Band structur e design of semiconduc tors for enhanced photocatalytic activity: The case of TiO2

General strategies are proposed by passivated co-doping in present paper to improve the photocatalytic activity of semiconductors for degradation of environmental pollutants.The ideal band gap of semiconductors for enhancement of photocatalytic activity can be lowered to match with visible light absorption and the location of the Conduction Band(CB) should be raised to meet the reducing capacity.Then we apply the strategy to anatase TiO2.It is predicted that nonmetal–metal co-doping TiO2can modify the catalyst band edges by raising the valence band(VB) edge signifcantly and making the CB edge increased 0.24 eV.Therefore,the band gap for co-doping system should be narrowed to about2.72 eV.(N,Ta) is predicted to be the target donor–acceptor combination with the band gap of 2.71 eV,which red-shifts the TiO2absorption edge to 457.6 nm in visible range.The band engineering principle will be ft to other wide-band-gap semiconductors for enhanced photocatalytic activity.     

Microstructure, mechanical and thermo-physical properties of hot-pressed Al2O3-GdAlO3-ZrO2 ceramics with eutectic composition

A low cost chemical co-precipitation method was employed to fabricate nanoscale Al_2O_3-GdAlO_3-ZrO_2 powder with eutectic composition. A careful control of reaction conditions was required during the preparation. The synthesized nanopowders exhibited a particle size of 20-200 nm, and were highly dispersive and uniform. The results showed that calcination temperature had an important influence on the phase constituents of the nanopowders. With increasing the calcination temperature, a phase transformation from θ-Al_2O_3 to α-Al_2O_3 and a thermal decomposition from Gd_3 Al_5O_(12)(GdAG) to GdAlO_3 and α-Al_2O_3 occurred in sequence. A calcination temperature of 1300 ℃ was needed for the crystallization of α-Al_2 O_3. These nanosized powders were consolidated via hot pressing to produce a fully densified ceramic composite with eutectic composition. The Al_2O_3-GdAlO_3-ZrO_2 ceramic hot-pressed at 1500 ℃ exhibited a relative density of 99.4%, a flexural strength of 485 MPa and a fracture toughness of 6.5 MPa m~(1/2). The ceramic had a thermal conductivity of 1.9 W m K~(-1) at 1200 ℃ and a thermal expansion coefficient of 9.49 ×10~(-6) K~(-1) at 1100 ℃.     

Synthesis of dental resins using diatomite and nano-sized SiO2 and TiO2

The mechanical properties of dental composites were improved by porous diatomite and nano-sized silica (OX-50) used as co-fillers.The resin composites,filled with silanized OX-50 and silanized diatomit...     

Bionic titania coating carbon multi-layer material derived from natural leaf and its superior photocatalytic performance

Bionic titania coating carbon multi-layer material was fabricated by employing canna leaves as substrate and carbon precursor. Titania nanocrystals were assembled and coated on the natural films. The carbonation treatment under pure N_2 atmosphere yielded the ultrathin multi-film hybrid material. The carbon layer was coated with small anatase titania crystallite(8–10 nm) and possessed a highly specific surface area of 248.3 m~2 g~(-1). Examination using UV–visible spectrophotometer(UV–vis) showed that the band gap of the multi-layer material was reduced to 2.75 eV, and the hydrogen production by photocatalytic splitting of water under visible light irradiation was about 302 μmol g~(-1) after six hour.     

Activated carbon derived from rice husk by NaOH activation and its application in supercapacitor

Four activated carbon(AC) samples prepared from rice husk under different activation temperatures have been characterized by N2adsorption–desorption isotherms, thermogravimetric analysis(TGA–DTA), Fourier transform infrared spectroscopy(FTIR) and scanning electron microscopy(SEM). The specific surface area of AC sample reached 2681 m2 g 1under activation temperature of 800 1C. The AC samples were then tested as electrode material; the specific capacitance of the as-prepared activated carbon electrode was found to be 172.3 F g 1using cyclic voltammetry at a scan rate of 5 mV s 1and 198.4 F g 1at current density 1000 mA g 1in the charge/discharge mode.& 2014 Chinese Materials Research Society. Production and hosting by Elsevier B.V. All rights reserved.     

