CaCO3/TiO2 Nanoparticles Based Dye Sensitized Solar Cell

In this communication,the synthesis and structural,morphological,optical,and photo-electrochemical properties of TiO_2 and CaCO_3/TiO_2 nanoparticles as well as their applications in dye sensitized solar cells(DSSCs),have been reported.In an X-ray diffraction pattern of CaCO_3/TiO_2 nanoparticles,the peak at 29.41°of CaCO_3 has been detected,demonstrating its coating on the surface of TiO_2,which is further verified using high resolution-transmission electron microscopy,energy dispersive X-ray spectroscopy and Fourier transform infrared spectroscopy.The strong quenching in photoluminescence emission,in the case of CaCO_3/TiO_2nanoparticles,has been attributed to the decrease in recombination rate of photo-generated electron—hole pairs.In the case of UV—visible reflectance spectra,the absorption edge for CaCO_3/TiO_2 nanoparticles has slightly been found to be blue-shifted as compared to bare TiO_2 nanoparticles,which corresponds to an increase in energy band gap of the former.The dye desorption studies reveal that CaCO_3/TiO_2 electrodes adsorbed more dye than the bare TiO_2 electrode.CaCO_3/TiO_2 based DSSC show improved photoelectrochemical properties compared to the bare TiO_2 based DSSC as CaCO_3 coating on TiO_2 forms an energy barrier,and,consequently suppressing the charge recombination,and,thus,improving the overall energy conversion efficiency(η) from 0.46%to 1.44%under the illumination of simulated light of 100 mW/cm~2.     

TiO2 coated urchin-like SnO2 microspheres for efficient dye-sensitized solar cells

Urchin-like SnO2 microspheres have been grown for use as photoanodes in dye-sensitized solar cells （DSSCs）. We observed that a thin layer coating of TiO2 on urchin-like SnO2 microsphere photoanodes greatly enhanced dye loading capability and light scattering ability, and achieved comparable solar cell per- formance even at half the thickness of a typical nanocrystalline TiO2 photoanode. In addition, this photoanode only required attaching -55% of the amount of dye for efficient light harvesting compared to one based on nanocrystalline TiO2. Longer decay of transient photovoltage and higher charge recombination resistance evidenced from electrochemical impedance spectroscopy of the devices based on TiO2 coated urchin-like SnO2 revealed slower recombination rates of electrons as a result of the thin blocking layer of TiO2 coated on urchin- like SnO2. TiO2 coated urchin-like SnO2 showed the highest value （76.1 ms） of electron lifetime （＇r） compared to 2.4 ms for bare urchin-like SnO2 and 14.9 ms for nanocrystalline TiO2. TiO2 coated SnO2 showed greatly enhanced open circuit voltage （Voc）, short-circuit current density （Jsc） and fill factor （FF） leading to a four-fold increase in efficiency increase compared to bare SnO2. Although TiO2 coated urchin-like SnO2 showed slightly lower cell efficiency than nanocrystalline TiO2, it only used a half thickness of photoanode and saved -45% of the amount of dye for efficient light harvesting compared to normal nanocrystalline TiO2.     

Direct synthesis of highly conductive poly（3,4- ethylenedioxythiophene）：poly（4-styrenesulfonate） （PEDOT：PSS）/graphene composites and their applications in energy harvesting systems

We report for the first time highly conductive poly（3,4-ethylenedioxythiophene）： poly（4-styrenesulfonate） （PEDOT：PSS）/graphene composites fabricated by in situ polymerization and their applications in a thermoelectric device and a platinum （Pt）-free dye-sensitized solar cell （DSSC） as energy harvesting systems. Graphene was dispersed in a solution of poly（4-styrenesulfonate） （PSS） and polymerization was directly carried out by addition of 3,4-ethylenedioxythiophene （EDOT） monomer to the dispersion. The content of the graphene was varied and optimized to give the highest electrical conductivity. The composite solution was ready to use without any reduction process because reduced graphene oxide was used. The fabricated film had a conductivity of 637 S.cm-1, corresponding to an enhancement of 41%, after the introduction of 3 wt.% graphene without any further complicated reduction processes of graphene being required. The highly conductive composite films were employed in an organic thermoelectric device, and the device showed a power factor of 45.7 μW·m^-1K^-2 which is 93% higher than a device based on pristine PEDOT：PSS. In addition, the highly conductive composite films were used in Pt-free DSSCs, showing an energy conversion efficiency of 5.4%, which is 21% higher than that of a DSSC based on PEDOT：PSS.     

