Efficient hydrogen production by photocatalytic water-splitting using Pt-doped TiO2 hollow spheres under visible light

Pt doped TiO₂ hollow spheres (Pt/HS-TiO₂) are prepared by a sol–gel method and characterized by XRD, SEM, TEM and UV-visible absorption spectra. In addition, Pt/HS-TiO₂ is employed as the catalyst for photocatalytic hydrogen production from water splitting under visible light irradiation. The results show that Pt/HS-TiO₂ with hollow sphere structure presents excellent photocatalytic hydrogen evolution performance. The hydrogen generation rate can reach more than 1023.71 μmol h⁻¹ g⁻¹ at room temperature and no obvious deactivation is observed after 30 h irradiation. Furthermore, the reactively of Pt/HS-TiO₂ could be reproduced in the repeated cycle. Therefore, Pt/HS-TiO₂ is a promising photocatalyst to efficiently generate hydrogen under visible-light irradiation at room temperature.     

Synthesis and characterization of titanium oxide nanotubes and its performance in epoxy nanocomposite coating

Titanium oxide nanotubes (TiO₂ nanotube, TNT) were prepared from hydrothermal treatment of TiO₂ particles in NaOH at 140 °C, followed by neutralization with HCl. The structure of the nanotubes was characterized by transmission electron microscopy (TEM) and X-ray diffraction (XRD). TNT synthesized under the optimal conditions with approximately 10–20 nm wide, and several (100–200) of nanometers long. TNT is used as white pigment for two component epoxy-based coating. Ultrasonication followed by mechanical stirring has been applied for dispersion of TNT powder in an epoxy matrix. The resulting perfect dispersion of TNT particles in epoxy coating revealed by scanning electron microscopy (SEM) ensured white particles embedded in the epoxy matrix. The effects of TNT particle concentrations on thermal, mechanical and corrosion resistance of epoxy coatings composite were studied and compared to that of submicron particles. It was found that the TNT significantly enhances the heat resistance, the thermal stability and the glass transition temperature of epoxy resin. Epoxy/TNT nanocomposite with 5.0 wt.% TNT shows the highest thermal stability, the temperature of 50% weight loss increased from 365 to 378 °C, the amount of char yields or residues at 600 °C increased from 7.13 to 13.50 wt.%, respectively to 1.0 and 5.0 wt.% TNT. The glass transition temperature (Tg) increased from 182 to 220 °C too. The mechanical properties and corrosion resistance of epoxy resin greatly improved by using reinforcing TNT and this improvement increases with increase TNT wt.%.     

TiO2 nanofibers doped with rare earth elements and their photocatalytic activity

In the present study rare earth doped (Ln³⁺–TiO₂, Ln = La, Ce and Nd) TiO₂ nanofibers were prepared by the sol–gel electrospinning method and characterized by XRD, SEM, EDX, TEM, and UV-DRS. The photocatalytic activity of the samples was evaluated by Rhodamine 6G (R6G) dye degradation under UV light irradiation. XRD analysis showed that all the synthesized pure and doped titania nanofibers contain pure anatase phase at 500 °C but at 700 °C it shows both anatase and rutile phase. XRD result also shows that Ln³⁺-doped titania probably inhibits the phase transformation. The diameter of nanofibers for all samples ranges from 200 to 700 nm. It was also observed that the presence of rare-earth oxides in the host TiO₂ could decrease the band gap and accelerate the separation of photogenerated electron–hole pairs, which eventually led to higher photocatalytic activity. To sum up, our study demonstrates that Ln³⁺-doped TiO₂ samples exhibit higher photocatalytic activity than pure TiO₂ whereas Nd³⁺-doped TiO₂ catalyst showed the highest photocatalytic activity among the rare earth doped samples.     

Sol–gel synthesis of Li1.5Al0.5Ge1.5(PO4)3 solid electrolyte

The effect of calcination on Li ion conductivity of Li_1.5Al_0.5Ge_1.5(PO₄)₃ (LAGP) solid electrolyte prepared by a sol–gel method is examined. The Li ion conductivity of LAGP increases with calcination temperature. After reaching maximum conductivity at 850 °C, the conductivity decreases with increase of the calcination temperature. The calcination holding time also strongly affects Li ion conductivity of LAGP. The conductivity increases with holding time until 12 h and then decreases. It is found that the control of crystallization rate is critical to obtain bulk LAGP with high Li ion conductivity. The highest bulk and total conductivities at 30 °C are 9.5×10⁻⁴ and 1.8×10⁻⁴ S cm⁻¹, respectively, obtained for the bulk LAGP calcined at 850 °C for 12 h.     

