Synthesis and characterization of Pt-MoOx-TiO2 electrodes for direct ethanol fuel cells

To enhance the CO-tolerance performance of anode catalysts for direct ethanol fuel cells,carbon nanotubes were modified by titanium dioxide (donated as CNTs@TiO2) and subsequently served as the support for the preparation of Pt/CNTs@TiO2 and Pt-Mo/CNTs@TiO2 electrocatalysts via a UV-photoreduction method.The physicochemical characterizations of the catalysts were carried out by using X-ray diffraction (XRD),transmission electron microscopy (TEM),X-ray photoelectron spectroscopy (XPS),and infrared spectroscopy of adsorbed probe ammonia molecules.The electrocatalytic properties of the catalysts for methanol oxidation were investigated by the cyclic voltammetry technique.The results show that Pt-Mo/CNTs@TiO2 electrode exhibits the highest performance in all the electrodes.It is explained that,the structure,the oxidation states,and the acid-base properties of the catalysts are influenced due to the strong interaction between Ti and Mo species by adding TiO2 and MoOx to the Pt-based catalysts.     

Heteroseneous oxidation of carbonyl sulfide on mineral oxides

Heterogeneous oxidation of carbonyl sulfide （OCS） on mineral oxides including SiO2, Fe2O3, CaO, MgO, ZnO and TiO2, which are the main components of atmospheric particles, were investigated using in situ diffuse reflectance infrared Fourier transform spectroscopy （in situ DRIFTS）, ion chromatography （IC）, temperature-programmed desorption （TPD）, X-ray diffraction （XRD） and Brunauer-Emmett-Teller （BET） methods. The main products and intermediates of the heterogeneous oxidation of OCS on these oxides were identified with in situ DRIFTS and IC. The reaction mechanism and kinetics were also discussed. It is found that the reaction mechanism on these mineral oxides is the same as that on Al2O3 for the same final products and the intermediates at room temperature. Namely, OCS can be catalytically oxidized to produce surface SO4^2- species and gaseous CO2 through the surface hydrogen thiocarbonate （HSCO2-） and HSO; species. The activity series for heterogeneous oxidation of OCS follows： Al2O3 ≈ CaO 〉 MgO 〉 TiO2 ≈ ZnO 〉 Fe2O3 〉 SiO2. The specific area, basic hydroxyl and surface basicity of these oxides have effect on the reactivity. This study suggests that heterogeneous reactions of OCS on mineral dust may be an unneglectable sink of OCS.     

Synthesis and characterization of nano/micro-structured crystalline germanium dioxide with novel morphology

Nano/micro-structured germanium oxide （GeO2） was prepared using GeCl4 and KOH by a simple solution method in alkalic alcoholic solution. Different morphologies of GeO2 were obtained by changing the reaction conditions. The effects of the reaction time, the concentration of the reactants, the reaction temperature and the dispersant upon the morphology of the deposited GeO2 have been investigated. The products were detected by X-ray diffraction （XRD）, atomic force microscope （AFM）, scanning electron microscope （SEM） and transmission electron microscope （TEM）. Novel cross-like structures were obtained by using n-butylamine as the dispersant. The formation of the cross-like structures has been discussed and a solution-liquid-solid （SLS） mechanism was proposed.     

Effect of niobium alloying level on the oxidation behavior of titanium aluminides at 850°C

This work addresses the alloying of titanium aluminides used in aircraft engine applications and automobiles. The oxidation resistance behavior of two titanium aluminides of α₂ + γ(Ti₃Al + TiAl) and orthorhombic Ti₂NbAl, recognized as candidates for high-temperature applications, was investigated by exposure of the alloys for 100 h in air. Thus, oxidation resistance was expressed as the mass gain rate, whereas surface aspects were analyzed using scanning electron microscopy in conjunction with energy-dispersive X-ray spectroscopy, and the type of oxidation products was analyzed by X-ray diffraction and Raman spectroscopy. The orthorhombic Ti₂NbAl alloy was embrittled, and pores and microcracks were formed as a result of oxygen diffusion through the external oxide layer formed during thermal oxidation for 100 h.     

