Search

In the present work, a series of CaTi 1- x Fe x O 3-δ (0 < x < 0.5) materials are prepared using a modified Pechini method based on citric acid and a polyol as chelating agents. The synthesis conditions are optimized with respect to the specific surface area and phase purity by varying polyols (ethylene glycol, glycerol, and 1.6-hexanediol) and the ratio between citric acid, polyols, and cations. The impact of the polyols and the iron content (up to 40 mol % on the B site) is studied with respect to the oxygen exchange rate, reducibility using H 2 -TPR, and catalytic performance for methane total oxidation. A correlation between the oxygen exchange rate studied using 18 O exchange in powdered samples of CaTi 1- x Fe x O 3-δ (0 < x < 0.5) and ferric sites determined using Mössbauer spectroscopy and H 2 -TPR is established. The oxygen activation and diffusion in CaTi 1- x Fe x O 3-δ (0 < x < 0.5) continuously increase in the studied range of Ti substitution. The methane oxidation performance does not increase above x = 0.3, showing that methane oxidation is not limited by surface oxygen activation and CH 4 is activated by specific iron sites in Fe-doped perovskites.

Herein, we investigate the interplay between a photocatalyst (TiO 2 ) and a catalyst (Pt/TiO 2 and Pt/CeO 2 ) for the oxidation of formaldehyde and toluene at room temperature. A luminous textile is used as support and as light source for the photocatalyst. Our results indicate that the presence of the catalyst and the photocatalyst increases the catalytic performance for the oxidation of formaldehyde, while the photocatalytic performance for toluene oxidation decreases. The overall performance (toluene and formaldehyde degradation) of the system can be optimized with respect to the choice of support for the catalyst (e.g. TiO 2 or CeO 2 ), the quantity of Pt used, and the ratio between the catalyst and photocatalyst. In addition, different configurations of the photocatalyst and the catalyst on the textile are studied: under leaching and flow-through gas streams, catalyst and photocatalyst deposition on the same and opposite site of the textile are tested. The performance of the system can be optimized by adapting a configuration where the gas stream goes through the textile, while the deposition side of the catalyst and/or photocatalyst with respect to the gas stream is of minor importance., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

Soft or rigid particles, suspended in a liquid melt, interact with an advancing solidification front in various industrial and natural processes, such as fabrication of particle-reinforced-composites, growth of crystals, cryopreservation, frost heave, and growth of sea ice. The particle dynamics relative to the front determine the microstructure as well as the functional properties of the solidified material. Previous studies have extensively investigated the interaction of foreign objects with a moving solid-liquid interface in pure melts while in most real-life systems, solutes or surface active impurities are almost always present. Here we study experimentally the interaction of spherical oil droplets with a moving planar ice-water interface, while systematically increasing the surfactant concentration in the bulk liquid, using in situ cryo-confocal microscopy. We demonstrate that a small amount of surfactant in the bulk liquid can instigate long-range droplet repulsion, extending over a length scale of 40 to 100 μm, in contrast to the short-range predicted previously (<1 μm). We report on the droplet deformation, while they are in contact with the ice-water interface, as a function of the bulk surfactant concentration, the droplet size, and the crystal growth rate. We also depict the dynamic evolution of solute-enriched premelted films (≈5 μm). Our results demonstrate how an increasing concentration of surfactant in the bulk and its subsequent segregation during solidification can dramatically alter the solidification microstructures. We anticipate that our experimental study can aid in the development of theoretical models incorporating solute effects.

The support material can play an important role in oxidation catalysis, notably for CO oxidation. Here, we study two materials of the Brownmillerite family, CaFeO 2.5 and SrFeO 2.5 , as one example of a stoichiometric phase (CaFeO 2.5, CFO) and one existing in different modifications (SrFeO 2.75 , SrFeO 2.875 and SrFeO 3 , SFO). The two materials are synthesized using two synthesis methods, one bottom-up approach via a complexation route and one top-down method (electric arc fusion), allowing to study the impact of the specific surface area on the oxygen mobility and catalytic performance. CO oxidation on 18 O-exchanged materials shows that oxygen from SFO participates in the reaction as soon as the reaction starts, while for CFO, this onset takes place 185 °C after reaction onset. This indicates that the structure of the support material has an impact on the catalytic performance. We report here on significant differences in the catalytic activity linked to long-term stability of CFO and SFO, which is an important parameter not only for possible applications, but equally to better understand the mechanism of the catalytic activity itself.

