Effect of synthesis parameters on the particle size, composition and colloid stability of polypyrrole–silica nanocomposite particles

 The effect of varying the oxidant, monomer and silica sol concentrations, silica sol diameter, polymerization temperature, stirring rate and oxidant type, on the particle size, polypyrrole content and conductivity of the resulting polypyrrole– silica colloidal nanocomposites has been studied. Surprisingly, nanocomposite formation appears to be relatively insensitive to most of the above synthesis parameters. One synthesis parameter which does have a significant and reproducible effect is the stirring rate: smaller, more monodisperse nanocomposite particles are obtained from rapidly stirred reaction solutions. However, this effect is only observed for the (NH₄)₂S₂O₈ oxidant. An alternative oxidant, H₂O₂/Fe³⁺, was found to give nanocomposites of similar particle size, polypyrrole content and conductivity to those obtained using the (NH₄)₂S₂O₈ oxidant. The colloid stability of these polypyrrole–silica nanocomposite particles depends on their silica content. The colloid stability of a silica-rich nanocomposite prepared using the (NH₄)₂S₂O₈ oxidant in the presence of electrolyte was comparable to that of a silica sol, whereas a polypyrrole-rich nanocomposite prepared using FeCl₃ had markedly poorer colloid stability under these conditions. These observations are consistent with a charge stabilization mechanism for these nanocomposite particles. Received: 5 March 1998 Accepted: 27 April 1998     

Kinetics of the formation of precipitates and the physicochemical properties of technetium-99 and rhenium sulfides according to small-angle X-ray scattering and ultramicrocentrifugation data

The interaction of technetium and rhenium with sulfides in aqueous solutions was studied by small-angle X-ray scattering and ultramicrocentrifugation. It was shown that, although the stoichiometry of technetium sulfide corresponds to the formula Tc₂S_7–x, the oxidation state of technetium in it is +4 and the excess sulfur is bound into a disulfide group so that its formula can correctly be written as [Tc₃(µ³-S)(µ²-S₂)₃(S₂)_(3n–n)/n)]_n. The determination of the solubility of technetium sulfide is complicated by its tendency to form colloids, which was the reason why the above methods were chosen to find features of its formation and describe its solubility in solutions.     

Gold colloid analysis by inductively coupled plasma-mass spectrometry in a single particle mode

Analysis in a single particle mode of gold colloids in water has been performed by inductively coupled plasma-mass spectrometry (ICP-MS). The signal induced by the flash of ions due to the ionization of a colloid in the plasma torch can be measured for the ions ¹⁹⁷Au⁺ by the mass spectrometer without interferences. The intensity of the MS signal is recorded in time scan. The recorded peak distributions were analysed as a function of the colloid size for five monodisperse colloids (80-250 nm). This study describes the experimental conditions to analyse gold colloids in a single particle mode. The size detection limit is around 25 nm corresponding to 0.15 fg colloids and one particle per ml may be detected during a 1 min time scan within standard procedure.     

Particle size dependence of electro-optical switching in ZrP nano colloid

Aqueous colloid of 2-dimensional (2D) α-ZrP nanoparticles can serve as an excellent material for Kerr devices. We investigate the influence of the particle size on the electro-optical switching for isotropic and biphasic α-ZrP colloids that exhibit stable Kerr effect. Smaller sized α-ZrP colloid has wider range of isotropic and biphasic phases, but since the anisotropic polarizability is approximately proportional to square diameter of particles, the larger sized α-ZrP colloid has higher birefringence at a given concentration. The dynamic response time is also dramatically influenced by the particle size. Smaller sized particle has lower viscosity, and the fall time monotonically increases with increasing particle size. However, the rise time has the minimum at around 0.6 μm owing to the competitive contributions of the anisotropic polarizability and the rotational viscosity. Thus, the particle size in α-ZrP colloid is an important factor to determine the electro-optical performance of a Kerr device based on 2D α-ZrP colloids. These findings will be important in developing electro-optical devices using lyotropic liquid crystal colloids.     