Effect of B2O3 on the aqueous tape casting and microwave properties of Li2O–Nb2O5–TiO2 ceramics

The effect of B2O3 addition on the aqueous tape casting, sintering, microstructure and microwave dielectric properties of Li2O-Nb2O5-TiO2 ceramics has been investigated. The tape casting slurries exhibit a typical shear-thinning behavior without thixotropy, but the addition of B2O3 increases the viscosity of the slurries significantly. It was found that doping of B2O3 can decrease the tensile strength, strain to failure and density of the green tapes. The sintering temperature could be lowed down to 900℃ with the addition of 2 wt% B2O3 due to the liquid phase effect. No secondary phase is observed. The addition of B2O3 does not induce much degradation on the microwave dielectric properties. Optimum microwave dielectric properties of εr 67, Q×f 6560 GHz are obtained for Li2O-Nb2O5-TiO2 ceramics containing 2 wt% B2O3 sintered at 900 1C. It represents that the ceramics could be promising for multilayer low-temperature co-fired ceramics (LTCC) application.     

Mechanical and thermal properties of NpO2 using LSDAt U approach

The elastic constants,bulk modulus,shear modulus,Young’s modulus,Debye temperature,isobaric heat capacity and minimum thermal conductivity are estimated for NpO2 using plane-wave pseudopotential method within the local spin density approximation plus Hubbard U(LSDAtU) theory.The computed lattice constants are in good agreement with the available experimental results and then three independent elastic constants were computed by means of the stress–strain method.From the knowledge of the elastic constants,the values of Young’s modulus,Poisson,Debye temperature and minimum thermal conductivity are obtained and they are 218 GPa,0.288,453.5 K and0.99 Wm-1K-1,respectively.The obtained mechanical and thermal properties of NpO2 are in agreement with the previous experimental and theoretical data.Our investigations which are unobtainable from previous report can provide valuable reference in the future.     

Novel approaches to produce Al2O3– TiC/TiCN– Fecomposite powders directly from ilmenite

Al2O3 –TiC/TiCN–Fe composite powders were successfully prepared directly from ilmenite at 1300–1400℃.The effects of Al/C ratio,sintering atmosphere,and reaction temperature and time on the reaction products were investigated.Results showed that the nitrogen atmosphere was bene cial to the reduction of ilmenite and the formation of Al2O3 –TiC/TiCN–Fe composite powders.When the reaction temperature was between 600 and 1100℃,the intermediate products,TiO2,Ti3O5 and Ti4O7 were found,which changed to TiC or TiCN at higher temperature.Al/C ratio was found to affect the reaction process and synthesis products.When Al addition was 0.5 mol,the Al2O3 phase did not appear.The content of carbon in TiCN rose when the reaction temperature was increased.     

Structure and properties of solid-state synthesiz ed poly (3,4-propylenedi oxythiophene) /nano-ZnO composite

Poly（3,4-propylenedioxythiophene）/nano-Zinic Oxide（PProDOT/ZnO） composites with the content of 3-7 wt%nano-ZnO were synthesized by the solid-state method with FeCl₃ as oxidant.The structure and morphology of the composites were characterized by Fourier transform infrared（FTIR）spectroscopy,ultraviolet-visible（UV-vis） absorption spectroscopy,X-ray diffraction（XRD） and transmission electron microscopy（TEM）.The electrochemical performances of the composites were investigated by galvanostatic charge-discharge,cyclic voltammetry and electrochemical impedance spectroscopy（EIS）.The photocatalytic activities of the composites were investigated by the degradation of methylene blue（MB） dyes in aqueous medium under UV light irradiation.The results from FTIR and UV-vis spectra showed that the PProDOT/ZnO composites were successfully synthesized by solid-state method,and nano-ZnO had great influences on the conjugation length and oxidation degree of the polymers.Furthermore,the PProDOT/5 wt%ZnO had the highest conjugation and oxidation degree among the composites.The results of XRD analysis indicated that there were some FeCl₄^- ions as doping agent in the PProDOT matrix,and the content of ZnO had no effect on diffraction pattern of PProDOT.Morphological studies revealed that the pure PProDOT and composites had similar morphological structure,and all the composites displayed an irregular sponge like morphology.The results of electrochemical tests showed that the PProDOT/5 wt%ZnO had a higher electrochemical activity with a specific capacitance value of 220 F g^-1 than others.The results from photocatalytic activities of the composites indicated that the PProDOT/5 wt%ZnO had better photocatalytic activity than other composites.     

