2279 (2017). https://doi.org/10.1007/s12274-017-1417-y
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DOI: https://doi.org/10.1007/s12274-017-1417-y