Shaping of Porous CeO2 Powders into Highly Active Catalyst Carriers.

CeO2 is attracting more and more attention because of its outstanding performance in heterogeneous catalysis, as an active support and a reaction promoter in reactions of industrial interest. We herein describe a novel and scalable manufacturing process of mm-sized CeO2 spheres by a combination of extrusion and spheronization of CeO2 porous powders. In this study, wet paste formulation and fabrication procedures were optimized, and as a result methylcellulose was identified as the best plasticizer for paste extrusion to provide well-defined spherical shapes and smooth surfaces, as well as reproducible batches. After nickel impregnation (10 wt %), the catalytic performance of CeO2 supports was evaluated in the CO2 methanation reaction (T = 250-350 °C, P = 5 bar·g) and compared with that of commercial Al2O3 spheres doped or not with CeO2. These novel CeO2-based catalysts are easily reduced at a moderate temperature and more active than the Al2O3 analogues, particularly at low reaction temperatures and small reactor volumes, properties that make their implementation in emerging reactor configurations very promising.

Characterization of 3D Printed Yttria-Stabilized Zirconia Parts for Use in Prostheses.

The main aim of the present paper is to study and analyze surface roughness, shrinkage, porosity, and mechanical strength of dense yttria-stabilized zirconia (YSZ) samples obtained by means of the extrusion printing technique. In the experiments, both print speed and layer height were varied, according to a 22 factorial design. Cuboid samples were defined, and three replicates were obtained for each experiment. After sintering, the shrinkage percentage was calculated in width and in height. Areal surface roughness, Sa, was measured on the lateral walls of the cuboids, and total porosity was determined by means of weight measurement. The compressive strength of the samples was determined. The lowest Sa value of 9.4 µm was obtained with low layer height and high print speed. Shrinkage percentage values ranged between 19% and 28%, and porosity values between 12% and 24%, depending on the printing conditions. Lowest porosity values correspond to low layer height and low print speed. The same conditions allow obtaining the highest average compressive strength value of 176 MPa, although high variability was observed. For this reason, further research will be carried out about mechanical strength of ceramic 3D printed samples. The results of this work will help choose appropriate printing conditions extrusion processes for ceramics.

Analysis of the Compression Behaviour of Reinforced Photocurable Materials Used in Additive Manufacturing Processes Based on a Mask Image Projection System.

Mask image projection based on stereolithography is an additive manufactured technology based on a Frontal Photopolymerization Process. Therefore, photocurable resins are used to build-up parts layer by layer. In this paper, alumina particles have been used as a reinforcement filler in order to improve the material stress-strain behaviour. In addition, the increment of the photoconversion ratio is a key factor to enhance the mechanical properties. Consequently, a numerical model has been used to determine the optimal printing parameters to enhance the elastic mechanical properties of printed parts according to the characteristics of photocurable materials. Stable and homogeneous reinforced materials have been obtained with an alumina content ranging from 5 to 15 wt%. Furthermore, the compression behaviour of reinforced materials has been analysed by means of experimental tests. The results show an enhancement of mechanical properties after the addition of reinforcement fillers, obtaining a maximum improvement in 10 wt% of solid load content. Finally, the influence of the sample's orientation on the construction platform has been discussed.

A Highly Stable Metal-Organic Framework-Engineered FeS2/C Nanocatalyst for Heterogeneous Electro-Fenton Treatment: Validation in Wastewater at Mild pH.