Aluminum titanate based ceramics from aluminum sludge waste

This work aims at obtaining aluminum titanate-based ceramics (Al₂TiO₅: AT) composites from industrial wastes. Al-sludge waste and rutile ore were used as rich sources of alumina and titania instead of pure materials. Sludge-(0–40 wt%) rutile mixtures were mixed, formed and fired at 1350 °C for various times. Phase composition, microstructure, densification, mechanical and thermal behaviors of the obtained AT composites have been investigated. Complete conversion of the starting materials to AT with bulk density of 3.199 g/cm³, compressive strength and modulus of rupture of 326.425 MPa and 30.84 MPa, respectively and very low CTE (−0.927*10⁻⁶ K⁻¹) were achieved by firing the sludge-(30 wt%) rutile at 1350 °C for 4 h. These results suggest that the obtained AT-ceramics from Al-sludge waste-rutile ore are a promising and an ecofriendly route.     

Sacrificial template synthesis of core-shell SrTiO3/TiO2 heterostructured microspheres photocatalyst

The core-shell SrTiO₃/TiO₂ heterostructure was obtained via a combined hydrothermal route and calcination treatment using amorphous spherical TiO₂ as both template and reactant. Adjusting the hydrothermal environments can control the morphology of the post-calcined sample when it is hydrothermally treated at 180 °C/3 h and 200 °C/6 h, respectively. Following the heat treatment at 700 °C/4 h, the obtained powder illustrates the core-shell heterostructure with a hierarchical surface, and the diameter of the microsphere is about 700 nm. This synthesizing route facilitates the formation of a concentration gradient of SrTiO₃ and TiO₂, and subsequently constructs a gradient energy level, which helps the samples exhibited an excellent de-colorize activity over the methylene blue. The possible formation mechanism of core-shell SrTiO₃/TiO₂ heterostructures was proposed to guide the further improvement of their photocatalytic activity.     

Highly dispersed Pt in MIL-101: An efficient catalyst for the hydrogenation of nitroarenes

Homogeneously dispersed Pt adatoms were fabricated in ordered mesoporous metal-organic framework (MIL-101) through a simple colloid method. N₂-adsorpton and time-resolved HRTEM analysis disclosed that Pt dispersed highly in the pores and/or outer surface of MIL-101. Pt@MIL-101 exhibited an extremely high activity for hydrogenation of nitroarenes under mild conditions. The turnover frequency of each Pt atom for nitrobenzene hydrogenation reached 1548 min^− 1 at 30 °C.     

Dielectric and thermal properties of AlN ceramics

The effects of slow-cooling and annealing conditions on dielectric loss, thermal conductivity and microstructure of AlN ceramics were investigated. Y₂O₃ from 0.5 to 1.25 mol% at 0.25% increments was added as a sintering additive to AlN powder and pressureless sintering was carried out at 1900 °C for 2 h in a nitrogen flowing atmosphere. To improve the properties, AlN samples were slow-cooled at a rate of 1 °C min⁻¹ from 1900 to 1750 °C, subsequently cooled to 970 °C at a rate of 10 °C min⁻¹ and then annealed at the same temperature for 4 h. AlN and YAG (5Al₂O₃/3Y₂O₃) were the only identified phases from XRD. AlN doped with 0.5 and 0.75 mol% Y₂O₃ had a low loss of <2.0 × 10⁻³ and a high thermal conductivity of >160 W m⁻¹ °C⁻¹.     

