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Selective oxidation with dioxygen by gold nanoparticle catalysts derived from 55-atom clusters


Supported gold nanoparticles have excited much interest owing to their unusual and somewhat unexpected catalytic properties1,2,3,4,5,6,7, but the origin of the catalytic activity is still not fully understood. Experimental work4 on gold particles supported on a titanium dioxide (110) single-crystal surface has established a striking size threshold effect associated with a metal-to-insulator transition, with gold particles catalytically active only if their diameters fall below 3.5 nm. However, the remarkable catalytic behaviour might also in part arise from strong electronic interaction between the gold and the titanium dioxide support2,3,5. In the case of industrially important selective oxidation reactions, explanation of the effectiveness of gold nanoparticle catalysts is complicated by the need for additives to drive the reaction5,7,8, and/or the presence of strong support interactions and incomplete understanding of their possible catalytic role1,2,3,5. Here we show that very small gold entities (1.4 nm) derived from 55-atom gold clusters and supported on inert materials are efficient and robust catalysts for the selective oxidation of styrene by dioxygen. We find a sharp size threshold in catalytic activity, in that particles with diameters of 2 nm and above are completely inactive. Our observations suggest that catalytic activity arises from the altered electronic structure intrinsic to small gold nanoparticles, and that the use of 55-atom gold clusters may prove a viable route to the synthesis of robust gold catalysts suited to practical application.

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Figure 1: High-resolution TEM images overlaid with corresponding particle size distributions for unsupported and supported Au55.
Figure 2: Au 4 f electron region of the X-ray photoelectron spectrum of 0.6-wt% Au 55 /BN (black curve) and the corresponding spectrum of a bulk Au reference (grey curve).

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M.T. and O.P.H.V. acknowledge financial support from the UK Engineering and Physical Sciences Research Council and King’s College, Cambridge, respectively.

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Correspondence to Richard M. Lambert.

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Supplementary Figures

This file contains Supplementary Figures 1 and 2 with Legends that describe the characterization of the 0.6 wt% Au/SiO2 catalyst prepared using PVP method and the characterization of the 1 wt% Au/C catalyst prepared using the microemulsion method, respectively; Supplementary Table 1 giving a full statistical breakdown of the particle size distributions of all catalysts; Supplementary Figures 3 and 4 with Legends and Supplementary Discussion describing the effect of catalyst thermal treatment; and additional references. (PDF 1878 kb)

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Turner, M., Golovko, V., Vaughan, O. et al. Selective oxidation with dioxygen by gold nanoparticle catalysts derived from 55-atom clusters. Nature 454, 981–983 (2008).

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