Photoelectrochemical Performance of Nb-doped TiO2 Nanoparticles Fabricated by Hydrothermal Treatment of Titanate Nanotubes in Niobium Oxalate Aqueous Solution

Nb-doped TiO2 nanoparticles were prepared by hydrothermal treatment of titanate nanotubes in niobium oxalate aqueous solution.The effect of Nb doping and rutile content on the photoelectrochemical performance based on TiO2 powder electrodes was investigated.The results show that Nb-doped TiO2 with a small amount of rutile exhibits the enhanced photoelectric conversion efficiency for dye-sensitized solar cell.The highest photoelectric conversion efficiency of 8.53%is obtained for 1%Nb—TiO2 containing a small amount of rutile.When a small amount of rutile contained in 2%Nb—TiO2,a higher photoelectric conversion efficiency of8.77%is achieved.     

Low-Temperature and Surfactant-Free Synthesis of Mesoporous TiO_2 Sub-Micron Spheres for Efficient Dye-Sensitized Solar Cells

Dye-sensitized solar cells(DSSCs) are one of the most promising next-generation solar cells due to their advantages over other counterparts. The photoanode of DSSCs has a great effect on the photovoltaic performance. Traditional photoanode includes a bottom nanoparticle layer and an upper scattering layer for better light capture in longer wavelength. Mesoporous nanostructures with size comparable to the wavelength of visible light are considered to be excellent light scattering centers by providing extra places for dye loading. Developing a green synthetic method is of great importance. Herein we report a facile and surfactant-free synthesis of mesoporous rutile TiO_2 submicrometer-sized spheres at temperature as low as 70°C. DSSCs based on photoanodes with an upper scattering layer composed of as-obtained mesoporous spheres on nanoparticle dense layer demonstrate an 18.0% improvement of power conversion efficiency. This simple approach may offer an energy-efficient and environmentally friendly alternative for DSSCs fabrication.     

Facile Synthesis of SnO2 Nanotube Arrays by Using ZnO Nanorod Arrays as Sacrificial Templates

SnO2 nanotube arrays have been synthesized by means of a simple and low-cost method. The ZnO nanorod arrays prepared by aqueous chemical growth method were used as templates. By liquid phase deposition, SnO2 nanotubes were obtained with proper deposition time. Scanning electron microscopy, transmission electron microscopy and X-ray diffraction were used to characterize the morphologies and structures of the products, and the formation mechanism was discussed according to the experimental results.     

Submicrometer-scale ZnO Composite Aggregate Arrays Photoanodes for Dye-sensitized Solar Cells

Submicrometer-scale ZnO composite aggregate arrays of nanorods and nanoparticles were prepared by simple wet-chemical route and studied as dye-sensitized solar cells（DSSCs）photoanodes.The ZnO composite aggregate arrays significantly improved the efficiency of DSSCs due to their relatively high surface area,fast electron transport,and enhanced light-scattering capability.A short current density(J_sc)of 11.7 mA/cm² and an overall solar-to-electric energy conversion efficiency（η）of 3.17%were achieved for the ZnO composite aggregate DSSCs,which were much higher than those obtained for the monodisperse aggregate DSSCs (J_sc=6.9 mA/cm²,η=1.51%)and ZnO nanorod array DSSCs(J_sc=4.2 mA/cm²,η=0.61%).     

A Self-supported Graphene/Carbon Nanotube Hollow Fiber for Integrated Energy Conversion and Storage

Wearable fiber-shaped integrated energy conversion and storage devices have attracted increasing attention,but it remains a big challenge to achieve a common fiber electrode for both energy conversion and storage with high performance.Here,we grow aligned carbon nanotubes(CNTs)array on continuous graphene(G)tube,and their seamlessly connected structure provides the obtained G/CNTs composite fiber with a unique self-supported hollow structure.Taking advantage of the hollow structure,other active materials(e.g.,polyaniline,PANI)could be easily functionalized on both inner and outer surfaces of the tube,and the obtained G/CNTs/PANI composite hollow fibers achieve a high mass loading(90%)of PANI.The G/CNTs/PANI composite hollow fibers can not only be used for high-performance fiber-shaped supercapacitor with large specific capacitance of 472 mF cm^-2,but also can replace platinum wire to build fiber-shaped dye-sensitized solar cell(DSSC)with a high power conversion efficiency of 4.20%.As desired,the integrated device of DSSC and supercapacitor with the G/CNTs/PANI composite hollow fiber used as the common electrode exhibits a total power conversion and storage efficiency as high as 2.1%.Furthermore,the self-supported G/CNTs hollow fiber could be further functionalized with other active materials for building other flexible and wearable electronics.     