Heterogeneous oxidation of carbonyl sulfide on mineral oxides

Heterogeneous oxidation of carbonyl sulfide (OCS) on mineral oxides including SiO2,Fe2O3,CaO,MgO,ZnO and TiO2,which are the main components of atmospheric particles,were investigated using in situ diffuse reflectance infrared Fourier transform spectroscopy (in situ DRIFTS),ion chromatography (IC),temperature-programmed desorption (TPD),X-ray diffraction (XRD) and Brunauer-Emmett-Teller (BET) methods. The main products and intermediates of the heterogeneous oxidation of OCS on these oxides were identified with in situ DRIFTS and IC. The reaction mechanism and kinetics were also discussed. It is found that the reaction mechanism on these mineral oxides is the same as that on Al2O3 for the same final products and the intermediates at room temperature. Namely,OCS can be catalytically oxidized to produce surface SO42- species and gaseous CO2 through the surface hydrogen thiocarbonate (HSCO2-) and HSO3- species. The activity series for heterogeneous oxidation of OCS follows: Al2O3 ≈ CaO > MgO > TiO2 ≈ ZnO > Fe2O3 > SiO2. The specific area,basic hydroxyl and surface basicity of these oxides have effect on the reactivity. This study suggests that heterogeneous reactions of OCS on mineral dust may be an unneglectable sink of OCS.     

The influence of molar ratios of Ce/Zr on the selective catalytic reduction of NOx with NH3 over Fe2O3-WO3/CexZrl-xO2 （0 〈 x 〈 1） monolith catalyst

A series of CexZrl_xO2 （0 ≤ x ≤ 1） with dif- ferent molar ratios of Ce/Zr were syhthesized via coprecip- itation method, and Fe2O3-WO3/CexZrl-xO2 monolithic catalysts were prepared, for selective catalytic reduction of nitrogen oxides by ammonia （NH3-SCR）. The structural properties and redox behavior of the catalysts were com- prehensively characterized by N2 physisorption, X-ray diffraction （XRD）, X-ray photoelectron spectra （XPS）, H2-temperature programmed reduction （H2-TPR） and activity measurement for NH3-SCR. The results showed that the NH3-SCR activities of the catalysts were gradually enhanced by increasing the molar ratios of Ce/Zr, especially the low- temperature catalytic activity and the reaction temperature window. Fe2O3-WO3/Ceo.68Zro.3202 monolithic catalyst presented the best NH3-SCR activity among the investigated catalysts, more than 90 % NOx could be removed in the temperature range of 247-454 ℃ on the catalyst under the gas hourly space velocities of 30,000 h- 1. And it always held more than 99 % N2 selectivity and less than 20 ppm （1 ppm =10-6 L/L ） N20 generation concentration between 200 and 500 ℃, the catalyst also displayed its strong resistance of H20 and SO2. Good textural and structural properties, more surface Fe, Ce and active oxygen were together contributed to the excellent NH3-SCR performance of Fe2O3-WO3/ Ce0.68Zr0.32O2 catalyst.     

Preparation of Zn-doped TiO2 nanotubes electrode and its application in pentachlorophenol photoelectrocatalytic degradation

