Continuous Polyol Synthesis of Metal and Metal Oxide Nanoparticles Using a Segmented Flow Tubular Reactor (SFTR).

Over the last years a new type of tubular plug flow reactor, the segmented flow tubular reactor (SFTR), has proven its versatility and robustness through the water-based synthesis of precipitates as varied as CaCO3, BaTiO3, Mn(1-x)NixC2O4·2H2O, YBa oxalates, copper oxalate, ZnS, ZnO, iron oxides, and TiO2 produced with a high powder quality (phase composition, particle size, and shape) and high reproducibility. The SFTR has been developed to overcome the classical problems of powder production scale-up from batch processes, which are mainly linked with mass and heat transfer. Recently, the SFTR concept has been further developed and applied for the synthesis of metals, metal oxides, and salts in form of nano- or micro-particles in organic solvents. This has been done by increasing the working temperature and modifying the particle carrying solvent. In this paper we summarize the experimental results for four materials prepared according to the polyol synthesis route combined with the SFTR. CeO2, Ni, Ag, and Ca3(PO4)2 nanoparticles (NPs) can be obtained with a production rate of about 1-10 g per h. The production was carried out for several hours with constant product quality. These findings further corroborate the reliability and versatility of the SFTR for high throughput powder production.

Cathode Catalyst Layer Design in PEM Water Electrolysis toward Reduced Pt Loading and Hydrogen Crossover.

Reducing the use of platinum group metals is crucial for the large-scale deployment of proton exchange membrane (PEM) water electrolysis systems. The optimization of the cathode catalyst layer and decrease of the cathode Pt loading are usually overlooked due to the predominant focus of research on the anode. However, given the close relationship between the rate of hydrogen permeation through the membrane in an operating cell and the local hydrogen concentration near the membrane-cathode interface, the structural design of the cathode catalyst layer is considered to be of pivotal importance for reducing H2 crossover, particularly in combination with the use of thin (≲50 µm) membranes. In this study, we have conducted a detailed investigation on the cathode structural parameters, covering the Pt wt % of the Pt/C electrocatalyst, the type of carbon support (Vulcan and high surface area carbon, HSAC), and the ionomer content, with a goal to reduce Pt loading to 0.025 mgPt/cm2 while minimizing the rate of cell hydrogen crossover. We found that the electrochemical performance is mainly influenced by the changes in the interfacial contact resistance due to variations in the cathode thickness. Both the Pt wt % in Pt/C and the ionomer content showed a positive correlation with the measured H2 in O2% in the anode outlet, whereas the Pt loading exhibited an opposite trend. The rate of hydrogen crossover was analyzed in relation to the calculated local volumetric current density within the cathode catalyst layer. Based on the obtained hydrogen mass transfer coefficient, a cathode catalyst layer comprising 40 wt % Pt on HSAC support with an ionomer-to-carbon (I/C) ratio of 0.35 was found to be an optimum configuration for achieving a low Pt loading of 0.025 mgPt/cm2 and a reduced rate of hydrogen crossover.

Airborne metal nanoparticles released by azides detonation: determination and potential public exposure.

Metal azides are highly energetic materials that release a large amount of gas upon detonation. They also release metal particles, generating an aerosol. The most common azide is sodium azide (NaN3), which is used nowadays in car airbags. If the decomposition is not complete, harmful azide particles might be inhaled. Heavy metal azides find application as a primary explosive (primer) in ammunition. Public health officials have raised concerns about heavy metal particles released during training in shooting ranges. We identify a lack of knowledge on airborne metal particles properties released from azide detonation and on the analytical methods applied to characterize them. As a case study, we detonated milligram amounts of silver azide, copper azide, and a mixture of them in a glove box. We then analyse the airborne particles with an ensemble analytical setup, able to measure real-time their particle size distribution and chemical composition. We detected spherical metal nanoparticles in the range of 2-500 nm. These findings and the developed analytical tools may allow identifying airborne nanoparticles the passenger compartments of vehicles after airbag activation as well as in indoor shooting ranges, contributing to the evaluation of public health risks.

Approaching Angstrom-Scale Resolution in Lithography Using Low-Molecular-Mass Resists (<500 Da).