Herein, the novel application of FeS2/C nanocomposite as a highly active, stable, and recyclable catalyst for heterogeneous electro-Fenton (EF) treatment of organic water pollutants is discussed. The simultaneous carbonization and sulfidation of an iron-based metal-organic framework (MOF) yielded well-dispersed pyrite FeS2 nanoparticles of ∼100 nm diameter linked to porous carbon. XPS analysis revealed the presence of doping N atoms. EF treatment with an IrO2/air-diffusion cell ensured the complete removal of the antidepressant fluoxetine spiked into urban wastewater at near-neutral pH after 60 min at 50 mA with 0.4 g L-1 catalyst as optimum dose. The clear enhancement of catalytic activity and stability of the material as compared to natural pyrite was evidenced, as deduced from its characterization before and after use. The final solutions contained <1.5 mg L-1 dissolved iron and became progressively acidified. Fluorescence excitation-emission spectroscopy with parallel factor analysis demonstrated the large mineralization of all wastewater components at 6 h, which was accompanied by a substantial decrease of toxicity. A mechanism with •OH as the dominant oxidant was proposed: FeS2 core-shell nanoparticles served as Fe2+ shuttles for homogeneous Fenton's reaction and provided active sites for the heterogeneous Fenton process, whereas nanoporous carbon allowed minimizing the mass transport limitations.

Feasible and pure P2O5-CaO nanoglasses: An in-depth NMR study of synthesis for the modulation of the bioactive ion release.

The use of bioactive glasses (e.g. silicates, phosphates, borates) has demonstrated to be an effective therapy for the restoration of bone fractures, wound healing and vascularization. Their partial dissolution towards the surrounding tissue has shown to trigger positive bioactive responses, without the necessity of using growth factors or cell therapy, which reduces money-costs, side effects and increases their translation to the clinics. However, bioactive glasses often need from stabilizers (e.g. SiO44-, Ti4+, Co2+, etc.) that are not highly abundant in the body and which metabolization is not fully understood. In this study, we were focused on synthesizing pure calcium phosphate glasses without the presence of such stabilizers. We combined a mixture of ethylphosphate and calcium 2-methoxyethoxide to synthesize nanoparticles with different compositions and degradability. Synthesis was followed by an in-depth nuclear magnetic resonance characterization, complemented with other techniques that helped us to correlate the chemical structure of the glasses with their physiochemical properties and reaction mechanism. After synthesis, the organically modified xerogel (i.e. calcium monoethylphosphate) was treated at 200 or 350 °C and its solubility was maintained and controlled due to the elimination of organics, increase of phosphate-calcium interactions and phosphate polycondensation. To the best of our knowledge, we are reporting the first sol-gel synthesis of binary (P2O5-CaO) calcium phosphate glass nanoparticles in terms of continuous polycondensated phosphate chains structure without the addition of extra ions. The main goal is to straightforward the synthesis, to get a safer metabolization and to modulate the bioactive ion release. Additionally, we shed light on the chemical structure, reaction mechanism and properties of calcium phosphate glasses with high calcium contents, which nowadays are poorly understood. STATEMENT OF SIGNIFICANCE: The use of bioactive inorganic materials (i.e. bioactive ceramics, glass-ceramics and glasses) for biomedical applications is attractive due to their good integration with the host tissue without the necessity of adding exogenous cells or growth factors. In particular, degradable calcium phosphate glasses are completely resorbable, avoiding the retention in the body of the highly stable silica network of silicate glasses, and inducing a more controllable degradability than bioactive ceramics. However, most calcium phosphate glasses include the presence of stabilizers (e.g. Ti4+, Na+, Co2+), which metabolization is not fully understood and complicates their synthesis. The development of binary calcium phosphate glasses with controlled degradability reduces these limitations, offering a simple and completely metabolizable material with higher transfer to the clinics.

A Study of Carbon Nanofibers and Active Carbon as Symmetric Supercapacitor in Aqueous Electrolyte: A Comparative Study.