Zn-doped titanium oxide （TiO2） nanotubes electrode was prepared on a titanium plate by direct anodic oxidation and immersing method in sequence. Field emission scanning electron microscopy （FESEM） showed that the Zn-doped TiO2 nanotubes were well aligned and organized into high density uniform arrays with diameter ranging from 50 to 90 nm. The length and the thickness were about 200 and 15 nm respectively. TiO2 anatase phase was identified by X-ray diffraction （XRD）. X-ray photoelectronspectroscopy （XPS） indicated that Zn ions were mainly located on the surface of TiO2 nanotubes in form of ZnO clusters. Compared with TiO2 nanotubes electrode, about 20 nm red shift in the spectrum of UV-vis absorption was observed. The degradation of pentachlorophenol （PCP） in aqueous solution under the same condition （initial concentration of PCP： 20 mg/L; concentration of Na2SO4：0.01 mol/L and pH： 7.03） was carried out using Zn-doped TiO2 nanotubes electrode and TiO2 nanotubes electrode. The degradation rates of PCP using Zn-doped TiO2 nanotubes electrode were found to be twice and 5.8 times as high as that using TiO2 nanotubes electrode by UV radiation （400 μw/cm^2） and visible light radiation （4500 μw/cm^2）, respectively. 73.5% of PCP was removed using Zn-doped TiO2 nanotubes electrode against 45.5% removed using TiO2 nanotubes electrode in 120 min under UV radiation. While under visible light radiation, the degradation efficiency of PCP was 18.4% using Zn-doped TiO2 nanotubes electrode against 3.2% using TiO2 nanotubes electrode in 120 min. The optimum concentration of Zn doping was found to be 0.909%. The PCP degradation efficiencies of the 10 repeated experiments by Zn-doped TiO2 nanotubes electrode were rather stable with the deviation within 3.0%.     

Synthesis,characterization and electrocatalytic studies of palladium–manganese oxyhydroxide nanocomposite towards direct ethylene glycol fuel cell

The palladium nanoparticle grafted manganese oxyhydroxide nanorod （MON） electrocatalyst has been synthesized and tested for the electrooxidation of ethylene glycol （EG） in an alkaline medium. The MON was prepared using the hydrothermal method and the Pd nano- particles were coated on the MON using an in situ reduction method. The nanocatalyst thus prepared was characterized by powder X-ray diffraction, scanning electron microscopy, high resolution transmission electron microscopy, energy dispersive X-ray spectroscopy and electrochemical methods. The microscopic studies confirm the formation of MON and reveal that the Pd nanoparticles were grafted uniformly on the MON. In the voltammetric studies, the Pd/MON catalyst exhibited a six-fold improved peak current for ethylene glycol electrooxidation compared with the C/Pd. The EG electrooxidation reaction performances of the Pd/MON nanocatalyst in the alkaline solutions containing different quantities of EG were tested through cyclic voltammetry. The catalytic removal of the poisonous intermediates formed during electrooxidation of EG was explained. The present study shows that MON can act as an active support for the Pd nanocatalyst.     

Effects of CeO_2 pre-calcined at different temperatures on the performance of Pt/CeO_2–C electrocatalyst for methanol oxidation reaction

Pt/CeO2–C catalysts with CeO_2 pre-calcined at 300–600°C were synthesized by combining hydrothermal calcination and wet impregnation. The effects of the pre-calcined CeO_2 on the performance of Pt/CeO_2–C catalysts in methanol oxidation were investigated. The Pt/CeO2–C catalysts with pre-calcined CeO_2 at 300–600°C showed an average particle size of 2.6–2.9 nm and exhibited better methanol electro-oxidation catalytic activity than the commercial Pt/C catalyst. In specific, the Pt/CeO_2–C catalysts with pre-calcined CeO_2 at 400°C displayed the highest electrochemical surface area value of 68.14 m~2·g~(-1) and If/Ib ratio(the ratio of the forward scanning peak current density(If)and the backward scanning peak current density(Ib)) of 1.26, which are considerably larger than those(53.23 m2·g~(-1) and 0.79, respectively) of the commercial Pt/C catalyst, implying greatly enhanced CO tolerance.     