Oil-in-water emulsions have been stabilized by functionalized cellulose nanofibrils bearing either a negative (oxidized cellulose nanofibrils, OCNF) or a positive (cationic cellulose nanofibrils, CCNF) surface charge. The size of the droplets was measured by laser diffraction, while the structure of the shell of the Pickering emulsion droplets was probed using small-angle neutron scattering (SANS), confocal laser scanning microscopy (CLSM), scanning electron microscopy (SEM), and rheology measurements. Both OCNF- and CCNF-stabilized emulsions present a very thick shell (>100 nm) comprised of densely packed CNF. OCNF-stabilized emulsions proved to be salt responsive, influencing the droplet aggregation and ultimately the gel properties of the emulsions, while CCNF emulsions, on the other hand, showed very little salt-dependent behavior.

The design of nanoporous perovskite oxides is considered an efficient strategy to develop performing, sustainable catalysts for the conversion of methane. The dependency of nanoporosity on the oxygen defect chemistry and the catalytic activity of perovskite oxides toward CH 4 and CO oxidation was studied here. A novel colloidal synthesis route for nanoporous, high-temperature stable SrTi 0.65 Fe 0.35 O 3-δ with specific surface areas (SSA) ranging from 45 to 80 m 2 /g and pore sizes from 10 to 100 nm was developed. High-temperature investigations by in situ synchrotron X-ray diffraction (XRD) and TG-MS combined with H 2 -TPR and Mössbauer spectroscopy showed that the porosity improved the release of surface oxygen and the oxygen diffusion, whereas the release of lattice oxygen depended more on the state of the iron species and strain effects in the materials. Regarding catalysis, light-off tests showed that low-temperature CO oxidation significantly benefitted from the enhancement of the SSA, whereas high-temperature CH 4 oxidation is influenced more by the dioxygen release. During isothermal long-term catalysis tests, however, the continuous oxygen release from large SSA materials promoted both CO and CH 4 conversion. Hence, if SSA maximization turned out to efficiently improve low-temperature and long-term catalysis applications, the role of both reducible metal center concentration and crystal structure cannot be completely ignored, as they also contribute to the perovskite oxygen release properties.

Pt-based materials are widely used as heterogeneous catalysts, in particular for pollutant removal applications. The state of Pt has often been proposed to differ depending on experimental conditions, for example, metallic Pt poisoned with CO being present at lower temperature before light-off, while an oxidized Pt surface prevails above light-off temperature. In stark contrast to all previous reports, we show herein that both metallic and oxidized Pt are present in similar proportions under reaction conditions at the surface of ca. 1 nm nanoparticles showing high activity at 30 °C. The simultaneous presence of metallic and oxidized Pt enables a synergy between these phases. The main role of the metallic Pt phase is to provide strong adsorption sites for CO, while that of oxidized Pt supposedly supplies reactive oxygen. Our results emphasize the complex dual oxidic-metallic nature of supported Pt catalysts and platinum's evolving nature under reaction conditions., (© 2020 Wiley-VCH GmbH.)

The interaction of objects suspended in a liquid melt with an advancing solidification front is of special interest in nature and engineering sciences. The front can either engulf the object into the growing crystal or repel it. Therefore, the object-front confrontation can have a strong influence on the microstructure and mechanical or functional properties of the solidified material. The past theoretical models and experimental studies have mostly investigated the interaction of isolated, spherical, and hard objects in pure melts. However, the outcome of object-front interactions in complex (more realistic) systems, where multiple objects and solutes are present, is still poorly understood. Here we show the interaction of multiple oil droplets with an ice-water front in the absence and presence of solute effects using in situ cryo-confocal microscopy. We report on how the object size, number of objects, and bulk solute concentration influence the the object-front interaction and the front morphology, as well as the subsequent object spatial distribution. We suggest that the volume fraction of objects suspended in a liquid melt in conjunction with the amount of bulk solute concentration are two important parameters to be incorporated in the development of object-front interaction models.

Hypothesis: Polyoxometalates (POMs) are metal oxygen clusters with a range of interesting magnetic and catalytic properties. POMs with attached hydrocarbon chains show amphiphilic behaviour so we hypothesised that mixtures of a nonionic surfactant and anionic surfactants with a polyoxometalate cluster as headgroup would form mixed micelles, giving control of the POM density in the micelle, and which would differ in size and shape from micelles formed by the individual surfactants. Due to the high charge and large size of the POM, we suggested that these would be nonideal mixtures due to the complex interactions between the two types of surfactants. The nonideality and the micellar composition may be quantified using regular solution theory. With supplementary information provided by small-angle neutron scattering (SANS), an understanding of this unusual binary surfactant system can be established., Experiments: A systematic study was performed on mixed surfactant systems containing polyoxometalate-headed amphiphiles (K 10 [P 2 W 17 O 61 OSi 2 (C n H 2n+1 ) 2 ], abbreviated as P 2 W 17 -2C n , where n = 12, 14 or 16) and hexaethylene glycol monododecyl ether (C 12 EO 6 ). Critical micelle concentrations (CMCs) of these mixtures were measured and used to calculate the interaction parameters based on regular solution theory, enabling prediction of micellar composition. Predictions were compared to micelle structures obtained from SANS. A phase diagram was also established., Findings: The CMCs of these mixtures suggest unusual unfavourable interactions between the two species, despite formation of mixed micelles. Micellar compositions obtained from SANS concurred with those calculated using the averaged interaction parameters for P 2 W 17 -2C n /C 12 EO 6 (n = 12 and 14). We attribute the unfavourable interactions to a combination of different phenomena: counterion-mediated interactions between P 2 W 17 units and the unfolding of the ethylene oxide headgroups of the nonionic surfactant, yet micelles still form in these systems due to the hydrophobic interactions between surfactant tails., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Inc. All rights reserved.)

