Aggregation Of Titanium Dioxide Nanoparticles Research Articles

Multi-Scale Modelling of Aggregation of TiO2 Nanoparticle Suspensions in Water.

Titanium dioxide nanoparticles have risen concerns about their possible toxicity and the European Food Safety Authority recently banned the use of TiO2 nano-additive in food products. Following the intent of relating nanomaterials atomic structure with their toxicity without having to conduct large-scale experiments on living organisms, we investigate the aggregation of titanium dioxide nanoparticles using a multi-scale technique: starting from ab initio Density Functional Theory to get an accurate determination of the energetics and electronic structure, we switch to classical Molecular Dynamics simulations to calculate the Potential of Mean Force for the connection of two identical nanoparticles in water; the fitting of the latter by a set of mathematical equations is the key for the upscale. Lastly, we perform Brownian Dynamics simulations where each nanoparticle is a spherical bead. This coarsening strategy allows studying the aggregation of a few thousand nanoparticles. Applying this novel procedure, we find three new molecular descriptors, namely, the aggregation free energy and two numerical parameters used to correct the observed deviation from the aggregation kinetics described by the Smoluchowski theory. Ultimately, molecular descriptors can be fed into QSAR models to predict the toxicity of a material knowing its physicochemical properties, enabling safe design strategies.

Influence of Aqueous Inorganic Anions on the Reactivity of Nanoparticles in TiO2 Photocatalysis.

The influence of inorganic anions on the photoreactivity and aggregation of titanium dioxide nanoparticles (NPs) was assessed by dosing carbonate, chloride, nitrate, phosphate, and sulfate as potassium salts at multiple concentrations. NP stability was monitored in terms of aggregate morphology and electrophoretic mobility (EPM). Aggregate size and fractal dimension were measured over time by laser diffraction, and the isoelectric point (IEP) as a function of anion and concentration was obtained by measuring EPM versus pH. Phosphate, carbonate, and to a lesser extent, sulfate decreased the IEP of TiO2 and stabilized NP suspensions owing to specific surface interactions, whereas this was not observed for nitrate and chloride. TiO2 NPs were exposed to UV-A radiation, and the photoreactivity was assessed by monitoring the production of reactive species over time both at the NP surface (photogenerated holes) and in the bulk solution (hydroxyl radicals) by observing their reactions with the selective probe compounds iodide and terephthalic acid, respectively. The generation of photogenerated holes and hydroxyl radicals was influenced by each inorganic anion to varying degrees. Carbonate and phosphate inhibited the oxidation of iodide, and this interaction was successfully described by a Langmuir-Hinshelwood mechanism and related to the characteristics of TiO2 aggregates. Chloride and nitrate do not specifically interact with TiO2, and sulfate creates relatively weak interactions with the TiO2 surface such that no decrease in photogenerated hole reactivity was observed. A decrease in hydroxyl radical generation was observed for all inorganic anions. Quenching rate constants for the reaction of hydroxyl radicals with each inorganic anion do not provide a comprehensive explanation for the magnitude of this decrease, which arises from the interplay of several physicochemical phenomena. This work shows that the reactivity of NPs will be strongly influenced by the makeup of the waters they are released into. The impact of anion species on hydroxyl radical inhibition was as follows: carbonate > chloride > phosphate > nitrate > sulfate.

Influences of anion concentration and valence on dispersion and aggregation of titanium dioxide nanoparticles in aqueous solutions

Dispersion and aggregation of nanoparticles in aqueous solutions are important factors for safe application of nanoparticles. In this study, dispersion and aggregation of nano-TiO2 in aqueous solutions containing various anions were investigated. The influences of anion concentration and valence on the aggregation size, zeta potential and aggregation kinetics were individually investigated. Results showed that the zeta potential decreased from 19.8 to −41.4mV when PO43− concentration was increased from 0 to 50mg/L, while the corresponding average size of nano-TiO2 particles decreased from 613.2 to 540.3nm. Both SO42− and NO3− enhanced aggregation of nano-TiO2 in solution. As SO42− concentration was increased from 0 to 500mg/L, the zeta potential decreased from 19.8 to 1.4mV, and aggregate sizes increased from 613.2 to 961.3nm. The trend for NO3− fluctuation was similar to that for SO42− although the range of variation for NO3− was relatively narrow. SO42− and NO3− accelerated the aggregation rapidly, while PO43− did so slowly. These findings facilitate the understanding of aggregation and dispersion mechanisms of nano-TiO2 in aqueous solutions in the presence of anions of interest.