Selective catalytic reduction of NO x by hydrogen over modified Pd/TiO2-Al2O3 catalyst under lean-burn conditions

A series of Ni, Sn and Ca modified Pd/TiO2-Al2O3 catalysts were prepared by the incipient wetness impregnation method and their catalytic performance for the selective catalytic reduction of NOx by H2 was evaluated. The results showed that the NOx conversion and N2 selectivity were improved over Pd-Sn/TiO2-Al2O3 and Pd-Ni/TiO2- Al2O3 catalysts above 200 ℃. More importantly, the N2 selectivity and high-temperature activity of Pd-Sn/TiO2- Al2O3 catalyst was far superior to the single Pd/TiO2-Al2O3 catalyst. The optimal Sn loading was 2 wt.%. X-ray diffrac- tion （XRD） results showed that the interaction between Pd and Sn promotes the dispersion of Pd over TiO2-Al2O3. Temper- ature-programmed reduction （Ha-TPR） results demonstrated that the addition of Sn contributes to the formation of PdO and improving the redox property of Pd/TiOz-Al2O3. The addi- tives of Ni and Sn also facilitated the absorption of NOx and the oxidation of NO to NOa, which play important roles in the selective catalytic reduction of NOx by hydrogen.     

Development of a new method for analyzing free aluminum ions （Al3＋） in seafood using HPLC-ICP-MS

This paper presents a novel method for simultaneous online examination of free aluminum ions （Al3＋） in seafood, using solid- phase extraction and high-performance liquid chromatography online with inductively coupled plasma mass spectrometry （SPE- HPLC-ICP-MS）, without post-column reaction. The optimum conditions for chromatographic separation of Al3＋ were achieved using an IonPac CS5A analytical column with an IonPac CG5A guard column. The mobile phase consisted of 0.040 mol/L LiOH, 0.0060 mol/L 2,6-pyridinedicarboxylic acid, and 0.090 mol/L CH3COOH （pH 4.7）. The free Al3＋ ions in seafood were extracted by shaking with the mobile phase at 70℃ for 2 h. SPE was conducted using an Oasis MCX, 3cc/60 mg, 30 μm column, which was activated and equilibrated with 2 mL of methanol and 4 mL of deionized water before use. HCl （0.075 mol/L, 2 mL） was used to wash inorganic Al from the SPE column. The standard recoveries of Al3＋ were all above 89% and the relative standard deviations were all below 5%. The proposed method was successfully used for the examination of Al3＋ in seafood samples, and the results were similar to those obtained using the static equilibrium method.     

Preparation and Application of Water Dispersible Graphene as Antistatic Agent for SMS Nonwovens

In this paper, glucose was used as a green reducing agent and a capping reagent in the synthesis of water dispersible graphene, while using exfoliated graphite oxide （GO） as the precursor with the modified Hummers method. Characterizations of the graphene were conducted by UV-visihle absorption spectroscopy and X-ray diffraction （XRD）. Then the spunlaid-melthlowing-spuulaid （SMS） nonwovens were treated with the graphene solution via pad-dry-cure process. The surface and the antistatic property of the obtained nonwovens were tested. The results showed that O. 1 mg/mL graphene solution exhibited good stability in water. When treated with this solution, the graphene could be evenly dispersed on SMS nonwovens and the nonwovens had an excellent antistatic performance and a high relatively antistatic durability.     

Microstructure and oxidation resistance of SiC–MoSi2 multi-phase coating for SiC coated C/C composites

In order to improve the anti-oxidation of C/C composites, a SiC–MoSi2multi-phase coating for SiC coated carbon/carbon composites(C/C)was prepared by low pressure chemical vapor deposition(LPCVD) using methyltrichlorosilane(MTS) as precursor, combined with slurry painting from MoSi2 powder. The phase composition and morphology were analyzed by scanning electron microscope(SEM) and X-ray diffraction(XRD) methods, and the deposition mechanism was discussed. The isothermal oxidation and thermal shock resistance were investigated in a furnace containing air environment at 1500 1C. The results show that the as-prepared SiC–MoSi2coating consists of MoSi2 particles as a dispersing phase and CVD–SiC as a continuous phase. The weight loss of the coated samples is 1.51% after oxidation at 1500 1C for 90 h, and 4.79% after 30 thermal cycles between 1500 1C and room temperature. The penetrable cracks and cavities in the coating served as the diffusion channel of oxygen, resulted in the oxidation of C/C composites, and led to the weight loss in oxidation.     