Preparation and catalytic properties of NR-stabilized palladium colloids

Palladium colloids revealing narrow particle size distributions can be obtained by chemical reduction using tetra–alkylammonium hydrotriorganoborates. Combining the stabilizing agent [NR] with the reducing agent [BEt₃H^?] provides a high concentration of the protecting group at the reduction centre. Alternatively, NR₄X (X = halogen) may be coupled to the metal salt prior to the reduction step: addition of N(octyl)₄Br to Pd(ac)₂ in THF, for example, evokes an active interaction between the stabilizing agent and the metal salt. Reduction of NR-stabilized palladium salts with simple reducing agents such as hydrogen at room temperature yields stable palladium organosols which may be isolated in the form of redispersible powders. The anion of the palladium salt is crucial for the success of the colloid synthesis. Electron microscopy shows that the mean particle size ranges between 1.8 and 4.0 nm. An X–ray–photoelectron spectrscopic examination demonstrated the presence of zerovalent palladium. These palladium colloids may serve as both homogeneous and heterogeneous hydrogenation catalysts. Adsorption of the colloids onto industrially important supports can be achieved without agglomeration of palladium particles. The standard activity of a charcoal catalyst containing 5% of colloidal palladium determined through the cinnamic acid standard test was found to exceed considerably the activity of the conventional technical catalysts. In addition, the lifespan of the catalyst containing a palladium colloid, isolated from the reduction of [N(octyl)₄]₂PdCl₂Br₂ with hydrogen, is superior to conventionally prepared palladium/charcoal (Pd/C) catalysts. For example, the activity of a conventional Pd/C catalyst is completely suppressed after 38×10³ catalytic cycles per Pd atom, whereas the colloidal Pd/C catalyst shows activity even after 96times;10³ catalytic cycles.     

Uranium colloid analysis by single particle inductively coupled plasma-mass spectrometry

Uranium single particle analysis has been performed by inductively coupled plasma-mass spectrometry (ICP-MS) and the performances are compared with that provided by scanning electron microsopy and single particle counting. The transient signal induced by the flash of ions due to the ionisation of an uranium colloidal particle in the plasma torch can be detected and measured for selected uranium ion masses (²³⁸U⁺, ²³⁵U⁺ or ²⁵⁴[²³⁸U¹⁶O]⁺) by the mass spectrometer. The signals recorded via time scanning are analysed as a function of particle size or fraction of the studied element or isotope in the colloid phase. The frequency of the flashes is directly proportional to the concentration of particles in the colloidal suspension. The feasibility tests were performed on uranium dioxide particles. The study also describes the experimental conditions and the choice of mass to detect uranium colloids in a single particle analysis mode.     

Quantized electroluminescence from Q–CdS films immersed in aqueous electrolytes

Quantum dot electrodes (QDEs) have been constructed by deposition of Q–CdS particles onto indium–tin oxide substrates. Upon application of cathodic potentials to the electrodes in electrolytes containing persulfate ions (S₂O₈²⁻), light emission is observed. The emission peak depends on the particle size, with electrolyte electroluminescence (EEL) being observed down to 478 nm (blue light) for CdS with a particle size of 3.6 nm.     

Ultrafiltration of suspensions

Suspensions of colloids and fine particles have been ultrafiltered with and without stirring. For the two colloids tested, the finer colloid gives the lower flux in the absence of stirring, but with stirring it gives the higher flux. This can be explained by assuming that under stirred conditions the polarisation of the colloids is more effectively controlled by diffusive back-transport. As particle size increases from 25 nm to 20 μm the flux passes through a minimum as the polarisation control changes from diffusive (decreasing with particle size) to non-diffusive (increasing with particle size). In the presence of a macrosolute the stirred ultrafiltration with the finer colloid is lowest. Interactions between the polarised species, such as the hindering of diffusive back-transport, can be inferred. With the larger particles flux can be enhanced provided the loading is high enough.     

Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>/Au composite nano-particles and their optical properties

Fe₃O₄/Au composite particles with core/shell structure were prepared by reduction of Au³⁺ with hydroxylamine in the presence of an excess of Fe₃ O₄ as seeds. The resultant colloids, with an average diameter of less than 100 nm, were obtained; the remaining non-reacted Fe₃O₄ seeds can be removed by treatment with diluted HCl solution. The Fe₃O₄/Au colloids exhibit a characteristic peak of UV-visible spectra, which largely depend on the size of the particle and the suspension medium. The localized surface plasmon resonance peaks red shift and broaden with increased nanoparticle diameter or increased solvent ionic strength. The optical property is very important in the establishment of means for the detection of biomolecules.     

