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The particle shape and size distribution of inorganic fillers play a crucial role in the scaffold buildability when those are incorporated in the viscoelastic polymers. In order to address this issue, the phase pure rod-shaped nanocrystalline hydroxyapatite (HAp) powders with varying particle sizes and shapes were synthesized by a one-pot hydrothermal method without any regulatory surfactant at an initial solution pH of 9. As-synthesized nanocrystalline HAp particles (0�5 wt) were incorporated into 15 wt pre-cross-linked gelatin methacryloyl (GelMA) hydrogel matrix to fabricate a predesigned scaffold architecture using a custom-made 3D bioprinter. The printing parameters (nozzle diameter, extrusion pressure, and printing speed) were optimized for each composition. The biophysical properties (uniaxial compression behavior, swelling ratio, and in vitro degradation) of the composite hydrogel scaffolds were critically analyzed to unravel the role of nano-sized HAp addition. The compression strength and modulus were substantially improved, while the rate of water uptake and bio-enzymatic degradation significantly reduced with HAp content. We propose that the inorganic�organic nanocomposite hydrogel could be efficiently assembled to formulate a potential bioink for 3D bioprinting applications toward tissue regeneration. © 2021 The American Ceramic Society

Chemistry - a European journal 27(45), 11600 - 11608 (2021). doi:10.1002/chem.202101117, Amorphous Ti$_x$O$_y$ with high surface area has attracted significant interest as photocatalyst with higher activity in ultraviolet (UV) light-induced water splitting applications compared to commercial nanocrystalline TiO$_2$. Under photocatalytic operation conditions, the structure of the molecular titanium alkoxide precursor rearranges upon hydrolysis and leads to higher connectivity of the structure-building units. Structurally ordered domains with sizes smaller than 7 Å form larger aggregates. The experimental scattering data can be explained best with a structure model consisting of an anatase-like core and a distorted shell. Upon exposure to UV light, the white Ti$_x$O$_y$ suspension turns dark corresponding to the reduction of Ti$^{4+}$ to Ti$^{3+}$ as confirmed by electron energy loss spectroscopy (EELS). Heat-induced crystallisation was followed by in situ temperature-dependent total scattering experiments. First, ordering in the Ti−O environment takes place upon to 350 °C. Above this temperature, the distorted anatase core starts to grow but the structure obtained at 400 °C is still not fully ordered., Published by Wiley-VCH, Weinheim

Zinc oxide thin films are fabricated by controlled oxidation of sputtered zinc metal films on a hotplate in air at temperatures between 250 and 450 °C. The nanocrystalline films possess high relative densities and show preferential growth in (100) orientation. Integration in thin‐film transistors reveals moderate charge carrier mobilities as high as 0.2 cm2 V−1s−1. The semiconducting properties depend on the calcination temperature, whereby the best performance is achieved at 450 °C. The defect structure of the thin ZnO film can be tracked by Doppler‐broadening positron annihilation spectroscopy as well as positron lifetime studies. Comparably long positron lifetimes suggest interaction of zinc vacancies (VZn) with one or more oxygen vacancies (VO) in larger structural entities. Such VO‐VZn defect clusters act as shallow acceptors, and thus, reduce the overall electron conductivity of the film. The concentration of these defect clusters decreases at higher calcination temperatures as indicated by changes in the S and W parameters. Such zinc oxide films obtained by conversion of metallic zinc can also be used as seed layers for solution deposition of zinc oxide nanowires employing a mild microwave‐assisted process. The functionality of the obtained nanowire arrays is tested in a UV sensor device. The best results with respect to sensor sensitivity are achieved with thinner seed layers for device construction., Thin‐film transistors: Zinc oxide layers can be obtained conveniently through the oxidation of sputter‐deposited thin films of zinc metal at temperatures between 250 and 450 °C. Positron annihilation studies hint at vacancy clusters rather than isolated point defects as the dominating feature in the defect chemistry of these films. This allows the description of the influence of annealing temperature on the resulting electronic performance of the semiconducting layers in thin‐film transistors.