Mesoporous iron oxide-silica supported gold catalysts for low-temperature CO oxidation

Mesoporous iron oxide-silica composite with a high silica content was synthesized by hydrothermal method, and another composite material with a high iron content was obtained by etching part of silica in alkaline solution. Gold catalysts were loaded onto both composites by a deposition-precipitation method, and used for CO oxidation. The samples were characterized by Brumauer- Emmet-Teller （BET）, X-ray diffraction （XRD）, X-ray photoelectron spectra （XPS）, transmission electron micro- scope （TEM） and scanning electron microscope （SEM） techniques. Both composites had high specific surface areas and were amorphous. The Au nanoparticles dispersed on the surface of the composites existed in metallic state. Composite with high silica content was not suitable for Au loading, and its supported gold catalyst showed poor per- formance in catalytic reaction. In contrast, composite with high iron content allowed efficient Au loading, and CO could be oxidized completely at low temperature on its supported gold catalyst. The effects of deposition-precipi- tation pH values on Au loading and activity of the catalyst were investigated, and the results indicated that Au loading was the highest and the catalyst was the most active for CO oxidation when the synthesis pH was adjusted to 8.     

Photocatalytic oxidation of gaseous benzene over nanosized TiO2 prepared by solvothermal method

Nanosized TiO2 particles were prepared by solvothermal method using tetrabutyl titanate as precursor,ethanol and water as solvents,and a facile immobilization method of nanosized TiO2 particles on woven glass fabric was developed. The samples obtained under various preparation conditions were charac-terized by means of thermo gravimetric analysis(TG) and differential scanning calorimetry(DSC) ,X-ray diffraction(XRD) ,transmission electron microscopy(TEM) ,high resolution-transmission electron mi-croscopy(HR-TEM) ,and Brunauer-Emmett-Teller(BET) . The results show that the cube-shape of TiO2 prepared by solvothermal method has good crystallinity of(101) surface,higher thermal stability and large specific surface area. Scanning electron microscopy(SEM) images confirmed that the immobi-lized TiO2 film was uniformly distributed and clung to the substrate firmly. The photocatalytic activity of the catalysts was tested using photocatalytic oxidation of gaseous benzene. The results show that the TiO2 calcined after solvothermal treatment suffers from lower specific surface area,and hence de-creases its photocatalytic activity. The photocatalytic activities of the TiO2 by solvothermal treatment with or without calcination in degradation 400 mg/m3 benzene are 3.7 and 4.1 times as high as catalyst without solvothermal treatment,respectively.     

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.     

Synthesis of titanium oxycarbonitride by carbothermal reduction and nitridation of ilmenite with recycling of polyethylene terephthalate (PET)

An innovative and sustainable carbothermal reduction and nitridation (CTRN) process of ilmenite (FeTiO₃) using a mixture of polyethylene terephthalate (PET) and coal as the primary reductant under an H₂-N₂ atmosphere was proposed.The use of PET as an alternative source of carbon not only enhances the porosity of the pellets but also results in the separation of Fe from titanium oxycarbonitride (TiO_xC_yN_z) particles because of the differences in surface tension.The experiments were carried out at 1250℃ for 3 h using four different PET contents ranging from 25wt% to 100wt% in the reductant.X-ray diffraction (XRD),scanning electron microscopy (SEM) in conjunction with energy-dispersive X-ray spectroscopy (EDX),and LECO elemental analysis were used to study the phases and microstructures of the reduced samples.In the case of 75wt% PET,iron distinctly separated from the synthesized TiO_xC_yN_z phase.With increasing PET content in the sample,the reduction and nitridation rates substantially increased.The synthesis of an oxycarbonitride with stoichiometry of TiO_0.02C_0.13N_0.85 with minimal intermediate titanium sub-oxides was achieved.The results also showed that the iron particles formed from CTRN of FeTiO₃ exhibited a spherical morphology,which is conducive for Fe removal via the Becher process.     