Current trends in the use of zero-valent iron (Fe0) for degradation of pharmaceuticals present in different water matrices

Zero-valent iron (Fe⁰) has recently been proposed as a potential candidate for the degradation of pharmaceuticals, because Fe⁰ can release dissolved iron species, activate molecular oxygen, and react with oxidant species. Additionally, due to its small particle size and large surface area, this catalyst can provide better degradation results, compared to traditional processes. This work focuses on the elimination of pharmaceuticals present in different water matrices, considering the potential harm that these substances can cause in the environment. The mechanisms of pharmaceutical removal using Fe⁰ particles include reduction, adsorption, precipitation, and oxidation processes. Most studies have focused on oxidation processes in the presence of Fe⁰ and radicals derived from oxidants such as hydrogen peroxide (H₂O₂), ozone (O₃), peroxysulfate (SO₅²⁻), peroxodisulfate (S₂O₈²⁻), and oxygen (O₂). Most of the results have shown that high percentages of pharmaceuticals can be removed, degraded, and mineralized. The mechanisms of oxidation and the parameters that influence the degradation of pharmaceuticals, as well as the possible degradation pathways, are discussed here. This review provides information on trends of different processes that use Fe⁰, considering aspects such as particle size, type of matrix, the pharmaceuticals studied, and the results obtained that can improve understanding of new advances in the field of advanced oxidation processes (AOPs) for the degradation and elimination of pharmaceuticals.     

Enhancement origin of SERS from pyridine adsorbed on AgCl colloids

SERS of pyridine molecules adsorbed on AgCl colloids are recorded. The enhancement origins are discussed by studying the effects of illumination, thiosulfate, hydrogen peroxide and ferricyanide on SERS of pyridine on AgCl colloids. In addition to an important contribution of local field enhancement on photolytic Ag particles in AgCl colloid, the surface Ag⁺ complexes on AgCl colloids as the SERS-active sites also make an important contribution to SERS of pyridine on AgCl colloid.     

Study on soap‐free P(MMA‐EA‐AA or MAA) latex particles with narrow size distribution

Soap‐free poly(methyl methacrylate‐ethyl acrylate‐acrylic acid or methacrylic acid) [P(MMA‐EA‐AA or MAA)] particles with narrow size distribution were synthesized by seeded emulsion polymerization of methyl methacrylate (MMA), ethyl acrylate (EA) and acrylic acid (AA) or methacrylic acid (MAA), and the influences of the mass ratio of core/shell monomers used in the two stages of polymerization ([C/S]_w) and initiator amount on polymerization, particle size and its distribution were investigated by using different monomer addition modes. Results showed that when the batch swelling method was used, the monomer conversion was more than 96.0% and particle size distribution was narrow, and the particle size increased first and then remained almost unchanged at around 600 nm with the [C/S]_w decreased. When the drop‐wise addition method was used, the monomer conversion decreased slightly with [C/S]_w decreased, and large particles more than 750 nm in diameter can be obtained; with the initiator amount increased, the particle size decreased and the monomer conversion had a trend to increase; the particle size distribution was broader and the number of new particles was more in the AA system than in the MAA system; but the AA system was more stable than the MAA system at both low and high initiator amount. Copyright © 2006 John Wiley & Sons, Ltd.     

Acid acting as redispersing agent to form stable colloids from photoactive crystalline aqueous sol–gel TiO<Subscript>2</Subscript> powder

In this work, the redispersion of three nanocrystalline TiO₂ colloids is studied: one pure and two Fe-doped titania. These three colloids are produced by an easy aqueous sol–gel synthesis using precipitation-acidic peptization of Ti precursor. For the two Fe-doped TiO₂, one is doped during synthesis (primary doping) and the other is doped after the synthesis (secondary doping). The initial colloids are composed of crystalline TiO₂ particles around 7?nm with good photocatalytic properties, tested on PNP degradation under visible light (wavelength >390?nm). The powders obtained by air drying of these three colloids are redispersed in water to produce colloids, which are compared to the initial colloid produced. For each colloid, five cycles of drying redispersion are achieved. The colloids are characterized by dynamic light scattering, zeta potential measurements, inductively coupled plasma–atomic emission spectroscopy, X-ray diffraction, nitrogen adsorption–desorption measurements, Mössbauer spectroscopy, diffuse reflectance spectroscopy, and photocatalytic tests. The results show that similar products are obtained between the cycles, maintaining homologous properties of colloids. This property of redispersion is mainly due to the acid (HNO₃, HCl, or H₂SO₄) which protonates the surface of the TiO₂ nanoparticle leading to high-surface charges and electrostatic repulsions between aggregates. This property can be very useful for industrial applications of this synthesis, especially as it allows the volume and weight to be reduced for transportation and storage. Moreover, results show that the pure TiO₂ powder can be doped during its redispersion step. The redispersion of the TiO₂ developed here is possible without surface functionalization or multiple step processes, contrary to commercial Degussa P25. A 2-year stability study of all the produced colloids has been performed by following the evolution of the macroscopic aspect and the physicochemical properties of these sols. This study showed high stability of the produced colloids.