Metallic spinel-type CuCo$_{2}$S$_{4}$ nanoparticles were deposited on nanocrystalline TiO$_{2}$ (P25®), forming heterostructure nanocomposites. The nanocomposites were characterized in detail by X-ray powder diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), nitrogen sorption (BET) and UV/Vis spectroscopy. Variation of the CuCo$_{2}$S$_{4}$:TiO$_{2}$ ratio to an optimum value generated a catalyst which shows a very high photocatalytic H$_{2}$ production rate at neutral pH of 32.3 µmol/h (0.72 mLh$^{–1}$), which is much larger than for pure TiO$_{2}$ (traces of H$_{2}$). The catalyst exhibits an extraordinary long-term stability and after 70 h irradiation time about 2 mmol H$_{2}$ were generated. An increased light absorption and an efficient charge separation for the sample with the optimal CuCo$_{2}$S$_{4}$:TiO$_{2}$ ratio is most probably responsible for the high catalytic activity.

Made available in DSpace on 2020-12-12T01:30:01Z (GMT). No. of bitstreams: 0 Previous issue date: 2020-11-01 Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) The development of stable and reproducible inorganic pigments is noteworthy for industrial applications mainly considering more intense shades and low toxicity. Among the various candidates to substitute non-hazardous red and yellow pigments, CeO2 and CeO2:Pr have been attracting attention because of their opacity and high-temperature stability besides being environmental-friendly and health-friendly. In this study, nanostructured CeO2 and CeO2:Pr samples were synthesized using the polymeric precursor method and structural and optical characterizations were performed. Scanning electron microscopy reveals the morphology of CeO2 nanoparticles in which the particle size ranges from 22 to 28 nm as a function of the annealing temperature. Pr-doping does not show influence on the particle size. XRD results show that CeO2 and CeO2:Pr samples crystallize in the cubic fluorite lattice with Fm3m space group. Raman spectra show the fluorite F2g mode, confirming the XRD results. With Pr-doping and the annealing of the samples, two bands are observed between 550 and 600 cm−1, which are related to the defects in the fluorite structure associated with oxygen vacancies. XPS spectra reveal an increase in the ratio of Ce3+ ions depending on the annealing temperature and Pr-doping. This increase is associated with the carbon removal from the lattice by annealing. This behavior causes a change in the hue of the powders as the annealing temperature increases. According to diffuse reflectance and colorimetric measurements, CeO2 shows a light-yellow color due to the O 2p­Ce 4f transitions whose b* parameter mainly decreases with annealing, becoming almost white. The CeO2:Pr sample exhibits a red-orange color because of the electronic transitions between 4f2 → 5d1 states of Pr3+. Upon annealing, L* and b* parameters decrease, resulting in a red-brown shade. The charge compensation or charge transfer is responsible for the modification of the hue of these pigments. Institute of Geosciences and Exact Sciences São Paulo State University (Unesp) CEITEC – Central European Institute of Technology Brno University of Technology São Carlos Institute of Physics University of São Paulo - USP Institute of Geosciences and Exact Sciences São Paulo State University (Unesp) FAPESP: 2013/12993-4

The authors built a prototype motor with NANOMET stator cores. NANOMET is one of the several nanocrystalline soft magnetic alloys [see ref. 1]. Motor iron loss and other characteristics were compared with 35A360 (Japanese Industrial Standards), which is one of the widely used conventional electromagnetic steel sheet, and the effectiveness of the new material is shown. This study describes the method to build NANOMET stator cores, and presents the evaluation results of the prototype motor.

Conversion/alloying materials (CAMs) are a potential alternative to graphite as Li‐ion anodes, especially for high‐power performance. The so far most investigated CAM is carbon‐coated Zn$_{0.9}$Fe$_{0.1}$O, which provides very high specific capacity of more than 900 mAh g$^{-1}$ and good rate capability. Especially for the latter the optimal particle size is in the nanometer regime. However, this leads to limited electrode packing densities and safety issues in large‐scale handling and processing. Herein, a new synthesis route including three spray‐drying steps that results in the formation of microsized, spherical secondary particles is reported. The resulting particles with sizes of 10–15 μm are composed of carbon‐coated Zn$_{0.9}$Fe$_{0.1}$O nanocrystals with an average diameter of approximately 30–40 nm. The carbon coating ensures fast electron transport in the secondary particles and, thus, high rate capability of the resulting electrodes. Coupling partially prelithiated, carbon‐coated Zn$_{0.9}$Fe$_{0.1}$O anodes with LiNi$_{0.5}$Mn$_{1.5}$O$_{4}$ cathodes results in cobalt‐free Li‐ion cells delivering a specific energy of up to 284 Wh kg$^{-1}$ (at 1 C rate) and power of 1105 W kg−1 (at 3 C) with remarkable energy efficiency (>93 % at 1 C and 91.8 % at 3 C).