Properties of garnet-type Li6La3ZrTaO12 solid electrolyte films fabricated by aerosol deposition method

The garnet-type Li_6La_3ZrTaO_(12)(LLZT) solid electrolyte films were fabricated by aerosol deposition(AD)method.Ball-milled LLZT powder with a cubic garnet structure and a particle size of 1-2 urn was used as raw material and deposited directly on a SUS316L or a glass substrate via impact consolidation.As-deposited LLZT film has a cubic garnet structure but contains Li_2CO_3 and La_2Zr_2O_7 phases.SEM observation revealed that the film consists of LLZT particles fractured into submicron size.The impurity phase formation during AD process was caused by the local heating by the collision between LLZT particles and deposition surface and reaction with CO_2.The Li~+ ion conductivity of LLZT film was estimated to be 0.24 × 10~(-5)S cm~(-1) at room temperature.Electronic conductivity of LLZT film was confirmed to be around 10~(-12) S cm~(-1),indicating the dominant Li~+ ion conduction of LLZT film.     

Synthesis of PbS–K2La2Ti3O10 composite and its photocatalytic activity for hydrogen production

Photocatalyst, lead sulfide (PbS )-intercalated layer perovskite-type compound (K2La2Ti3O10), was synthesized via ion-exchange reaction, butylamine pillaring and sulfuration processes under the assistance of the microwave irradiation. The structure of the photoc atalysts was determined by means of powder X-ray diffraction, scanning electron microscope, ultraviolet- visible diffuse reflection spectra and photoluminescence measu rement. And the photocatalytic activity of the composite compound for hydrogen production was also investigated. The experimental results showed that the intercalation of PbS in the layered space of K2La2Ti3O10 greatly improved the absorption edge and the photocatalytic activity. Hydrogen production of the PbS–K2La2Ti3O10 was 127.19 mmol/(g cat) after 3 h irradiation of ultraviolet light.     

Effect of CuO addition on the sintering temperature and microwave dielectric properties of CaSiO3– Al2O3 ceramics

CuO-doped CaSiO3–1 wt% Al2O3 ceramics were synthesized via a traditional solid-state reaction method, and their sintering behavior,microstructure and microwave dielectric properties were investigated. The results showed that appropriate CuO addition could accelerate the sintering process and assist the densification of CaSiO3–1 wt% Al2O3 ceramics, which could effectively lower the densification temperature from1250 1C to 1050 1C. However, the addition of CuO undermined the microwave dielectric properties. The optimal amount of CuO addition was found to be 0.8 wt%, and the derived CaSiO3–Al2O3ceramic sintered at 1100 1C presented good microwave dielectric properties of εr?7.27,Q f?16,850 GHz and τf? 39.53 ppm/1C, which is much better than those of pure CaSiO3 ceramic sintered at 1340oC(Q f?13,109 GHz).The chemical compatibility of the above ceramic with 30 Pd/70 Ag during the cofiring process has also been investigated, and the result showed that there was no chemical reaction between palladium–silver alloys and ceramics.& 2014 Chinese Materials Research Society. Production and hosting by Elsevier B.V. All rights reserved.     

Fabrication of fine spongy nanoporous Ag-Au alloys with improved catalysis properties

Fine NP-AgAu(nanoporous AgAu) alloys with spongy structure was fabricated by chemical dealloying from rapidly solidified amorphous precursors Ag_(38.75-x)Cu_(38.75)Si_(22.5)Au_x(x=0, 0.5, 1 and 5). The results indicate that the addition of small content Au in precursor can refine both the ligaments and pores obviously. Among the present components of the precursors, NP-AgAu alloys dealloying from Ag_(37.75)Cu_(38.75)Si_(22.5)Au_1 had the finest spongy structure. The size of pores was 5–10 nm and the grain size of ligaments was 10–20 nm. It also had the highest surface area of 106.83 m~2g~(-1) and the best catalytic activity towards electro-oxidation of formaldehyde with the peak current of 665 mA mg~(-1).     