Supported Manganese Oxide on Graphite Oxide: Catalytic Oxidation of Nitrogen Oxide in Waste Gas

The catalytic oxidation of nitrogen oxide( NO) from waste gas was investigated using advanced oxidation process based on sulfate radicals. The manganese oxide immobilized on graphene oxide( GO) can activate peroxymonosulfate( PMS) for the oxidation of NO in waste gas. The Mn3O4 / GO catalyst system was characterized via X-ray diffraction( XRD), Fourier transform infrared spectrocopy( FT-IR), Raman spectroscopy, X-ray photoelectron spectroscopy( XPS), energy dispersive X-ray spectroscopy( EDS),and scanning electron microscope( SEM).The results showed that Mn3O4 was distributed on GO. The Mn3O4 /GO catalyst system exhibited efficient activity for NO oxidation when the Mn3O4 /GO catalyst had an optimum Mn3O4 loading. In addition,the best catalytic oxidation could be achieved within 60 min with 0. 25 mmol /L Mn3 O4 /GO catalyst, and2 mmol /L PMS dosage at 25 ℃. The catalysts also exhibited stable performance after several rounds of regeneration. Therefore,the results may have significant technical implication for utilizing Mn3O4 /PMS to oxidize NO for offgas treatment.     

Inter-phase selective corrosion of γ -TiAl alloy in molten salt environment at high temperature

Hot corrosion behavior of Ti-48Al-2Cr-2Nb alloy in molten salt environment of 75% Na2SO4 and 25% NaCl (mass fraction) at 800 °C was studied using oxida tion kinetics analysis, scanning electron microscopy, X-ray energy dispersive and X- ray diffraction analyses. The inter-phase selective corrosion, which caused the corrosion pits initiated from lamellar interfaces and the preferential corrosion of α2 phases, was observed during the hot corrosion of the alloy. The common controls of thermodynamic and kinetics in corrosion reactions with fluxing and active oxidation process were considered the essential hot corrosion mechanisms of the alloy. Moreover, lamellar refinement was proved to be an effective way to mitigate the inter-phase selective corrosion of the alloy in molten salts.     

Influence of polymer solution on the morphology and local structure of NH4ZnPO4powders synthesized by a simple precipitation method at room temperature

NH₄Zn PO₄powders were synthesized using a simple precipitation method at room temperature.The effects of polyvinyl pyrrolidone(PVP),polyvinyl alcohol(PVA),glucose,and hexadecyltrimethylammonium bromide(CTAB)solutions on the morphology and structure of the prepared samples were investigated.The phase composition and morphology of the prepared samples were characterized using X-ray diffraction and scanning electron microscopy,respectively.Depending on the polymer sources,the hexagonal structure prepared using non-surfactant of water completely changed to monoclinic structure when CTAB was added.X-ray absorption near-edge structure(XANES)and X-ray photoelectron spectroscopy(XPS)were performed to study the local structure and surface electronic structure of the prepared samples,confirming that the oxidation states of P and Zn ions are⁵⁺and²⁺,respectively.On the basis of the results of inductively coupled plasma atomic emission spectroscopy(ICP-OES),the NH₄Zn PO₄powders can be classified as a slow-release fertilizer where less than 15%of the ions were released in 24 h.A simple precipitation method using water,PVP,PVA,sucrose,and CTAB as a template can be used to synthesize NH4 Zn PO4 powders.In addition,this method may be extended for the preparation of other oxide materials.