The range of validity of sorption kinetic models

Several hundred papers are published yearly reporting liquid-phase adsorption kinetics data. In general the data is analyzed using a variety of standard models such as the pseudo first- and second-order models and the Intraparticle-Diffusion model. The validity of these models is often assessed empirically via their ability to fit the data, independently of their physicochemical soundness. The aim of the present paper is to rationalize the analysis of liquid-phase adsorption kinetics data, and to investigate experimental factors that influence the adsorption kinetics, in addition to the characteristics of the adsorbent material itself. For that purpose we use a simple Langmuir adsorption–diffusion model, which enables us to identify three dimensionless numbers that characterize the working regime of any batch adsorption experiment: an adsorption Thiele modulus, a saturation modulus, and a loading modulus. The standard models are found to be particular cases of the general adsorption–diffusion model for specific values of the dimensionless numbers. This provides sound physicochemical criteria for the validity of the models. Based on our modeling, we also propose a general yet simple data analysis procedure to practically estimate the diffusion coefficient in adsorbent pellets starting from adsorption halftimes

Core-shell AgSiO2-Protoporphyrin IX nanoparticle: Effect of the Ag core on reactive oxygen species generation

peer reviewedPhotodynamic therapy (PDT) for cancer is based on the use of a light sensitive molecule to produce, under specific irradiation, toxic reactive oxygen species (ROS). A way to improve the therapy efficiency is to increase the amount of produced ROS near cancer cells. This aim can be achieved by using a metal enhanced process arising when an optically active molecule is located near a metallic nanoparticle (NP). Here, the coupling effect between silver (Ag) NPs and protoporphyrin IX (PpIX) molecules, a clinically approved photosensitizer, is studied compared first, to PpIX fluorescence yield and second, to ROS production efficiency. By applying a modified Stöber process, PpIX was encapsulated into a silica (SiO2) shell, surrounding a 60 nm sized Ag core. We showed that, compared to SiO2-PpIX NPs, Ag coated SiO2-PpIX NPs dramatically decreased PpIX fluorescence together with singlet oxygen production efficiency. However, after incubation time in the dark, the amount of superoxide anions generated by the Ag doped sample was higher than the control sample one

Protoporphyrin IX Functionalised AgSiO2 Core-shell Nanoparticle: Plasmonic Enhancement of Fluorescence and Singlet Oxygen Production

Metal-enhanced processes arising from the coupling of a dye with metallic nanoparticles (NPs) have been widely reported. However, few studies have simultaneously investigated these mechanisms from the viewpoint of dye fluorescence and photoactivity. Herein, protoporphyrin IX (PpIX) is grafted onto the surface of silver core silica shell NPs in order to investigate the effect of silver (Ag) localized surface plasmon resonance (LSPR) on PpIX fluorescence and PpIX singlet oxygen (1O2) production. Using two Ag core sizes, we report a systematic study of these photophysical processes as a function of silica (SiO2) spacer thickness, LSPR band position and excitation wavelength. The excitation of Ag NP LSPR, which overlaps the PpIX absorption band, leads to the concomitant enhancement of PpIX fluorescence and 1O2 production independently of the Ag core size, but in a more pronounced way for larger Ag cores. These enhancements result from the increase in the PpIX excitation rate through the LSPR excitation and decrease when the distance between PpIX and Ag NPs increases. A maximum fluorescence enhancement of up to 14-fold, together with an increase in photogenerated 1O2 production of up to five times are obtained using 100 nm Ag cores coated with a 5 nm thick silica coating

Li7La3Zr2O12/LiCoO2 - cathode for all-solid-state batteries

EnS

Heterogeneous singlet oxygen generation: in-operando visible light EPR spectroscopy