Resists that enable high-throughput and high-resolution patterning are essential in driving the semiconductor technology forward. The ultimate patterning performance of a resist in lithography is limited because of the trade-off between resolution, line-width roughness, and sensitivity; improving one or two of these parameters typically leads to a loss in the third. As the patterned feature sizes approach angstrom scale, the trade-off between these three metrics becomes increasingly hard to resolve and calls for a fundamental rethinking of the resist chemistry. Low-molecular-mass monodispersed metal-containing resists of high atom economy can provide not only very high resolution but also very low line-width roughness without sacrificing sensitivity. Here we describe a modular metal-containing resist platform (molecular mass <500 Da) where a molecular resist consists of just two components: a metal and a radical initiator bonded to it. This simple system not only is amenable to high-resolution electron beam lithography (EBL) and extreme ultraviolet lithography (EUVL) but also unites them mechanistically, giving a consolidated perspective of molecular and chemical processes happening during exposure. Irradiation of the resist leads to the production of secondary electrons that generate radicals in the initiator bonded to metal. This brings about an intramolecular rearrangement and causes solubility switch in the exposed resist. We demonstrate record 1.9-2.0 nm isolated patterns and 7 nm half-pitch dense line-space features over a large area using EBL. With EUVL, 12 nm half-pitch line-space features are shown at a dose of 68 mJ/cm2. In both of these patterning techniques, the line-width roughness was found to be ≤2 nm, a record low value for any resist platform, also leading to a low-performance trade-off metric, Z factor, of 0.6 × 10-8 mJ·nm3. With the ultimate resolution limited by instrumental factors, potential patterning at the level of a unit cell can be envisaged, making low-molecular-mass resists best poised for angstrom-scale lithography.

Kinetics and Mechanism of Metal Nanoparticle Growth via Optical Extinction Spectroscopy and Computational Modeling: The Curious Case of Colloidal Gold.

An overarching computational framework unifying several optical theories to describe the temporal evolution of gold nanoparticles (GNPs) during a seeded growth process is presented. To achieve this, we used the inexpensive and widely available optical extinction spectroscopy, to obtain quantitative kinetic data. In situ spectra collected over a wide set of experimental conditions were regressed using the physical model, calculating light extinction by ensembles of GNPs during the growth process. This model provides temporal information on the size, shape, and concentration of the particles and any electromagnetic interactions between them. Consequently, we were able to describe the mechanism of GNP growth and divide the process into distinct genesis periods. We provide explanations for several longstanding mysteries, for example, the phenomena responsible for the purple-greyish hue during the early stages of GNP growth, the complex interactions between nucleation, growth, and aggregation events, and a clear distinction between agglomeration and electromagnetic interactions. The presented theoretical formalism has been developed in a generic fashion so that it can readily be adapted to other nanoparticulate formation scenarios such as the genesis of various metal nanoparticles.

Visualization of supercritical water pseudo-boiling at Widom line crossover.

Supercritical water is a green solvent used in many technological applications including materials synthesis, nuclear engineering, bioenergy, or waste treatment and it occurs in nature. Despite its relevance in natural systems and technical applications, the supercritical state of water is still not well understood. Recent theories predict that liquid-like (LL) and gas-like (GL) supercritical water are metastable phases, and that the so-called Widom line zone is marking the crossover between LL and GL behavior of water. With neutron imaging techniques, we succeed to monitor density fluctuations of supercritical water while the system evolves rapidly from LL to GL as the Widom line is crossed during isobaric heating. Our observations show that the Widom line of water can be identified experimentally and they are in agreement with the current theory of supercritical fluid pseudo-boiling. This fundamental understanding allows optimizing and developing new technologies using supercritical water as a solvent.

Formation and transformation of calcium phosphate phases under biologically relevant conditions: Experiments and modelling.

