Diffusive equilibrium properties of O2 in amorphous SiO2 nanoparticles probed via dependence of concentration on size and pressure

An experimental study on the diffusive equilibrium value of interstitial O2 in silica nanoparticles was carried out on samples with average particles diameter 40, 14, and 7 nm. The investigation was performed by measuring the concentration of interstitial O2 by Raman and photoluminescence techniques. The dependence of diffusive equilibrium concentration on pressure and temperature was investigated in the pressure range from 0.2 to 76 bar and in the temperature range from 98 to 244 °C. The equilibrium concentration of interstitial O2 follows Henry’s law at pressures below 13 bar whereas a departure from this model is observed at higher pressures. In particular, O2 concentration saturates abo…

Effects of Pressure, Temperature, and Particles Size on O2 Diffusion Dynamics in Silica Nanoparticles

The O2 diffusion process in silica nanoparticles is experimentally studied in samples of average radius of primary particles ranging from 3.5 to 20 nm and specific surface ranging from 50 to 380 (m2/g). The investigation is done in the temperature range from 98 to 177 °C at O2 pressure ranging from 0.2 to 66 bar by measuring the interstitial O2 concentration by Raman and photoluminescence techniques. The kinetics of diffusion can be described by the Fick’s equation with an effective diffusion coefficient depending on the temperature, O2 pressure, and particles size. In particular, the dependence of the diffusion coefficient on the pressure and nanoparticles size is more pronounced at lower …

Interstitial O2 distribution in amorphous SiO2 nanoparticles determined by Raman an Photoluminescence spectroscopy

The O2 content and emission properties in silica nanoparticles after thermal treatments in oxygen rich atmosphere have been investigated by Raman and photoluminescence measurements. The nanoparticles have different sizes with average diameter ranging from 7 up to 40 nm. It is found that O2 concentration in nanoparticles monotonically increases with nanoparticles size. This finding is independent on the measurement technique and evidences that oxygen molecules are not present in all the nanoparticles volume. This dependence is interpreted on the basis of a structural model for nanoparticles consisting of a core region able to host the oxygen molecules and a surface shell of fixed size and fr…

Optical and morphological properties of infrared emitting functionalized silica nanoparticles

Abstract The loading process of functionalized silica nanoparticles was investigated in order to obtain nanoparticles having functional groups on their surface and Near-Infrared (NIR) emission properties. The NIR emission induced by O 2 loading was studied in silica nanoparticles, produced by pyrogenic and microemulsion methods, with size ranging from 20 to 120 nm. Loading was carried out by thermal treatments in O 2 atmosphere up to 400 °C and 90 bar. The effects of the thermal treatments on the NIR emission and on the structural properties were studied by luminescence and Raman techniques, whereas the morphological features were investigated by Transmission Electron Microscopy and Atomic …

O2 Diffusion in Amorphous SiO2 Nanoparticles Probed by Outgassing

An experimental study of the O2 diffusion process in nanoparticles of amorphous SiO2 in the temperature range from 98 to 157 °C was carried out by Raman and photoluminescence techniques. We studied O2 diffusion in high purity silica nanoparticles with a mean diameter of 14, 20, and 40 nm detecting the outgassing of molecules trapped during the manufacturing. The kinetics of diffusion is well described for all the investigated nanoparticles by the Fick’s equation proving its applicability to nanoscale systems. The diffusion coefficient features an Arrhenius law temperature dependence in the explored temperature range, and the diffusion coefficient values are in good agreement with extrapolat…

Properties of HO2• radicals induced by γ-ray irradiation in silica nanoparticles

Abstract We report an experimental investigation on the effects of γ -ray irradiation in several types of silica nanoparticles previously loaded with O 2 molecules. They differ in specific surface and average diameter. By electron paramagnetic resonance (EPR) measurements we observe the generation of about 10 18 HO 2 • /cm 3 interstitial radicals. These radicals are induced by reaction of interstitial O 2 molecules with radiolytic H atoms, as previously suggested for O 2 -loaded bulk a-SiO 2 samples. However, at variance with respect to bulk materials, our experimental evidences suggest a different generation process of HO 2 • radical. In fact, by a detailed study of samples exposed to D 2 …