Extraction kinetics of pre-pelletized Jalapeño peppers with supercritical CO2

The aim of this work was to assess and model supercritical carbon dioxide (ScCO₂) extraction kinetics of pre-pelletized Jalapeño peppers (Capsicum annuum L.). Pepper flakes were conditioned to low moisture, ground finely and pelletized at high pressure, and pellets were subsequently ground and size classified. The effects of average sample particle size (D_p=0.28–3.19 mm) and superficial solvent velocity (U_s=0.14–2.62 mm s⁻¹) were evaluated at 40 °C and 120 or 320 bar. Extraction rate increased as a result of a decrease in D_p. It also increased as a result of an increase in U_s at 120 bar, but the effect was almost negligible at 320 bar. Integral extraction yields of capsicum oleoresin and capsaicinoids were ≈0.102 g g⁻¹ and ≈240 mg kg⁻¹, respectively, independent of extraction conditions. External mass transfer coefficients (k_f) increased with U_s, but this effect was less pronounced than commonly reported in the literature. Values of k_f increased as D_p or process pressure decreased, due respectively to increments in specific area and improvements in transport properties. Internal mass transfer coefficients, on the other hand, were 5.3×10⁻⁸ m s⁻¹ at 40 °C and 120 bar, and 34.7×10⁻⁸ m s⁻¹ at 40 °C and 320 bar. Solutes were effectively liberated from the original matrix with our multistage pretreatment, so that the fraction of free solute did not depend on D_p (α=0.46). Pseudosolubilities for capsicum oleoresin in ScCO₂ (≈2100 mg l⁻¹ at 40 °C and 120 bar; ≈13,700 mg l⁻¹ solute/CO₂ at 40 °C and 320 bar) were of the same order of magnitude as corresponding true solubilities of capsaicin (5600 and 11,800 mg l⁻¹, respectively). Estimated true solubilities of chlorophyll-a in ScCO₂ (2 mg l⁻¹ at 40 °C and 120 bar; 18 mg l⁻¹ at 40 °C and 320 bar), on the other hand, were orders of magnitude smaller, which justifies a much slower extraction rate for green pigments than pungent compounds. Thus, oleoresin obtained after 4 h at 40 °C and 120 bar had a very attractive light yellow tinge.     

Synergy effect in the photocatalytic degradation of methylene blue on a suspended mixture of TiO2 and N-containing carbons

N-containing carbon materials were obtained from waste plum stones submitted to pyrolysis under Ar flow at 700 °C or to activation under steam at 800 °C and enriched with nitrogen by heating in a NH₃/air mixture at 270 °C or in NO at 300 °C. In situ mixtures of TiO₂ and carbons were prepared by the slurry method and methylene blue photodegradation was chosen as a model reaction to verify the influence of N-containing carbons on the photocatalytic activity of TiO₂ under artificial visible light irradiation. From the kinetics of methylene blue degradation an important synergy effect between both solids was detected with a remarkable increase up to a factor of 5.3 higher in the photocatalytic activity on TiO₂–C than that on TiO₂ alone. A mechanism for the photoassisting role of N-containing carbons upon the photoactivity of TiO₂ under visible light is discussed.     

Application of BaO–CaO–Al2O3–B2O3–SiO2 glass–ceramic seals in large size planar IT-SOFC

BaO–CaO–Al₂O₃–B₂O₃–SiO₂ (BCAS) glass–ceramics can be used as sealant for large size planar anode-supported solid oxide fuel cells (SOFCs). BCAS glass–ceramics after heat treatment for different times were characterized by means of thermal dilatometer, X-ray diffraction (XRD) and scanning electron microscopy (SEM). The results show that the coefficients of thermal expansion (CTE) of BCAS glass–ceramics are 11.4×10⁻⁶ K⁻¹, 11.3×10⁻⁶ K⁻¹ and 11.2×10⁻⁶ K⁻¹ after heated at 750 °C for 0 h, 50 h, and 100 h, respectively. The CTE of BCAS matches that of YSZ, Ni–YSZ and the interconnection of SOFC. Needle-like barium silicate, barium calcium silicate and hexacelsian are crystallized in the BCAS glass after heat-treatment for above 50 h at 750 °C. The glass–ceramics green tape prepared by aqueous tape casting can be directly applied in sealing the cell of SOFCs with 10 cm×10 cm. The open circuit voltage (OCV) of the cell keeps 1.19 V after running for 280 h at 750 °C and thermal cycling 10 times from 750 °C to room temperature. The maximum power density is 0.42 W/cm² using pure H₂ as fuel and air as oxidation gas. SEM images show no cracks or pores exist in the interface of BCAS glass–ceramics and the cell.     

Low temperature hydrothermal synthesis of monodispersed flower-like titanate nanosheets

Monodispersed flower-like titanate superstructure was successfully prepared by simple hydrothermal process without any surfactant or template. N₂-sorption analysis, scanning electron microscopy (SEM), and X-ray diffraction (XRD) observation of as-synthesized product revealed the formation of flower-like titanate with diameter of about 250–450 nm and BET surface area (S_BET) of 350.7 m² g^?1. Upon thermal treatment at 500 °C, the titanate nanosheets were converted into anatase TiO₂ with moderate deformation of their structures. The as-prepared flower-like titanate showed high photocatalytic activity for H₂ evolution from water splitting reaction. Moreover, the sample heat treated at 500 °C exhibited higher photocatalytic activity than that of commercial TiO₂ anatase powder (ST-01).     