Molybdenum-based compounds are considered as a potential replacement for expensive precious-metal electrocatalysts for the hydrogen evolution reaction (HER) in acid electrolytes. However, coating of thin films of molybdenum nitride or carbide on a large-area self-standing substrate with high precision is still challenging. Here, MoNx is uniformly coated on carbon cloth (CC) and nitrogen-doped carbon (NC)-modified CC (NCCC) substrates by atomic layer deposition (ALD). The as-deposited film has a nanocrystalline character close to amorphous and a composition of approximately Mo2 N with significant oxygen contamination, mainly at the surface. Among the as-prepared ALD-MoNx electrodes, the MoNx /NCCC has the highest HER activity (overpotential η≈236 mV to achieve 10 mA cm-2 ) owing to the high surface area and porosity of the NCCC substrate. However, the durability of the electrode is poor, owing to the poor adhesion of NC powder on CC. Annealing MoNx /NCCC in H2 atmosphere at 400 °C improves both the activity and durability of the electrode without significant change in the phase or porosity. Annealing at an elevated temperature of 600 °C results in formation of a Mo2 C phase that further enhances the activity (η≈196 mV to achieve 10 mA cm-2 ), although there is a huge reduction in the porosity of the electrode as a consequence of the annealing. The structure of the electrode is also systematically investigated by electrochemical impedance spectroscopy (EIS). A deviation in the conventional Warburg impedance is observed in EIS of the NCCC-based electrode and is ascribed to the change in the H+ ion diffusion characteristics, owing to the geometry of the pores. The change in porous nature with annealing and the loss in porosity are reflected in the EIS of H+ ion diffusion observed at high-frequency. The current work establishes a better understanding of the importance of various parameters for a highly active HER electrode and will help the development of a commercial electrode for HER using the ALD technique.

The conversion of CO2 to useful chemicals, especially to atom economical products, is the best approach to utilize an excess of CO2 present in the atmosphere. In this study, a metal-organic framework (ZIF-8) is integrated with nanocrystalline zirconosilicate zeolite to develop an integrated porous catalyst for CO2 insertion reactions. The catalyst exhibits excellent activity for the CO2 insertion reaction of epoxide to produce cyclic carbonate in neat condition without the addition of any co-catalyst. The catalyst is stable and recyclable during the cyclic carbonate synthesis. Further, the catalyst also exhibits very good activity in another CO2 insertion reaction to produce quinazoline-2,4(1H, 3H)-dione.

Cubic silicon carbide (3C‐SiC) material feature a suitable bandgap and high resistance to photocorrosion. Thus, it has been emerged as a promising semiconductor for hydrogen evolution. Here, the relationship between the photoelectrochemical properties and the microstructures of different SiC materials is demonstrated. For visible‐light‐derived water splitting to hydrogen production, nanocrystalline, microcrystalline and epitaxial (001) 3C‐SiC films are applied as the photocathodes. The epitaxial 3C‐SiC film presents the highest photoelectrochemical activity for hydrogen evolution, because of its perfect (001) orientation, high phase purity, low resistance, and negative conduction band energy level. This finding offers a strategy to design SiC‐based photocathodes with superior photoelectrochemical performances., Thin films: For visible‐light‐derived water splitting to hydrogen production, nanocrystalline, microcrystalline and epitaxial (001) 3C‐SiC films are applied as photocathodes. The epitaxial 3C‐SiC film presents the highest photoelectrochemical activity for hydrogen evolution, because of its perfect (001) orientation, high phase purity, low resistance, and negative conduction band energy level.

Nanocrystalline (NC) materials exhibit many unique properties over their coarse‐grained counterparts due to the high grain boundary density and the small grain size, but they are too difficult to be used in engineering environment because of the poor thermal stability. With regard of this, two strategies are previously proposed to enhance the thermal stability (or impede the grain growth) of NC materials, that is, the thermodynamic and the kinetic approaches. Recent investigations increasingly support that the two approaches may be physically interacted and acted on each other, and they can be treated together within a unified thermo‐kinetic framework. This paper reviews the progress in the investigation of thermo‐kinetic correlation during grain growth in NC materials. First, the theoretical models to describe the concept of the thermo‐kinetic correlation and the grain growth equations developed based on the thermo‐kinetic correlation are reviewed. Second, experimental and simulated evidences to support the coexistence of thermodynamic and kinetic effects are summarized. Third, the potential application of thermo‐kinetic correlation is analyzed and discussed. This paper shows that the stabilization of NC materials can be tailored by the selection of the suitable strategies. Finally, several directions that require further exploration are identified.