The experimental data on calcium phosphates formation were collected in dilute solution at constant pH (7.40) and temperature (37.0 °C) at different levels of ionic strength (IS). The evolution of the solid phase formation is described in detail using a thermodynamic-kinetic model. The thermodynamic model takes into account all relevant chemical species as well as Posner's clusters; the kinetic model, based on the discretized population balance approach, accounts for the solid formation from solution. The experimental data are consistent with an initial formation of dicalcium phosphate dihydrate (DCPD, brushite), which dominates the nucleation rate, and its rapid transformation into octacalcium phosphate (OCP) or hydroxyapatite (HA), which dominates the growth rate. Depending on the experimental conditions and, including the influence of the IS level, OCP may be further transformed into apatite. The classical nucleation theory is able to describe the experimental results very well and the solid phase growth is limited by the diffusion of Ca2+ ions. The precipitation pathway described by a complete thermodynamic-kinetic model is expected to contribute to the understating of the in vivo osteogenesis. STATEMENT OF SIGNIFICANCE: The formation mechanism of calcium phosphates under biomimetic conditions is unraveled. The formation pathway is mathematically described based on a thermodynamic-kinetic model in which (i) the nucleation stages (primary and secondary) are dominated by the formation of dicalcium phosphate dihydrate (DCPD) and (ii) the fast growth stage is limited by the diffusion of Ca2+ ions under the driving force of octacalcium phosphate (OCP), or hydroxyapatite (HA), solubility. The obtained solid phase seems correlated to the activity coefficient of phosphate ions, thus to the ionic strength and local phosphate speciation. The model, being able to highlight the details of the precipitation pathway, is expected to contribute to the understanding of the apatitic phase formation in the biomineralization-biodemineralization processes under in-vivo conditions.

One-Pot Polyol Synthesis of Pt/CeO2 and Au/CeO2 Nanopowders as Catalysts for CO Oxidation.

The facile one-pot synthesis of CeO2-based catalysts has been developed to prepare a relatively large amount of nanopowders with relevant catalytic activity towards CO oxidation. The method consists of a two-steps process carried out in ethylene glycol: in the first step, 5 nm well-crystallized pure CeO2 is prepared. In a subsequent second step, a salt of a noble metal is added to the CeO2 suspension and the deposition of the noble metal on the nanocrystalline CeO2 is induced by heating. Two catalysts were prepared: Pt/CeO2 and Au/CeO2. The as-prepared catalysts, the thermally treated catalysts, as well as the pure CeO2, are characterized by XRD, TGA, XPS, FTIR, HR-TEM, STEM, particle size distribution, and N2-physisorption. In spite of the identical preparation protocol, Au and Pt behave in a completely different way: Au forms rather large particles, most of them with triangular shape, easily identifiable and dispersed in the CeO2 matrix. In contrast, Pt was not identified as isolated particles. The high resolution X-ray diffraction carried out on the Pt/CeO2 thermally treated sample (500 degrees C for 1 h) shows a significant CeO2 lattice shrinkage, which can be interpreted as an at least partial incorporation of Pt into the CeO2 crystal lattice. Moreover, only Pt2+ and Pt4+ species were identified by XPS. In literature, the incorporation of Pt into the CeO2 lattice is supported by first-principle calculations and experimentally demonstrated only by combustion synthesis methods. To the best of our knowledge this is the first report where ionically dispersed Pt into the CeO2 lattice is obtained via a liquid synthesis method. The thermally treated Pt/CeO2 sample revealed good activity with 50% CO conversion at almost room temperature.

Optimizing the photocatalytic properties of hydrothermal TiO2 by the control of phase composition and particle morphology. a systematic approach.

The possibility of controlling the photocatalytic activity of TiO2 nanoparticles by tailoring their crystalline structure and morphology is a current topic of great interest. In this study, a broad variety of well-faceted particles with different phase compositions, sizes, and shapes have been obtained from concentrated TiOCl2 solutions by systematically changing temperature, pH, and duration of the hydrothermal treatment. The guide to select the suitable experimental conditions was provided by thermodynamic modeling based on available thermochemical data. By combining the results of TEM, HRTEM, XRD, density, and specific surface area measurements, a complete structural and morphological characterization of the particles was performed. Correlation between the photocatalytic activity in the UV photodegradation of phenol solutions and the particle size was established. Prismatic rutile particles with length/width ratio around 5 and breadth of 60-100 nm showed the highest activity. The surface chemistry of the particles was also investigated. Treatments that decrease the surface acidity, such as washing the powders with ammonia solution and/or calcining at 400 degrees C, have detrimental effect on photocatalytic activity. The overall results suggest correlation between particle morphology and photocatalytic activity and indicate that both electron-hole recombination and adsorption at the surface can be rate-controlling processes. The systematic approach presented in this study demonstrates that a substantial improvement of the photocatalytic activity of TiO2 can be achieved by a careful design of the particle morphology and the control of the surface chemistry.