Hot corrosion behavior of nanostructured Gd2O3 doped YSZ thermal barrier coating in presence of Na2SO4 + V 2O5 molten salts

Nickel-based superalloy DZ125 was first sprayed with a NiCrAlY bond coat and followed with a nanostructured 2 mol% Gd_2O_3-4.5 mol% Y_2 O_3-ZrO_2(2 GdYSZ) topcoat using air plasma spraying(APS). Hot corrosion behavior of the as-sprayed thermal barrier coatings(TBCs) were investigated in the presence of 50 wt%Na_2SO_4 + 50 wt% V_2O_5 as the corrosive molten salt at 900 ℃ for 100 h. The analysis results indicate that Gd doped YVO_4 and m-ZrO_2 crystals were formed as corrosion products due to the reaction of the corrosive salts with stabilizers(Y_2O_3, Gd_2O_3) of zirconia. Cross-section morphology shows that a thin layer called TGO was formed at the bond coat/topcoat interface. After hot corrosion test, the proportion of m-ZrO_2 phase in nanostructured 2GdYSZ coating is lower than that of nano-YSZ coating. The result reveals that nanostructured 2GdYSZ coating exhibits a better hot corrosion resistance than nano-YSZ coating.     

Growth, structural, optical, thermal and dielectric properties of a novel semi-organic nonline ar optical crystal: Dichloro-diglycine zinc II

Dichloro-diglycine zinc II(DCDGZ II),a semi-organic nonlinear optical material has been synthesized and single crystals were grown from the aqueous solution up to dimensions 20×10×3 mm3.The title compound,DCDGZ II(C4H10Cl2N2O4Zn H2O) crystallizes into monoclinic structure with the space group of C2/c.The unit-cell parameters were found to be a=14.4191(7),b=6.9180(2),c=12.9452(6) and Z=4.In the crystal structure,DCDGZ II layer is building up alternatingly with layers of water in which the zinc ions lie on a twofold axis.Theoretical calculations for polarizability,which are useful for device fabrication were made using Clausius–Mosotti equation and Penn analysis and the results were compared.Fourier transform infrared(FTIR) spectroscopic studies were performed for the identification of the different functional groups presented in the compound.The UV–vis–NIR absorption spectrum reveals that the lower UV cut-off wavelength is 240 nm.The optical band gap of the crystal was estimated as 2.2 eV.The surface morphology,thermal behaviour,dielectric properties have been studied using SEM,TG/DTA and LCR HITESTER analyzer.The nonlinear optical property of the crystal was also confirmed using Kurtz powder technique.     

Fabrication and character ization of electrospun TiO2/CuS micro–nano-scaled composite fibers

A process to fabricate a kind of novel micro–nano scaled TiO2/CuS composite fibers by electrospinning technique and chemical precipitation method was developed in the present study. The microstructures and photoelectronic properties of the fibers were characterize d using SEM, FT-IR, UV–vis and fluorescence spectroscopy. The results revealed that the TiO2 portion in the composite fibers was a mixture rutile and anatase phases while TiO2 and CuS had been fully composite. The fibers had smooth surface with a diameter of 50–300 nm. Comparing with pure TiO2 fiber, the TiO2/CuS micro–nano-scaled composite fibers exhibited a strong absorption in the visible light region and the efficiency of photo-induced charge separation were enhanced. This composite system is of widely potential applications in the areas such as solar cells, supercapacity, photocatalysis, etc.     

Influence of catalyst on structural and morphological properties of TiO2 nanostructured films prepared by sol–gel on glass

Transparent TiO2 thin films have been prepared by the sol-gel method using titanium alkoxides as precursors.Thin films were deposited on glass supports by the dip-coating technique.The TiO2 layer acts as a self-cleaning coating generated from its photocatalysis and photoinduced superhydrophilicity.The crystalline structure of TiO2 films was dominantly identified as the anatase phase,consisted of uniform spherical particles of about 14-50 nm in size,which strongly depends upon catalyst-type and heat treatment temperature.Increasing heat treating temperature can lead to an increase in crystalline size.The results indicated that the sample S.S(sample derived from sol containing sulfuric acid as catalyst) exhibits superhydrophilic nature and better photocatalytic activity,which can be attributed to its higher anatase content and lower crystalline size.Morphological studies,carried out using Atomic Force Microscopy(AFM),confirm the presence of crystalline phase with such a grain size and low surface roughness.Thus,the applied films exhibiting high photocatalytic activity,superhydrophilic behavior,and low surface roughness can be used as an efficient self-cleaning coating on glass and other optical applications.     

