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A spectroscopic study of the gold nanoparticle (NP) formation by high-intensity femtosecond laser irradiation of a gold ion solution was reported. The effect of varying energy density of the laser on the formation of gold NPs was also investigated. The surface plasmon resonance (SPR) peak of the gold nanocolloid in real-time UV-visible absorption spectra during laser irradiation showed a distinctive progress; the SPR absorption peak intensity increased after a certain irradiation time, reached a maximum and then gradually decreased. During this absorption variation, at the same time, the peak wavelength changed from 530 to 507 nm. According to an empirical equation derived from a large volume of experimental data, the estimated mean size of the gold NPs varied from 43.4 to 3.2 nm during the laser irradiation. The mean size of gold NPs formed at specific irradiation times by transmission electron microscopy showed the similar trend as that obtained in the spectroscopic analysis. From these observations, the formation mechanism of gold NPs during laser irradiation was considered to have two steps. The first is a reduction of gold ions by reactive species produced through a non-linear reaction during high intensity laser irradiation of the solution; the second is the laser fragmentation of produced gold particles into smaller pieces. The gold nanocolloid produced after the fragmentation by excess irradiation showed high stability for at least a week without the addition of any dispersant because of the negative charge on the surface of the nanoparticles probably due to the surface oxidation of gold nanoparticles. A higher laser intensity resulted in a higher efficiency of gold NPs fabrication, which was attributed to a larger effective volume of the reaction

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Resonant high-energy X-ray diffraction coupled to atomic pair distribution function analysis and computer simulations is used to study the atomic-scale structure of group 11 nanosized metals and binary alloy catalysts. We find that nanosized Cu is quite disordered structurally whereas nanosized Ag and especially Au exhibit a very good degree of crystallinity. We resolve Cu−Cu and Ag−Ag atomic correlations from Auinvolving ones in Au−Cu and Au−Ag nanoalloys and show that depending on the synthetic route group 11 binary alloys may adopt structural states that obey or markedly violate Vegard's law. In the latter case, Cu and Ag atoms undergo substantial size expansion and contraction by as much as 0.3 and 0.03 Å, respectively, while heavier Au atoms remain practically intact. The size change of Cu and Ag atoms does not follow Pauling's rule of electronegativity predicting charge flow toward the more electronegative Au but occurs in a way such that Cu/Au and Ag/Au atomic size ratios in the nanoalloys become closer to one. Atomic size adjusting and the concurrent charge redistribution result in a synergistic effect of oxygen inactive Au and oxygen very active Cu and Ag leading to nanoalloys with very good activity for low-temperature oxidation of CO.

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