Oxidation of gold metal particles supported on TiO2: an FTIR study by means of low-temperature CO adsorption
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Two Au/TiO2 samples with different gold loadings (0.7 and 4.0 wt.% Au) were prepared by deposition-precipitation with urea and calcined at 673 K. TEM revealed gold particles of 3.2 and 3.9 nm for the 0.7 and 4.0 wt.% samples, respectively. The samples were subjected to different red-ox treatments and then the state of gold was determined by the FTIR spectra of CO adsorbed at low temperature. Several kinds of gold carbonyl species were detected during the experiments: (i) Au0–CO at around 2107 cm−1; (ii) Au+–CO at ca. 2175 cm−1; (iii) Auδ+–CO in the region of 2140–2137 cm−1 and (iv) Auδ′+–CO (δ′ > δ) at around 2155 cm−1. The 4.0 wt.% sample contained mainly metallic gold after evacuation at 673 K. Subsequent interaction with oxygen at 373 K leads to oxidation of a fraction of the surface metallic gold sites to Auδ+ sites. These sites were considered as cations located on the surface of the metal particles with a partially positive charge δ+ (0 < δ < 1) because of electron transfer from the gold bulk. Evacuation at 673 K leads to back reduction of the Auδ+ sites to metallic gold. The oxidation of gold particles was more efficient when performed with a NO + O2 mixture. It resulted in creation of Auδ′+ sites with a higher positive charge than that of the Auδ+ sites. In this case the oxidation involved a higher number of Au0 sites. A similar treatment of the 0.7 wt.% Au sample, however, resulted in formation of “isolated” Au+ species. The results indicate that small metal particles are more easily oxidized by a NO + O2 mixture. A model of the formation of the different sites, explaining well the experimental results, is proposed.
KeywordsGold Particle Gold Atom Metallic Gold Carbonyl Band Gold Particle Size
The authors are grateful to Egide, France (Project ECO-NET No 101186SH). We also thank S. Pronier for the TEM analyses and L.T.N. Nguyen for the preparation of the Au/TiO2 (0.7 Au wt %) sample.
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