The effect of humic acid on the aggregation of titanium dioxide nanoparticles under different pH and ionic strengths

With the increasingly widespread use of titanium dioxide nanoparticles (TiO2 NPs), the particles' environmental impacts have attracted concern, making it necessary to understand the fate and transport of TiO2 NPs in aqueous media. In this study, we investigated TiO2 NP aggregation caused by the effects of humic acid (HA), ionic strength (IS) and different pH using dynamic light scattering (DLS) to monitor the size distribution of the TiO2 NPs continuously. It was determined that HA can influence the stability of TiO2 NPs through charge neutralization, steric hindrance and bridging effects. In the absence of IS, aggregation was promoted by adding HA only when the pH (pH=4) is less than the point of zero charge for the TiO2 NPs (pHPZC≈6) because HA reduces the zeta potential of the TiO2 NPs via charge neutralization. At pH=4 and when the concentration of HA is 94.5μg/L, the zeta potential of TiO2 NPs is close to zero, and they reach an aggregation maximum. A higher concentration of HA results in more negatively charged TiO2 NP surfaces, which hinder their aggregation. When the pH is 5.8, HA enhances the negative zeta potential of the TiO2 NPs and increases their stability via electrostatic repulsion and steric hindrance. When the pH (pH=8) is greater than pHpzc, the zeta potential of the TiO2 NPs is high (~40mV), and it barely changes with increasing HA concentration. Thus, the TiO2 NPs are notably stable, and their size does not grow at pH8. The increase in the critical coagulation concentration (CCC) of TiO2 NPs indicated that there is steric hindrance after the addition of HA. HA can enhance the coagulation of TiO2 NPs, primarily due to bridging effect. These findings are useful in understanding the size change of TiO2 NPs, as well as the removal of TiO2 NPs and HA from aqueous media.

Effects of material properties on sedimentation and aggregation of titanium dioxide nanoparticles of anatase and rutile in the aqueous phase

This study investigated the sedimentation and aggregation kinetics of titanium dioxide (TiO 2) nanoparticles with varying material properties (i.e., crystallinity, morphology, and chemical composition). Used in the study were various types of commercially available TiO 2 nanoparticles: three spherical anatase (nominal diameters of 5, 10, and 50 nm) and two rutile nanoparticles (10 × 40 and 30 × 40 nm). The 50 nm anatase and 10 × 40 nm rutile showed higher stability in deionized water and 5 mM NaCl solutions at pH 7 than the 5, and 10 nm anatase nanoparticles in sedimentation experiments. In aggregation experiments, critical coagulation concentration values for the 50 nm anatase were the highest, followed by the 10 × 40 nm rutile and the 5 nm anatase nanoparticles in NaCl and CaCl 2 solutions. The aggregation kinetics was fitted reasonably well with the Derjaguin–Landau–Verwey–Overbeek (DLVO) equations for the TiO 2 nanoparticles tested. Results showed that crystallinity and morphology are not influential factors in determining the stability of TiO 2 nanoparticle suspensions; however, the differences in their chemical compositions, notably, the varying concentrations of impurities (i.e., silicon and phosphorus) in the pristine materials, determined the surface charge and therefore the sedimentation and aggregation of TiO 2 nanoparticles in the aqueous phase.

Aggregation of titanium dioxide nanoparticles: role of calcium and phosphate

Environmental context. The increasing use of nanomaterials in consumer products has led to increased concerns about their potential environmental and health impacts. TiO2 is a widely used nanoparticle found in sunscreens and electronic products. In order to understand and predict the mobility of TiO2 in the natural environment, it is essential to determine its state of aggregation under environmentally relevant conditions of pH, ionic strength, ion and natural organic matter content. Aggregation is likely to lead to both reduced mobility and bioavailability in soils and natural waters. Abstract. The physicochemical characterisation of nanomaterials is crucial to predict their environmental and health impacts. Ion adsorption is known to influence the surface properties of nano-metal oxides in natural systems. The role of calcium and phosphate adsorption on aggregation was examined in the presence and absence of natural organic matter. Fluorescence correlation spectroscopy (FCS) was performed in order to determine the diffusion coefficients of TiO2 nanoparticles having a nominal size between 3 to 5 nm. Based upon FCS and electrophoretic mobility measurements, the presence of calcium resulted in a destabilisation and aggregation of the TiO2 nanoparticles, even in presence of Suwannee River fulvic acid (SRFA). Conditions which favoured phosphate adsorption also resulted in a destabilisation of the TiO2 sample but for low SRFA concentrations only.

Aggregation of Titanium Dioxide Nanoparticles: Role of a Fulvic Acid

The increasing use of nanomaterials in consumer products has led to increased concerns abouttheir potential environmental and health impacts. To better understand the transport, fate, and behavior of nanoparticles in aquatic systems, it is essential to understand their interactions with different components of natural waters including natural organic matter over a broad range of physicochemical conditions. Fluorescence correlation spectroscopy was used to determine the diffusion coefficients of TiO2 nanoparticles having a nominal size of 5 nm. The effects of a various concentrations of the Suwannee River Fulvic Acid (SRFA) and the roles of pH and ionic strength were evaluated. Aggregation of the bare TiO2 nanoparticles increased for pH values near the zero point of charge. At any given pH, an increase in ionic strength generally resulted in increased aggregation. Furthermore, conditions which favored adsorption of the SRFA resulted in less aggregation of the TiO2 nanoparticles, presumably due to increased steric repulsion. Under the conditions studied here, nanoparticle dispersions were often stable for environmentally relevant conditions of SRFA, pH, and ionic strength, suggesting that in the natural environment, TiO2 dispersion might occur to a greater extent than expected.