An effective and stable Ni2P/TiO2 catalyst for the hydrogenation of dimethyl oxalate to methyl glycolate

An effective and stable bifunctional Ni₂P/TiO₂ catalyst was proposed for gas-phase hydrogenation of dimethyl oxalate to corresponding alcohols. A 93.0% conversion of DMO with a selectivity of 88.0% to methyl glycolate was observed under 210 °C. Moreover, the catalyst showed an excellent stability which can be performed for 3600 h under the reaction conditions of 230 °C, 3 MPa H₂ and the weight space velocity of 0.1 h^− 1.     

The size and dispersion effect of modified graphene oxide sheets on the photocatalytic H2 generation activity of TiO2 nanorods

Nano graphene oxide (NGO) was produced by further refluxing graphene oxide (GO) sheets in HNO₃, and carboxylic acid functionalized graphene oxide (GO–COOH) was obtained by a simple etherification reaction between GO and chloroacetic acid. The GO, GO–COOH and NGO sheets are combined with TiO₂ nanorods by a two-phase assembling method, and confirmed by transmission electronic microscopy. The GO–TiO₂, GO–COOH–TiO₂ and NGO–TiO₂ composites are used in a comparative study of photocatalytic H₂ generation activity under UV light irradiation. The H₂ generation rate of TiO₂ nanorods was slightly increased from 15 to 30 mL h⁻¹ g⁻¹ by replacing oleic acid ligands with hydrophilic dopamine, and significantly increased to 105 mL h⁻¹ g⁻¹ after combining with GO sheets. The further comparative study shows that GO–COOH–TiO₂ composite has higher H₂ generation rate of 180 mL h⁻¹ g⁻¹ than that of GO–TiO₂ and NGO–TiO₂ composites.     

Microwave sintered Bi0.90La0.10Fe0.95Mn0.05O3 nanocrystalline ceramics: Impedance and modulus spectroscopy

Multiferroic Bi_0.90La_0.10Fe_0.95Mn_0.05O₃ (BLFMO) nanoceramics were synthesized by PVA sol-gel method, followed by microwave sintering. The structural, microstructural and electrical properties of BLFMO were investigated. The crystal symmetry and unit cell dimensions were determined from the experimental data using Rietveld analysis. BLFMO revealed only one electroactive region as verified from impedance and modulus spectroscopy. Overlapping large polaron tunneling transport mechanism was observed from AC conductivity analysis. Conduction below 250 °C (−30 °C≤T≤250 °C) was attributed to translational hopping while above 250 °C (250 °C≤T≤350 °C) corresponds to electron hopping between charge defects. The relative permittivity varies from 66 to 203 at 1 kHz over the measured temperature range (−150 °C≤T≤350 °C). The electrical conductivity of the microwave sintered BLFMO has been discussed based on defect reaction with Mn doping. The measured DC conductivity in the range of 10⁻¹³ S/cm at −130 °C to 10⁻⁴ S/cm at 350 °C revealed the insulating behavior of the sample. At room temperature, the DC resistivity of the sample was over ~50 MΩ cm. The stretching constant (β) obtained from KWW (Kohlrausch-Williams-Watts) equation indicates that the sample inclined towards ideal Debye behavior as the temperature increases.     

Structural and electrical properties of Sr2NaNb4O13 thin film grown by electrophoretic method using nanosheets synthesized from K(Sr2Na)Nb4O13 compound

Sr₂NaNb₄O₁₃⁻ (SNNO⁻) nanosheets were exfoliated from the K(Sr₂Na)Nb₄O₁₃ compound that was synthesized at 1200 °C. The SNNO⁻ nanosheets were deposited on a Pt/Ti/SiO₂/Si substrate at room temperature by the electrophoretic method. Annealing was conducted at various temperatures to remove organic defects in the SNNO film. A crystalline SNNO phase without organic defects was formed in the film annealed at 500 °C. However, a SrNb₂O₆ secondary phase was formed in the films annealed above 600 °C, probably due to the evaporation of Na₂O. The SNNO thin film annealed at 500 °C showed a dielectric constant of 74 at 1.0 MHz with a dielectric loss of 2.2%. This film also exhibited a low leakage current density of 9.0 × 10⁻⁸ A/cm² at 0.6 MV/cm with a high breakdown electric field of 0.72 MV/cm.     