The use of photosensitizers immobilized on mesoporous materials to produce singlet oxygen (1O2) has opened a new way to synthetic and environmental applications due to the fast development of flow photochemistry and continuous-flow microreactors. 1O2-based photosensitized processes can be employed for the degradation of organic pollutants in aqueous medium and the photosensitizer can be covalently attached to the support and separated from the effluent reducing the environmental impact. The aim of the present paper is to evaluate the 1O2 generation of Rose Bengal (RB) in homogeneous and heterogeneous systems using in-operando evaluation. Mesoporous SiO2 nanoparticles (MSNs) were successfully conjugated with RB (MSN-RB) and Electron Paramagnetic Resonance (EPR) spectroscopy in combination with the spin trap TEMP was employed to obtain paramagnetic TEMPO via generated 1O2 when RB or MSN-RB are exposed to visible light. Additionally, EPR/DMPO was used to exclude the possible generation of other reactive oxygen species (ROS) by the functionalized nanoparticles. We found that in situ 1O2 generation was enhanced when the same amount of RB is immobilized inside of mesoporous SiO2

Photocatalytic decomposition of hydrogen peroxide over nanoparticles of TiO2 and Ni(II)-porphyrin doped TiO2: a relationship between activity and porphyrin anchoring mode

peer reviewedThe nickel tetra(4-carboxyphenyl)porphyrin (TCPPNi) was chimisorbed on Degussa P25 TiO2 at different concentrations. Diffuse reflectance spectroscopy in the UV/vis region, Fourier transform infrared spectroscopy and thermal gravimetry combined with differential scanning calorimetry measurements allowed the determination of the TCPPNi anchoring mode. At low TCPPNi concentrations, this anchoring on Degussa P25 TiO2 took place through all four carboxylic groups, while at higher concentrations the anchoring occurred through one or two carboxylic groups. For the firsttime,the effect of UV/vis light irradiation on the H2O2-degradation activity of TiO2 and TCPPNi-doped TiO2 was studied using the method of following the production of O2 by gas pressure monitoring. The activity of seven different catalysts was related to the TCPPNi anchoring mode and the percentage of TiO2 Degussa P25 coverage. An optimum degradation of H2O2 was observed for 0.0115 mol TCPPNi × g−1 P25. In that case, the TCPPNi was anchored through the four carboxylic groups, corresponding to a strong interaction with Degussa P25 TiO2. Moreover, the TCPPNi did not cover the surface completely, therefore allowing the light to reach and activate the TiO2

Photocatalytic degradation of water pollutants with visible light-sensitized TiO2 xerogels

peer reviewedTo extend its photocatalytic activity to visible light, TiO2 has been doped in situ through the cogelation sol-gel proces with two dyes : free metal tetra(4-carboxyphenyl)porphyrin and nickel tetra(4-carboxyphenyl)porphyrin. DR and FT-IR spectroscopies have been performed to determine the interaction between porphyrins and TiO2. Cristallinity and specific surface area have been measured by XRD and N2 adsorption. The photoactivity of the doped TiO2 xerogels has been evaluated for p-nitrophenol (a model water pollutant) degradation under visible light and a kinetic study has been performed. The samples allow the degradation of 40% of p-nitrophenol in 6 h which makes them very promising for water decontamination under natural light. A kinetic study of p-nitrophenol degradation with the Ni-doped catalyst has shown that the best kinetic model involves one type of active site corresponding to the hole h+ of electron-hole pairs created at the TiO2 surface by light. The rate determining step consists of the surface reaction between adsorbed p-nitrophenol and adsorbed OH• radicals

Characterization of photoactive coatings of SiO2 nanoparticles and Rose Bengal onto glass surfaces

The fluorescence emission and singlet oxygen (1O2) production have been widely investigated over the last decade due to high-value added applications such as organic chemical synthesis1, wastewater treatment2 or photodynamic cancer therapy3. This work is dedicated to the synthesis and deposition of SiO2 nanoparticles on glass surfaces using Stober’s process and dip coating, respectively. The adherence was improved through the incorporation of different concentrations of these nanoparticles into a TiO2 matrix. Additionally, the speed of dip coating was used to modify SiO2 thicknesses. Rose bengal was covalently anchored to SiO2 coatings through (3-aminopropyl)triethoxysilane (APTES) linker. UV, IR, fluorescence, SEM and profilometry were used to characterize the corresponding films and the efficiency for singlet oxygen production was measured by oxidation of the amino acid methionine. The immobilization of SiO2 nanoparticles photosensitized with rose bengal showed promising results for the production of singlet oxygen