Cryopreservation is the only fully established procedure to extend the lifespan of living cells and tissues, a key to activities spanning from fundamental biology to clinical practice. Despite its prevalence and impact, the central aspects of cryopreservation, such as the cell's physicochemical environment during freezing, remain elusive. Here we address that question by coupling in situ microscopic directional freezing to visualize cells and their surroundings during freezing with the freezing-medium phase diagram. We extract the freezing-medium spatial distribution in cryopreservation, providing a tool to describe the cell vicinity at any point during freezing. We show that two major events define the cells' local environment over time: the interaction with the moving ice front and the interaction with the vitreous moving front, a term we introduce here. Our correlative strategy may be applied to cells relevant to clinical research and practice and may help in the design of new cryoprotective media based on local physicochemical cues.

Hybrid anisotropic microgels were synthesised using mesoporous silica as core particles. By finely controlling the synthesis conditions, the latter can be obtained with different shapes such as platelets, primary particles or rods. Using the core particles as seeds for precipitation polymerisation, a crosslinked poly( N -isopropylacrylamide) (PNIPAM) microgel shell could be grown at the surface, conferring additional thermo-responsive properties. The different particles were characterised using scattering and imaging techniques. Small angle X-ray scattering (SAXS) was employed to identify the shape and porous organisation of the core particles and dynamic light scattering (DLS) to determine the swelling behaviour of the hybrid microgels. In addition, cryogenic transmission electron microscopy (cryo-TEM) imaging of the hybrids confirms the different morphologies as well as the presence of the microgel network and the core-shell conformation. Finally, the response of the particles to an alternating electric field is demonstrated for hybrid rod-shaped microgels in situ using confocal laser scanning microscopy (CLSM)., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Surface hydrophobization of cellulose nanomaterials has been used in the development of nanofiller-reinforced polymer composites and formulations based on Pickering emulsions. Despite the well-known effect of hydrophobic domains on self-assembly or association of water-soluble polymer amphiphiles, very few studies have addressed the behavior of hydrophobized cellulose nanomaterials in aqueous media. In this study, we investigate the properties of hydrophobized cellulose nanocrystals (CNCs) and their self-assembly and amphiphilic properties in suspensions and gels. CNCs of different hydrophobicity were synthesized from sulfated CNCs by coupling primary alkylamines of different alkyl chain lengths (6, 8, and 12 carbon atoms). The synthetic route permitted the retention of surface charge, ensuring good colloidal stability of hydrophobized CNCs in aqueous suspensions. We compare surface properties (surface charge, ζ potential), hydrophobicity (water contact angle, microenvironment probing using pyrene fluorescence emission), and surface activity (tensiometry) of different hydrophobized CNCs and hydrophilic CNCs. Association of hydrophobized CNCs driven by hydrophobic effects is confirmed by X-ray scattering (SAXS) and autofluorescent spectroscopy experiments. As a result of CNC association, CNC suspensions/gels can be produced with a wide range of rheological properties depending on the hydrophobic/hydrophilic balance. In particular, sol-gel transitions for hydrophobized CNCs occur at lower concentrations than hydrophilic CNCs, and more robust gels are formed by hydrophobized CNCs. Our work illustrates that amphiphilic CNCs can complement associative polymers as modifiers of rheological properties of water-based systems.

When a suspension freezes, a compacted particle layer builds up at the solidification front with noticeable implications on the freezing process. In a directional solidification experiment of monodisperse suspensions in thin samples, we evidence a link between the thickness of this layer and the sample depth. We attribute it to an inhomogeneity of particle density that is attested by the evidence of crystallization at the plates and of random close packing far from them. A mechanical model based on the resulting modifications of permeability enables us to relate the layer thickness to this inhomogeneity and to select the distribution of particle density that yields the best fit to our data. This distribution involves an influence length of sample plates of about 11 particle diameters. Altogether, these results clarify the implications of boundaries on suspension freezing. They may be useful to model polydisperse suspensions with large particles playing the role of smooth boundaries with respect to small ones.