The influence of nano alumina additions on the coefficient of thermal expansion of a LZS glass–ceramic composition

In this work a 19.58Li₂O·11.10ZrO₂·69.32SiO₂ (mol%) glass–ceramic matrix was prepared and milled in order to determine its coefficient of thermal expansion (CTE) and to study how it is influenced by the addition of nanosized Al₂O₃ particles (1–5 vol%) and submicrometric Al₂O₃ particles (5 vol%). Comminution studies from the LZS parent glass frit showed that a powder with an adequate particle size (3.5 µm) is achieved after 120 min of dry milling followed by a second step of 60 h wet milling. The obtained LZS glass–ceramic samples (fired at 900 °C/30 min) showed an average relative density of ∼98% with zirconium silicate and lithium disilicate as main crystalline phases. Prepared composites with 1, 2.5 and 5 vol% of nanosized Al₂O₃ and 5 vol% submicrometric Al₂O₃ showed average relative densities varying from 97% to 94% as the alumina content increased. The formation of β-spodumene in the obtained composites leads to reduce the CTEs, whose values ranged from 9.5 to 4.4×10⁻⁶ °C⁻¹. Composites with 5% nanosized alumina showed a CTE lower than that of the equivalent formulation with submicrometric alumina.     

Thermal cycling induced capacity enhancement of graphite anodes in lithium-ion cells

Graphite electrodes were electrochemically cycled in Li-ion cells at 50 and 60 °C in order to determine the changes in their surface properties in comparison to the electrodes tested at 25 °C. A 17% drop in planar capacity occurred during the first cycle at 60 °C compared to a 40% at 25 °C and reduced the amount of damage that occurred to graphite due to a rapidly formed solid electrolyte interphase (SEI). During the following cycles, a planar capacity of 3.11 ± 0.12 mAh cm⁻² was attained at 60 °C rather than 0.53 ± 0.03 mAh cm⁻² at 25 °C. The SEI layer formed at 60 °C predominantly consisted of Li₂CO₃ and was devoid of residual LiClO₄ detected at 25 °C. At 25 °C, the diffusion coefficient of Li⁺ (D_Li⁺) was calculated as 1.07 × 10⁻⁸ cm² s⁻¹, whereas at 60 °C, D_Li⁺ increased to 3.25 × 10⁻⁸ cm² s⁻¹. A pre-treatment conducted at 60 °C enhanced the cyclic performance of graphite subsequently cycled at 25 °C; a Li₂CO₃-enriched SEI, generated during the 60 °C pre-treatment, covered the graphite surface uniformly and resulted in a 28% increase in battery capacity at 25 °C.     

Low temperature sintering and microwave dielectric properties of TiO2 ceramics

The TiO₂ ceramics were prepared by a solid-state reaction in the temperature range of 920–1100 °C for 2 h and 5 h using TiO₂ nano-particles (Degussa-P25 TiO₂) as the starting materials. The sinterability and microwave properties of the TiO₂ ceramics as a function of the sintering temperature were studied. It was demonstrated that the rutile phase TiO₂ ceramics with good compactness could be readily synthesized from the Degussa-P25 TiO₂ powder in the temperature range of 920–1100 °C without the addition of any glasses. Moreover, the TiO₂ ceramics sintered at 1100 °C/2 h and 920 °C/5 h demonstrated excellent microwave dielectric properties, such as permittivity (Ɛ_r) value >100, Q × f  > 23,000 GHz and τ_f ≅ 200 ppm/°C.     

Hydrothermal synthesis of titanate nanostructures with high UV absorption characteristics

The titanate nanostructures with high UV absorption characteristics could be fabricated by hydrothermal method within a temperature range of 90–150 °C. TEM, XRD, BET analyses, and UV–vis spectroscopy were employed to elucidate the synthesized titanate nanostructure characteristics which were microstructure, phase transformation, specific surface area, and band gap energy, respectively. With an increase in the hydrothermal treating temperature from 90 to 120 °C, the specific surface area of titanate nanostructures was increased from 83 to 258 m²/g, while the band gap energy of titanate nanostructures was increased from 3.44 to 3.84 eV and then slightly decreased to 3.81 eV at 150 °C. The fabricated titanate nanostructures could exhibit higher UV adsorption capability but lower photocatalytic activity when compared with that of commercial TiO₂ powders.