Optical and magnetic properties of SiO2:C nanopowders obtained by chemical and thermal modification of fumed silica were studied by Fourier transform infrared spectroscopy, Raman, continuous wave (CW) electron paramagnetic resonance (EPR), echo-detected EPR and pulsed electron nuclear double resonance (ENDOR) spectroscopy. Two overlapping signals of Lorentzian lineshape were detected in CW EPR spectra of the initial SiO2:C. The EPR signal at g = 2.0055(3) is due to the silicon dangling bonds, which vanishes after thermal annealing, and the second EPR signal at g = 2.0033(3) was attributed to the carbon-related defect (CRD). The annealing of the SiO2:C samples gives rise to the increase of the CRD spin density and shift to the higher g-values due to the appearance of the oxygen in the vicinity of the CRD. Based on the temperature-dependent behavior of the CRD EPR signal intensity, linewidth and resonance field position we have attributed it to the spin system with non-localized electrons hopping between neighboring carbon dangling bonds, which undergo a strong exchange interaction with a localized spin system of carbon nanodots. The observed motional narrowing of the CRD EPR signal in the temperature interval from 4 to 20 K indicates that electrons are mobile at 4 K which can be explained by a quantum character of the conductivity in the vicinity of the carbon layer. The electrons trapped in quantum wells move from one carbon nanodot to another by hopping process through the energy barrier. The fact that echo-detected EPR signal at g = 2.0035(3) was observed in SiO2:C sample annealed at T ann ≥ 700 °C serves as evidence that non-localized electrons coexist with localized electrons that have the superhyperfine interaction with surrounding 13C and 29Si nuclei located at the SiO2:C interface. The presence of the superhyperfine interaction of CRD with 1H nuclei indicates the existence of hydrogenated regions in SiO2:C sample.

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Fumed silica with a specific area of 295 m 2 /g was carbonized by successive phenyltrimethoxysilane treatments followed by annealing in inert atmosphere up to 650 C. Emission, excitation, kinetics, and photo-induced bleaching effects were investigated by steady state and time-resolved photoluminescence spectroscopies. The local chemistry was also studied by infrared transmission spectroscopy. Strong ultraviolet and visible photoluminescence was observed in the samples after the chemical treatments/modifications and thermal annealing. It has been shown that ultraviolet photoluminescence in chemically modified fumed silica is associated with phenyl groups, while near ultraviolet and visible emission in annealed samples originated from inorganic pyrolytic carbon precipitates dispersed in the silica host matrix. Two types of emission bands were identified as a function of the annealing temperature: one is in the near UV and the other is in the visible range. Based on the emission/excitation analysis of these two bands, as well as on correlations with the synthesis conditions, a structural-energy concept of light-emitting centers has been proposed. According to this model, the light-emitting centers are associated with carbon clusters that can be bonded or adsorbed on the silica surface. This has been validated by a detailed (S)TEM-electron energy-loss spectroscopy study, confirming the inhomogeneous distribution of nanoscale carbon precipitates at the surface of the silica nanoparticles. These carbon precipitates are mostly amorphous although they possess some degree of graphitization and local order. Finally, the fraction of sp 2 carbon in these nanoclusters has been estimated to be close to 80%. Published by AIP Publishing. https://doi.

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