La2O3–Al2O3 –SiO2 glass-infiltrated 3Y-TZP all-ceramic composite for the dental restora tive application

The 3 mol% yttria stabilized tetragonal zirconia polycrystals (3Y-TZP) powder had three particle size distributions, while the fine one was lower than 100 nm. The 3Y-TZP compact was prepared by dry-pressing under pressures ranged from 10 to 30 MPa and then presintered at 1250°C for 2 h. The matrix dry-pressed under the pressure of 20 MPa had a porosity of 16.7% and could be easily processed by computer aided design and computer aided manufacturing (CAD/CAM), and which had been infiltrated by the La2O3–Al2O3–SiO2 glass at 1200°C for 4 h. The flexural strength and fracture toughness of the composite were 710.7 MPa and 6.51 MPa m^1/2, respectively. The low shrinkage (0.3%) of the composite can satisfy the net-shape fabrication standard. XRD results illustrated that zirconia in the La2O3–Al2O3–SiO2 glass-infiltrated 3Y-TZP all-ceramic composite was mainly in the tetragonal phase. SEM and EDS results indicated that the pores of the matrix were almost filled by the La2O3–Al2O3 –SiO2 glass     

Zr-pillared montmoril lonite supported cobalt nanoparticles for Fischer – Tropsch synthesis

In this article Fischer–Tropsch(FT) synthesis was studied over cobalt nanoparticles supported on modifed Montmorillonite(Zr-PILC).Co-loaded/Zr-PILC catalysts were synthesized by hydrothermal methods and were characterized by XRD,XRF,BET,H2-TPR,TGA and SEM techniques.FT reactions were carried out in fxed bed microreactor(T 225 1C,260 1C and 275 1C,P 1,5 and 10 bars).The FT-products obtained over Co-loaded/Zr-PILC catalysts showed increased selectivity of C2–C12hydrocarbons and decreased selectivity towards CH4and higher molecular weight hydrocarbons(C21) at a TOS of 2–30 h as compared to the Co-loaded/NaMMT catalysts.With increase in reaction temperature from225 1C to 275 1C,CO-conversion and CH4selectivity increases while that of C5+hydrocarbons decreases.Decrease in CH4selectivity while increase in C5+hydrocarbons and CO-conversion were observed on increasing the pressure of reaction.     

High-energy ion treatments of amorphous As40Se60 thin films for optical applic ations

The treatment of 100 MeV Ag swift-heavy ion(SHI) irradiation with five different fluences(3 1010, 1 1011, 3 1011, 1 1012, and3 1012ions/cm2) was used to design optical and structural properties of amorphous(a-) As40Se60 chalcogenide thin films. Swanepoel method was applied on transmission measurements to determine the changes in optical bandgap, Tauc parameter and linear optical parameters, i.e., linear optical absorption, extinction coefficient and linear refractive index. Dispersion of the material was determined by Wemple–DiDomenico relation.Changes in nonlinear optical parameters of third-order optical susceptibility and nonlinear refractive index were determined using semi-empirical relations. Changes in surface morphology of the films were investigated using SEM observation, which indicated that fluence 3 1012ions/cm2was upper threshold limit for these films for ion treatment. It is observed that optical bandgap reduces from 1.76 eV to 1.64 eV, and nonlinear refractive index increases from 1.31 10 10[esu] to 1.74 10 10[esu]. Linear refractive index initially increases from 2.80 to 3.52(for fluence3 1010ions/cm2) and then keeps decreasing. The observed changes in optical properties upon irradiation were explained in terms of structural rearrangements by Raman measurement. The study was compiled with the previous literature to propose SHI as an effective optical engineering technique to achieve desired changes according to the need of optical/photonic applications.