Diffusion and outgassing of O<inf>2</inf> in amorphous SiO<inf>2</inf> silica nanoparticles with specific surface properties

O2 trapping in silica nano-structures with high specific surfaces

We report an experimental investigation regarding the entrapping of O2 molecules inside various silica nano– structured systems having specific surfaces from 50 to 1000 m2/g. By recording Raman spectra and Near Infrared O2 emission we studied the O2 content per mass unit. Our data show that the internal voids of these nanostructured systems can trap O2 molecules diffusing from the surrounding air or from a pure O2 atmosphere, whereas the concentration of O2 that can be trapped in the silica near–surface layer is at least one order of magnitude lower. This low ability is consistently observed in non–porous and porous silica nanoparticles and in mesoporous silica systems. Furthermore, we obse…

Photoluminescence and diffusion properties of O2 molecules in amorphous SiO2 nanoparticles

An experimental study by Raman and Photoluminescence (PL) spectroscopies on the emission and diffusion properties of O2 molecules in amorphous SiO2 nanoparticles of commercial origin with diameters from 14 to 40 nm is reported. Stationary and time resolved PL measurements have been carried out to characterize the Near Infrared (NIR) emission at 1272 nm of O2. Emission features similar to those of bulk silica systems with a sharp PL band and excitation channels in the NIR, at 1070 nm, and in the visible, at 765 and 690 nm are found, with peculiarities arising from embedding O2 in nanostructures. The study of the NIR PL lifetime as a function of temperature down to 10 K enabled to reveal the …

Dependence of O2 diffusion dynamics on pressure and temperature in silica nanoparticles

An experimental study of the molecular O2 diffusion process in high purity non-porous silica nanoparticles having 50 m2/g BET specific surface and 20 nm average radius was carried out in the temperature range from 127 to 177 °C at O2 pressure in the range from 0.2 to 66 bar. The study was performed by measuring the volume average interstitial O2 concentration by a Raman and photoluminescence technique using a 1,064 nm excitation laser to detect the singlet to triplet emission at 1,272 nm of the molecular oxygen in silica. A dependence of the diffusion kinetics on the O2 absolute pressure, in addition to temperature dependence, was found. The kinetics can be fit by the solution of Fick’s dif…

Entrapping of O2 Molecules in Nanostructured Silica Probed by Photoluminescence

We studied the emission of the O2 molecules embedded in fumed silica (amorphous silicon dioxide) nanoparticles differing for diameters and specific surface. By using a 1064 nm laser as a source we recorded both the O2 emission and the Raman signal of silica. Our experimental data show that the O2 emission/Raman signal (at 800cm-1) ratio decreases with increasing the specific surface both for the as received and the loaded samples. By performing a thermal treatment (600 °C for 2h) we modified the structure and the water content of the smallest nanoparticles without observing any significant change in the O2 emission/Raman signal ratio. Our data are explained by a shell model showing that the…

Thermally induced structural modifications and O2 trapping in highly porous silica nanoparticles

Abstract In this work we investigate by Raman spectroscopy the effect of isochronal (2 h) thermal treatments in air in the temperature range 200–1000 °C of amorphous silicon dioxide porous nanoparticles with diameters ranging from 5 up to 15 nm and specific surface 590–690 m2/g. Our results indicate that the amorphous structure changes similarly to other porous systems previously investigated, in fact superficial SiOH groups are removed, Si–O–Si linkages are created and the ring statistic is modified, furthermore these data evidence that the three membered rings do not contribute significantly to the Raman signal detected at about 495 cm−1. In addition, after annealing at 900 and 1000 °C we…