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A combined spectroscopic and light scattering study of hydrolysis of uranium(VI) leading to colloid formation in aqueous solutions

This study mainly focuses hydrolysis reactions of uranium(VI) under an ambient atmosphere leading to colloid formation in near neutral solution using light scattering, UV–Vis and FTIR-ATR studies. UV–Vis and IR spectrum was recorded for uranyl solution at different pH range. U(VI) hydrolyzed colloids were detected and it was confirmed by the appearance of a band at 941 cm^?1 in the IR spectra. Light scattering measurements were performed on colloidal U(VI) solutions formed at pH range of 7–8. The average particle diameter was determined as 32–36 nm using dynamic light scattering. Well defined colloidal species are formed with no considerable change in particle size with increasing U(VI) concentration. The weight average molecular weight of colloidal species was predicted as 763 Da by Debye plot. The second virial coefficient (A₂) was found to be ?0.1139 ml g^?1 Da. The present study confirms that behaviour of U(VI) contradicts conventional Zr(IV), Th(IV) and Pu(IV) solution chemistry. U(VI) polymerization is less extensive and in neutral solutions it forms only oligomers with 2–3 uranyl units.     

Characterization of heavy-metal-containing seepage water colloids by flow FFF, ultrafiltration, ELISA and AAS

Heavy-metal-containing humic colloids from seepage water samples of three different municipal waste disposal plants were characterized in terms of molecular weight, hydrodynamic radius and heavy metal content. The size distribution of the colloids was determined with ultrafiltration (UF) and flow field-flow fractionation (flow FFF). The humic colloids in the seepage water samples were characterized using an off-line coupling of flow FFF with an enzyme-linked immunosorbent assay (ELISA) for humic substances. The heavy metals in the different size fractions obtained by UF and flow FFF were determined using atomic absorption spectroscopy (AAS). The colloid size distributions obtained with UF showed a maximum of the distribution in the range 1–10 nm. Seepage water samples with high colloid concentrations had a second maximum in the range 0.1–1 m. The determination of colloid size with flow FFF gave different colloid size distributions for the three waste disposal seepage waters, whereas water from the oldest disposal plant showed the smallest colloid size with a maximum at 0.9 nm and water from the most recent plant showed the largest colloid size with a maximum at 1.3 nm. The determination of particle classes with regard to the chemical composition using a scanning electron microscope with energy dispersive X-ray fluorescence detector (SEM/EDX) showed that the particles can be divided into five classes: silicates, insoluble salts, iron(hydr)oxides, carbonates and organic colloids (humic colloids). Flow FFF/ELISA off-line coupling showed that the most frequently occurring colloids of the seepage waters were humic colloids and investigation of the UF-size-fractions with AAS showed that up to 77% of the total mass of a heavy metal element can be bound to particles, especially to humic colloids. Additionally, the distributions of the heavy metals Fe, Cu and Zn were investigated with flow FFF/AAS off-line coupling. These results also showed that a substantial amount of these heavy metals (up to 46%) was bound to humic colloids.     

Synthesis of citrate-stabilized hydrocolloids of hydroxyapatite through a novel two-stage method: a possible aggregates-breakdown mechanism of colloid formation

Long-term stable (>2 years) hydrocolloids of hydroxyapatite (HA) were synthesized via a low-temperature (18-50 °C) reaction of aqueous ammonium phosphate with calcium nitrate in the presence of citrate ions, followed by an aging process at high temperature (80-99 °C) for 4 h. Changing the reaction and/or aging temperature seldom yielded stable HA hydrocolloids. The as-prepared hydrocolloids were desalinated through ultrafiltration where their average particle size gradually decreased, bottomed out at 100-400 μS/cm, and sharply increased in parallel with a decrease in solution conductivity. The colloid formation is most likely through a temperature-sensitive aggregates-breakdown process. During low-temperature reaction, citrate-calcium chelation bridges the growing HA particles into loose aggregates. High-temperature aging disrupts these inter-particle links and thus breaks the aggregates, imparting negative charges to the HA, forming colloidal particles stabilized by surface charge. The decrease in mean particle size during early ultrafiltration suggested that the aggregate breakdown further proceeded through desalination. In conclusion, the temperature-dependent interactions between citrate ions and calcium sites on HA particles played key roles in the synthesis and stability of the HA colloids.     