Annealing Effect of ZnO on the Performance of Inverted Organic Photovoltaic Devices

ZnO nanoparticles films were prepared via sol-gel process and incorporated into inverted organic photovoltaic devices with a structure of ITO/ZnO/P3HT:PCBM/MoO_3/Ag,in which ZnO film served as an electron selective layer.The effects of annealing temperature of ZnO film on the device performance were investigated.When the annealing temperature was 300 ℃,a well-arranged ZnO thin film was obtained,and the optimized device had doubled short circuit current density(J_(SC)) and seven-fold higher power conversion efficiency(PCE)compared to the devices without ZnO film.This improvement could be attributed to the enlarged interfacial area of ZnO/active layer and better energy band matching which causes an efficient electron extraction and a decreased interface energy barrier.At particularly high annealing temperature,dramatically increased sheet resistance of indium tin oxide(ITO) was found to cause PCE deterioration.Our finding indicates that it is highly important to investigate both morphology and electrical effects for understanding and optimizing organic photovoltaic(OPV) performance.     

Mesocrystalline TiO<Subscript>2</Subscript> nanosheet arrays with exposed {001} facets: Synthesis via topotactic transformation and applications in dye-sensitized solar cells

A facile,fluorine-free approach for synthesizing vertically aligned arrays of mesocrystalline anatase TiO2 nanosheets with highly exposed {001} facets was developed through topotactic transformation.Unique mesocrystalline {001}-faceted TiO2 nanosheet arrays vertically aligned on conductive fluorine-doped tin oxide glass were realized through topotactic conversion from single-crystalline precursor nanosheet arrays based on lattice matching between the precursor and the anatase crystals.The morphology and microstructure of the {001}-faceted TiO2 nanosheets could be readily modulated by changing the reactant concentration and annealing temperature.Owing to enhanced dye adsorption,reduced charge recombination,and enhanced light scattering arising from the exposed {001} facets,in addition to the advantageous features of low-dimensional structure arrays (e.g.,fast electron transport and efficient charge collection),the obtained TiO2 nanosheet arrays exhibited superior performance when they were used as anodes for dye-sensitized solar cells (DSSCs).Particularly,{001}-faceted TiO2 nanosheet arrays ～15 μm long annealed at 500 ℃ showed a power conversion efficiency of 7.51％.Furthermore,a remarkable efficiency of 8.85％ was achieved for a DSSC based on double-layered TiO2 nanosheet arrays ～35 μm long,which were prepared by conversion from the precursor nanoarrays produced via secondary hydrothermal growth.     

Effects of Strontium,Magnesium Addition,Temperature Gradient,and Growth Velocity on AI-Si Eutectic Growth in a UnidirectionaUy-solidified Al-13 wt% Si Alloy

Al-Si eutectic growth mechanism was investigated in a directionally-solidified AI-1 3 wt% Si alloy with different strontium （Sr） and magnesium （Mg） additions, growth velocities and temperature gradients. Macro- and micro- scale metallographic analyses revealed that addition level of Sr and Mg, temperature gradient and growth velocity are important factors affecting stability of solidifying AI-Si eutectic front and the final morphology of eutectic grains in the solidified A1-13 wt% Si alloys. By varying （tailoring） these factors, a variety of eutectic grain structures and morphologies such as planar front, cellular structure, a mix of cellular and columnar, or equiaxed dendrites, can be obtained. Increasing temperature gradient, reducing growth velocity, or decreasing Sr and Mg contents is beneficial to stabilizing planar growth front of eutectic grains, which is qualitatively in accordance with constitutional supercooling criterion for binary eutectic growth. In contrast, adding more Sr and Mg, increasing growth velocity, or decreasing temperature gradient produces large constitutional supercooling, leading to columnar-equiaxed transition （CET） of eutectic structure, which can be interpreted on the basis of Hunt＇s Model. It is also found that both solute concentration and solidification variables have significant impact not only on eutectic growth, but also on gas porosity formation.     

