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X-ray Photoelectron Spectroscopy (XPS) Analysis of Ultrafine Au Nanoparticles Supported over Reactively Sputtered TiO2 Films

https://doi.org/10.3390/nano12203692

“The impact of a titania (TiO2) support film surface on the catalytic activity of gold nanoparticles (Au NP) was investigated. Using the reactive dc-magnetron sputtering technique, TiO2 films with an amorphous, anatase, and nitrogen-doped anatase crystal structure were produced for a subsequent role as a support material for Au NP. Raman spectra of these TiO2 films revealed that both vacuum and NH3 annealing treatments promoted amorphous to anatase phase transformation through the presence of a peak in the 513–519 cm−1 spectral regime. Furthermore, annealing under NH3 flux had an associated blue shift and broadening of the Raman active mode at 1430 cm−1, characteristic of an increase in the oxygen vacancies (VO). For a 3 to 15 s sputter deposition time, the Au NP over TiO2 support films were in the 6.7–17.1 nm size range. From X-ray photoelectron spectroscope (XPS) analysis, the absence of any shift in the Au 4f core level peak implied that there was no change in the electronic properties of Au NP. On the other hand, spontaneous hydroxyl (–OH) group adsorption to anatase TiO2 support was instantly detected, the magnitude of which was found to be enhanced upon increasing the Au NP loading. Nitrogen-doped anatase TiO2 supporting Au NP with ~21.8 nm exhibited a greater extent of molecular oxygen adsorption. The adsorption of both –OH and O2 species is believed to take place at the perimeter sites of the Au NP interfacing with the TiO2 film. XPS analyses and discussions about the tentative roles of O2 and –OH adsorbent species toward Au/TiO2 systems corroborate very well with interpretations of density functional theory simulations.”

“For surface chemical studies, X-ray photoelectron spectroscopy (XPS) measurements were carried out on a K-Alpha instrument (Thermo Scientific, East Grinstead, UK) using a monochromatic X-ray beam (Al Kα) with a spot size of 300 × 300 μm2. The spectrometer is equipped with a flood gun for charge compensation, any charge-induced energy shift being corrected by fixing the C 1s line at 284.4 eV. For the peak-fitting procedure, a Shirley-type background was subtracted from the spectra while the peaks were fitted with symmetric Gaussian functions.”

The XPS valence band spectra of the three TiO2 films are presented in Figure 3. The TiO2-annealed600-NH3 sample shows a band gap spectrum markedly different from the other samples with the presence of a clear and intense band close to the Fermi-level. This band culminating at ~0.84 eV can be attributed either to the Ti 3d (Ti3+) defect states related to the VO, or to Ti interstitial defects in the TiO2 lattice [32]. This peak also confirms that annealing under NH3 flux leads to the generation of surface defects such as oxygen vacancies, in good agreement with the results of the Raman analysis of the same films.
Figure 3. X-ray photoelectron spectroscope valence band spectra of different titania films.
Upon curve fitting of the N 1s XPS core level spectrum, appears a β-N peak representative of the nitrogen doping via substitution at or near the surface (Figure S1). The generation of oxygen vacancies in the TiO2 anatase phase upon doping with nitrogen was also reported earlier [33,34,35]. The surface of the TiO2-annealed600-NH3 film should, therefore, contain a considerable amount of oxygen vacancies. Nitrogen incorporation into the TiO2 lattice was also quantitatively confirmed using the XPS survey spectrum of the TiO2-annealed600-NH3 film (Figure S2), showing a nitrogen content of 18.5 at.% besides the other detected elements; namely, carbon, titanium, and oxygen. The atomic percent values of Ti, O, C and N in different TiO2 films, calculated from XPS spectra, have been given in Table S1.

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