A carbon‐rich melt fragment from the Gardnos impact structure has been studied for a better understanding of the preservation and structural form(s) of carbon that have been processed by impact melting. The carbon was analyzed in situ in its original petrographic context within the melt fragment, using high‐resolution techniques including focused ion beam‐transmission electron microscopy and electron energy loss spectroscopy. Results show that the carbon is largely uniform and has a nanocrystalline grain size. The Gardnos carbon has a graphitic structure but with a large c/a ratio indicating disorder. The disorder could be a result of rapid heating to high temperatures during impact, followed by rapid cooling, with not enough time to crystallize into highly ordered graphite. However, temperature distribution during impact is extremely heterogenous, and the disordered Gardnos carbon could also represent material that avoided extreme temperatures, and thus, it was preserved. Understanding the structure of carbon during terrestrial impacts is important to help determine if the history of carbon within extraterrestrial samples is impact related. Furthermore, the degree of preservation of carbon during impact is key for locating and detecting organic compounds in extraterrestrial samples. This example from Gardnos, together with previous studies, shows that not all carbon is lost to oxidation during impact but that impact melting can encapsulate and preserve carbon where it is available.

Understanding ammonia oxidation over metal oxide surfaces is crucial for improving its detection with resistive type gas sensors. Formation of NOx during this process makes sensor response and calibration unstable. Cr-doping of nanocrystalline metal oxides has been reported to suppress NO2 sensitivity and improve response towards NH3 , however the exact mechanism of such chromium action remained unknown. Herein, by using EPR spectroscopy we demonstrate formation of Cr(VI) lattice defects on the surface of nanocrystalline Cr-doped SnO2 . Enhancement of Cr-doped SnO2 surface acidity and ammonia adsorption as a result has been revealed by using in situ IR spectroscopy. Moreover, a decrease in concentration of free electrons in the conduction band has been shown as a result of substitutional Cr(III) defects formation. Weaker NOx chemisorption during ammonia oxidation over SnO2 surface after Cr doping has been found with the use of mass-spectrometry assisted NH3 thermo-programmed desorption. The given example of surface acidity adjustment and electronic configuration by means of doping may find use in the design of new gas-sensing metal oxide materials.

A templating method is developed to produce porous nanocrystalline anatase materials for negative electrodes in lithium‐ion batteries (LIBs). Amphiphilic diblock copolymers are used to generate template films with phase‐separated internal structure. Subsequent swelling with acidified titanium(IV) bis(ammonium lactato) dihydroxide (TALH) solution yielded structured hybrid films. Upon heating, the formation of TiO₂ nanocrystals is induced, resulting in a three‐dimensional mesoporous structure directed by the bulk morphology of the polymer template. In comparison to commercial nanosized anatase, the structured anatase shows significant performance improvements in lithium‐ion coin cell batteries in terms of capacity, stability, and rate capability. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1890–1896

Nanocrystalline metals and ceramics with

International audience; A simple and efficient procedure is described for the electrochemical determination of ledipasvir (LDP) in presence of co-formulated drug sofosbuvir (SOF). Herein, a highly sensitive, low-cost electrochemical protocol was utilized to fabricate a zeolite modified carbon paste electrode (ZY/CPE) through mixing of zeolite nanostructures with graphite powder. The fabricated sensor displayed high sensitivity, allowing optimal charge transfer/electrode kinetics. Different experimental and chemical factors, including electrode composition, effect of pH, scan rate and amount of ZY were evaluated carefully to obtain the highest electrochemical response. Under optimized conditions and using square wave voltammetry (SWV), the current response of the ZY/CPE electrochemical sensing platform exhibited a detection limit of 7.5×10-9 M and a large linear range from 5.0×10-8 to 1.0×10-4 M. The practical applicability of the suggested electrochemical platform was verified in the assessment of LDP in pharmaceutical formulations with excellent recoveries in the range of 99.50-98.87 %. Moreover, a biological relevance of the developed sensor was established by the analysis of LDP in human urine and plasma samples with satisfactory recoveries of 99.00 and 99.68 %, respectively. Due to the simplicity and ease of preparation of the proposed sensor, it can be used in quality control laboratories and for clinical analysis.