Fabrication of (Ti,Hf)-rich NiTiHf Alloy Using Graphitic Mold and Crucible

In this research, fabrication of a(Ti,Hf)-rich NiTiHf alloy by using vacuum induction melting(VIM) process and a graphitic crucible was investigated. For this purpose, casts with the nominal composition of Ni49Ti36Hf15 were prepared in graphitic crucible and mold. Optical microscopy(OM), scanning electron microscopy(SEM), energy dispersive X-ray spectroscopy(EDS), X-ray diffraction(XRD), and differential scanning calorimetry(DSC) tests were employed to characterize the samples. Results demonstrated that microstructure of the first cast was composted of a B2 austenite phase as well as a great amount of two differently formed(Ti,Hf)C carbides.Moreover, no austenite 4 martensite transformation peak was detected in the DSC curve of this sample,indicating a drastic decline in the transformation temperatures. In the succeeding cast, however, owing to the formation of carbide layers on the inner surfaces of the graphitic crucible and mold during the initial casting process, the amounts of carbides decreased remarkably. This cast exhibited transformation temperatures above100° C, while XRD pattern denoted the presence of B190 monoclinic martensite phase at room temperature.All in all, results confirmed that VIM process using graphitic mold and crucible can be considered as an appropriate method for the fabrication of(Ti,Hf)-rich NiTiHf high temperature shape memory alloys.     

Development and Characterization of Al2O3 Dispersed Al/Mg/Cu/Ti Matrix Composite

The effect of dispersion with different weight fractions of Al2O3 particles in metallic matrices （AI/Mg/Ti/Cu） fabricated by powder metallurgy was investigated. In the case of 15 wt% Al2O3 reinforced composites, peak hardness was attained which subsequently decreased with increasing the content of Al2O3. A correlation between the microhardness and nanomechanical properties at submicron scale was examined for all the composites. Specific strength and specific modulus were measured in order to figure out the performance of the composites.     

Microstructure,Phase Transformation,Precipitation Behavior and Mechanical Properties of P/M Cu40Zn-1.0 wt% Ti Brass Alloy via Spark Plasma Sintering and Hot Extrusion

The effect of titanium addition on the microstructure and mechanical properties of brass Cu4OZn has been studied via the powder metallurgy （P/M） route. The water-atomized Cu4OZn-1.0 wt% Ti alloy powder was consolidated at different temperatures in the range of 400-600℃ using spark plasma sintering （SPS） and hot extrusion subsequently. Results show that the super-saturated solid solution titanium element in rapidly cooled brass Cu4OZn powder created high chemical potential for a precipitate reaction, showing significant grain refinement effects on the consolidated Cu4OZn matrix. Consequently, excellent mechanical properties were obtained by precipitation hardening and work hardening after sintering and extrusion, with yield strength of 390 MPa, ultimate tensile strength of 617 MPa, and Vickers micro-hardness of 192 HV, which are 28.7%, 23.4%, and 23.9% higher values than those of extruded Cu4OZn brass, respectively.     

Role of Double Oxide Film Defects in the Formal ion ol’ Gas Porosity in Commercial Purity and Sr-containing A1 Alloys

The role of double oxide film （bifilm） defects in the formation of gas porosity in commercial purity and Srcontaining AI alloys was investigated by means of a reduced pressure test （RPT） technique. The liquid metal was poured from a height into a crucible to introduce oxide defects into the melt. The melt was then subjected to different ＂hydrogen addition＂ and ＂holding in liquid state＂ regimes before RPT samples were taken. The RPT samples were then characterized by determining their porosity parameters and examining the internal surfaces of the pores formed in them by scanning electron microscopy. The results indicated oxide defects as the initiation sites for the growth of gas porosity, both in commercial purity and Sr-containing AI alloys. The results also rejected reduction of the surface tension of the melt, increase in the volumetric shrinkage and reduction in interdendritic feeding as the possible causes of an increase in the porosity content of the AI castings modified with strontium. The change in the composition of the oxide layers of double oxide film defects was suggested to be responsible for this behaviour.     

Fabrication of Shape-Controlled Au Nanoparticles in a TiO2-Containing Mesoporous Template Using UV Irradiation and Their Shape-Dependent Photocatalysis简

A SiO_2-TiO_2 template with ordered tubular mesochannels has been prepared by the sol—gel method.Au nanorods are deposited in the tubular mesochannels of the SiO_2—TiO_2 template,and the shape of Au is changed from nanorods to nanospheres by ultraviolet irradiation during thermal deposition.The photocatalytic activity of mesoporous SiO_2—TiO_2 with/without Au nanorods/nanospheres is evaluated.Deposition of Au in the mesoporous SiO_2—TiO_2 template enhances the photocatalysis of TiO_2.Interestingly,the sample containing Au nanorods exhibits higher photocatalytic activity than that with Au nanospheres.Photocatalysis by exciting surface plasmon resonance is not detected in the composite samples regardless of the shape of the deposited Au nanoparticles.     