Symmetric supercapacitors are fabricated by carbon nanofibers (CNF) and activated carbon (AC) using similar proportions of 7 wt% polyvinylidene fluoride (PVDF) polymer binder in an aqueous electrolyte. In this study, a comparison of porous texture and electrochemical performances between CNFs and AC based supercapacitors was carried out. Electrodes were assembled in the cell without a current collector. The prepared electrodes of CNFs and AC present Brunauer-Emmett-Teller (BET) surface area of 83 and 1042 m2/g, respectively. The dominant pore structure for CNFs is mesoporous while for AC is micropore. The results showed that AC provided higher specific capacitance retention up to very fast scan rate of 500 mV/s. AC carbon had a specific capacitance of 334 F/g, and CNFs had 52 F/g at scan rate 5 mV/s in aqueous solution. Also, the results indicate the superior conductivity of CNFs in contrast to AC counterparts. The measured equivalent series resistance (ESR) showed a very small value for CNFs (0.28 Ω) in comparison to AC that has an ESR resistance of (3.72 Ω). Moreover, CNF delivered higher specific power (1860 W/kg) than that for AC (450 W/kg). On the other hand, AC gave higher specific energy (18.1 Wh/kg) than that for CNFs (2 Wh/kg).This indicates that the AC is good for energy applications. Whereas, CNF is good for power application. Indeed, the higher surface area will lead to higher specific capacitance and hence higher energy density for AC. For CNF, lower ESR is responsible for having higher power density.Both CNF and AC supercapacitor exhibit an excellent charge-discharge stability up to 2500 cycles.

Highly Specific and Wide Range NO2 Sensor with Color Readout.

We present a simple and inexpensive method to implement a Griess-Saltzman-type reaction that combines the advantages of the liquid phase method (high specificity and fast response time) with the benefits of a solid implementation (easy to handle). We demonstrate that the measurements can be carried out using conventional RGB sensors; circumventing all the limitations around the measurement of the samples with spectrometers. We also present a method to optimize the measurement protocol and target a specific range of NO2 concentrations. We demonstrate that it is possible to measure the concentration of NO2 from 50 ppb to 300 ppm with high specificity and without modifying the Griess-Saltzman reagent.

Angiogenesis in bone regeneration: tailored calcium release in hybrid fibrous scaffolds.

In bone regeneration, silicon-based calcium phosphate glasses (Bioglasses) have been widely used since the 1970s. However, they dissolve very slowly because of their high amount of Si (SiO2 > 45%). Recently, our group has found that calcium ions released by the degradation of glasses in which the job of silicon is done by just 5% of TiO2 are effective angiogenic promoters, because of their stimulation of a cell-membrane calcium sensing receptor (CaSR). Based on this, other focused tests on angiogenesis have found that Bioglasses also have the potential to be angiogenic promoters even with high contents of silicon (80%); however, their slow degradation is still a problem, as the levels of silicon cannot be decreased any lower than 45%. In this work, we propose a new generation of hybrid organically modified glasses, ormoglasses, that enable the levels of silicon to be reduced, therefore speeding up the degradation process. Using electrospinning as a faithful way to mimic the extracellular matrix (ECM), we successfully produced hybrid fibrous mats with three different contents of Si (40, 52, and 70%), and thus three different calcium ion release rates, using an ormoglass-polycaprolactone blend approach. These mats offered a good platform to evaluate different calcium release rates as osteogenic promoters in an in vivo subcutaneous environment. Complementary data were collected to complement Ca(2+) release analysis, such as stiffness evaluation by AFM, ζ-potential, morphology evaluation by FESEM, proliferation and differentiation analysis, as well as in vivo subcutaneous implantations. Material and biological characterization suggested that compositions of organic/inorganic hybrid materials with a Si content equivalent to 40%, which were also those that released more calcium, were osteogenic. They also showed a greater ability to form blood vessels. These results suggest that Si-based ormoglasses can be considered an efficient tool for calcium release modulation, which could play a key role in the angiogenic promoting process.

Oxide Wizard: an EELS application to characterize the white lines of transition metal edges.

Physicochemical properties of transition metal oxides are directly determined by the oxidation state of the metallic cations. To address the increasing need to accurately evaluate the oxidation states of transition metal oxide systems at the nanoscale, here we present "Oxide Wizard." This script for Digital Micrograph characterizes the energy-loss near-edge structure and the position of the transition metal edges in the electron energy-loss spectrum. These characteristics of the edges can be linked to the oxidation states of transition metals with high spatial resolution. The power of the script is demonstrated by mapping manganese oxidation states in Fe3O4/Mn3O4 core/shell nanoparticles with sub-nanometer resolution in real space.