Preparation and Ultrafast Optical Characterization of Metal and Semiconductor Colloidal Nano-Particles

The ultrafast dynamics of photoinduced electrons in several metal and semiconductor colloidal nanoparticle systems are characterized using femtosecond laser spectroscopy. Various preparation methods are used and, in several cases, modified for making particles with long-term stability and narrow and controllable size distributions. The particle size and size distribution are determined using transmission electron microscopy and electronic absorption spectroscopy. For aqueous gold and silver colloids, spatial size confinement is found to cause substantially slower electronic relaxation due to reduction of non-equilibrium electron transport and weaker electron-phonon coupling. In gold colloids, photoejection of electrons into the liquid is observed, which is attributed to a two-photon enhanced ionization process. The effect of surfactant on the electron dynamics in CdS colloids is examined and found to be significant, substantiating the notion that electrons are dominantly trapped at the liquid-solid interface. In Ru³⁺-doped TiO₂ colloids, the electronic decay is found to be as fast as or even faster than in undoped TiO₂ and other semiconductor colloids such as CdS, suggesting that ion doping of large bandgap semiconductor colloids is not necessarily effective in lengthening the electron lifetime. In almost all cases studied, the majority of the photoinduced electrons are found to decay within a few tens of picoseconds due to non-radiative relaxation. The results are discussed in the context of the potential applications of metal and semiconductor nano-particles in areas including photocatalysis and photoelectrochemistry.     

Effects of Ni particle size on amination of monoethanolamine over Ni-Re/SiO2 catalysts

Ni-Re/SiO₂ catalysts with controllable Ni particle sizes (4.5–18.0 nm) were synthesized to investigate the effects of the particle size on the amination of monoethanolamine (MEA). The catalysts were characterized by various techniques and evaluated for the amination reaction in a trickle bed reactor at 170°C, 8.0 MPa, and 0.5 h^?1 liquid hourly space velocity of MEA (LHSV_MEA) in NH₃/H₂ atmosphere. The Ni-Re/SiO₂ catalyst with the lowest Ni particle size (4.5 nm) exhibited the highest yield (66.4%) of the desired amines (ethylenediamine (EDA) and piperazine (PIP)). The results of the analysis show that the turnover frequency of MEA increased slightly (from 193 to 253 h^?1) as the Ni particle sizes of the Ni-Re/SiO₂ catalysts increased from 4.5 to 18.0 nm. Moreover, the product distribution could be adjusted by varying the Ni particle size. The ratio of primary to secondary amines increased from 1.0 to 2.0 upon increasing the Ni particle size from 4.5 to 18.0 nm. Further analyses reveal that the Ni particle size influenced the electronic properties of surface Ni, which in turn affected the adsorption of MEA and the reaction pathway of MEA amination. Compared to those of small Ni particles, large particles possessed a higher proportion of high-coordinated terrace Ni sites and a higher surface electron density, which favored the amination of MEA and NH₃ to form EDA.     

Influence of hydrodynamic coupling on the density dependence of quasi-one-dimensional diffusion

The effect on the short time one particle diffusion coefficient of hydrodynamic interaction between pairs of colloid particles, and between colloid particles and the walls of a quasi-one-dimensional cylindrical channel, are calculated using the method of reflections. The nonzero size of the colloid particle is accounted for in the analysis, and the theoretical predictions are compared with the experimental data of Lin, Cui, Lee, and Yu for the short time one particle diffusion coefficient of colloids in a square open channel [Europhys. Lett. 57, 724 (2002)].     

In-vivo fluorescence imaging technique using colloid solution of multiple quantum dots/silica/poly(ethylene glycol) nanoparticles

This paper describes a method for producing silica particles containing multiple quantum dots (QD/SiO₂), a method for surface-modifying the particles with poly(ethylene glycol) (QD/SiO₂/PEG), and an in vivo fluorescence imaging technique using colloid solution of the QD/SiO₂/PEG particles. The QDs used were ZnS-coated CdSe_xTe_1?x nanoparticles surface-modified with carboxyl groups, and had an average size of 10.3 ± 2.1 nm. The QD/SiO₂ particles were fabricated by performing sol–gel reaction of tetraethyl orthosilicate using NaOH as a catalyst in the presence of the QDs. The produced particles formed core–shell structure composed of multiple QDs and silica shell, and had an average size of 50.2 ± 17.9 nm. Surface-modification of the QD/SiO₂ particles with PEG, or PEGylation of the particle surface, was performed by using methoxy polyethylene glycol silane. Fluorescence of QD colloid solution was not quenched even through the silica-coating and the PEGylation. Tissues of a mouse could be imaged by injecting the concentrated colloid solution into it and measuring fluorescence intensity emitted from the tissues.