Isothermal Oxidation Behavior of Dysprosium/S-Doped β-NiAl Alloys at 1200°C

A β-NiAl alloy with normal purity, a S-doped and a Dy and S co-doped b-NiAl alloys were prepared by arc-melting and their corresponding S contents were less than 20×10 6, 33×10-6 and 22×10-6, respectively. The isothermal oxidation behavior of the alloys at 1200° C was investigated and the extent of S segregation at the scalee alloy interface was determined by scanning Auger microscopy. S-doping had no significant effect on the phase transformation rate from q- to a-Al2O3, while the addition of Dy retarded this process. For the Sdoped alloy, scale rumpling occurred only after 2 h thermal exposure and numerous large voids were observed at the scalee alloy interface where S segregated. In contrast to this, the oxide scale formed on the Dy and S co-doped alloy still remained flat even after 50 h isothermal oxidation and only small voids existed at the interface where S segregation was not detected.     

Optical and Microstructural Characterisations of Pulsed rf Magnetron Sputtered Alumina Thin Film

Alumina thin films were deposited on fused quartz and SS304 substrate by pulsed rf magnetron sputtering with both direct and reactive methods. The films were characterised by energy dispersive X-ray spectroscopy, X-ray diffraction, scanning electron microscopy, field emission scanning electron microscopy and atomic force microscopy to reveal the microstructure, surface morphology and topography of thin films. Transmittance and reflectance of alumina thin film were evaluated after deposition on the quartz substrate. Transmittance of the quartz remains almost un-altered when alumina was deposited by the reactive sputtering. A marginal decrease of ~4% in the transmittance of quartz was, however, observed after deposition of alumina by direct sputtering. Infrared emittance of the substrate also remains almost constant after deposition of thin alumina film. Further, as-deposited alumina on SS304 obtained by both direct and reactive sputtering process was amorphous in nature. However, after annealing crystalline peaks were observed.     

Influence of Features of Interphase Boundaries on Mechanical Properties and Fracture Pattern in Metal--Ceramic Composites

The results of a theoretical study on the influence of strength of interphase boundaries in metal-ceramic composite on macroscopical characteristics of composite response such as strength, deformation capacity, fracture energy and fracture pattern are presented. The study was conducted by means of computer-aided simulation by means of movable cellular automaton method taking account of a developed ＂mesoscopical＂ structural model of particle-reinforced composite. The strength of interphase boundaries is found to be a key structural factor determining not only the strength properties of metal-ceramic composite, but also the pattern and rate of fracture. The principles for achievement of the high-strength values of particle/binder interfaces in the metal-ceramic composition due to the formation of the wide transition zones （areas of variable chemical composition） at the interphase boundaries are discussed. Simulation results confirm that such transition zones provide a change in fracture mechanism and make the achievement of a high-strength and a high deformation capacity of metal-ceramic composite possible.     

Corrosion Behavior of Extruded near Eutectic Al—Si—Mg and 6063 Alloys

In this work,a comparison study on corrosion behavior of extruded near eutectic Al—12.3%Si—0.26%Mg and 6063 alloys has been carried out by mass loss test in 4%H₂SO₄ aqueous solution in the open air and potentiodynamic polarization test in 3.5 wt.%NaCI aqueous solution.Results indicate that the corrosion resistance of the near eutectic Al—Si—Mg alloy is less than that of 6063 alloy.Macro/microscopy and scanning electron microscopy results clearly show the difference of the corrosion progress of these two alloys in 4%H₂SO₄ aqueous solution.The corrosion type of 6063 alloy is pitting corrosion.The Mg₂Si and AlFeSi particles and surface defects act as nucleation sites for pitting,and the amount and distribution of them have a significant effect on the pitting behavior.For the near eutectic alloy,there are two types of corrosion cells. One is between the extruded primaryα-AI and the eutectic,the other is between the eutectic Al and eutectic Si particles.Combination of these two types of corrosion cells leads to a lower corrosion resistance,a higher mass loss of the near eutectic alloy compared with 6063 alloy,and the formation of the paralleling corroded grooves.