The induced synthesis of mixed phase niobate by Cu doping and its photocatalytic property

Cu-doped KNb₃O₈ photocatalysts were prepared using a simple solid-state method. The catalysts were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), photoluminescence (PL), X-ray photoelectron spectroscopy (XPS) and UV-vis diffuse reflectance spectrum. XRD and SEM analyses suggest that Cu doping can induce the formation of the compound K₆Nb_10.8O₃₀ with tungsten-bronze structure and the relative content of K₆Nb_10.8O₃₀ in the Cu-doped samples increased with increasing Cu doping amount. When the Cu doping amount reaches 2 wt.%, the as-prepared sample is mainly composed of K₆Nb_10.8O₃₀. The photocatalytic properties of the catalysts were evaluated using the degradation of acid red G. The results showed that Cu-doping significantly increased the photocatalytic activity of the KNb₃O₈ catalyst. The optimum dopant concentration range of Cu was found to be 0.3-1 wt.%. The synergistic effect of Cu doping and mixed phase niobate compounds is responsible for the enhanced photocatalytic activity.     

无模板剂的溶胶-水热法合成具有可见光响应的氮掺杂混晶 TiO2(锐钛矿/金红石/板钛矿)纳米棒束

采用无模板剂的溶胶-水热法制备了具有可见光响应的N掺杂锐钛矿/金红石/板钛矿型TiO_2(N-TiO_2)纳米棒束,并利用X射线衍射(XRD)、透射电镜(TEM)、紫外-可见光漫反射光谱(UV-Vis DRS)、傅里叶变换红外光谱(FTIR)和X射线光电子能谱(XPS)等手段对获得的样品进行了表征。以甲基橙为模型反应物,评价了N-TiO_2纳米棒束的光催化活性。表征结果结合光催化活性评价结果显示,与P25-TiO_2相比,N掺杂、混晶及纳米棒束之间的协同作用是所制备的混晶N-TiO_2纳米棒束具有良好光催化活性的主要原因,并对混晶N-TiO_2纳米棒束光催化降解甲基橙的机理进行了探讨。     

The effect of milling atmospheres on photocatalytic property of Fe-doped TiO2 synthesized by mechanical alloying

The Fe-doped TiO₂ powders were, respectively, milled in argon, air and oxygen atmospheres, the oxygen partial pressure (P_O2) of which increase in turn. The Fe concentration was found to be 4.468, 4.227 and 4.473 at.% for the powders milled in argon, air and oxygen, respectively. The rietveld refined of X-ray diffraction (XRD) revealed that the milled samples were pure rutile structure. The Raman spectra confirmed the results of XRD. Furthermore, it indicated that the amount of oxygen vacancies increased with the decrease of P_O2. Fe dissolved in TiO₂ was found to take Fe²⁺/Fe³⁺ ionic valences. The absorption edge was shifted to visible light range by the doping of Fe. And visible light photocatalytic activity enhanced with the decrease of P_O2 due to the increase of oxygen vacancies.     

Synthesis and photocatalytic performance of Ag-loaded β-Bi2O3 microspheres under visible light irradiation

The visible-light-driven photocatalyst Ag/β-Bi₂O₃ microspheres were synthesized by a simple chemical method. First, β-Bi₂O₃ microspheres were obtained by a thermal treatment of sphere-like Bi₂O₂CO₃ precursor at 360 °C for 3 h in air and then Ag nanoparticles were in situ incorporated into β-Bi₂O₃ microspheres by impregnation method. The as-synthesized samples were characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), UV-vis spectroscopy and photoluminescence measurements. The experimental results demonstrated that the visible light absorption of β-Bi₂O₃ photocatalyst is greatly enhanced with the incorporation of Ag nanoparticles. The SEM and TEM observations revealed that the Ag nanoparticles can be homogenously incorporated in the β-Bi₂O₃ microspheres. The photocatalytic activity of Ag/β-Bi₂O₃ sample was evaluated by the photodegradation of the Rhodamine-B under visible light irradiation as a function of Ag content. It is found that the photocatalytic efficiency of β-Bi₂O₃ can be significantly improved with the incorporation of Ag nanoparticles up to 2.0 wt% Ag. The mechanism for the enhanced photocatalytic activity is also presented.     

Influence of the structure of TiO<Subscript>2</Subscript>, CeO<Subscript>2</Subscript>, and CeO<Subscript>2</Subscript>-TiO<Subscript>2</Subscript> supports on the activity of Ru catalysts in the catalytic wet air oxidation of acetic acid

Ru catalysts, supported on TiO₂, CeO₂, and CeO₂-TiO₂, were prepared by the impregnation method. The effect of the structure of the supports on the activity of Ru catalysts was investigated in the catalytic wet air oxidation (CWAO) of acetic acid under 230°C and 5 MPa in a batch reactor. Physical properties including the surface area, crystalline phase, and surface components of the Ru catalysts were characterized by N₂ adsorption, X-ray powder diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). The CeO₂-based Ru catalysts had good activity, and the prepared RuO₂/CeO₂ catalyst showed markedly higher activity than the RuO₂/CeO₂-TiO₂ catalyst. The surface structure, the high amount of chemisorbed oxygen on the catalyst surface, and the suitable pH_pzc value of the supports played an important role in the activity of the Ru catalysts in CWAO of acetic acid.     

硫氧化物La3NbS2O5的硫化合成及其光催化活性

采用H2S硫化的方法合成硫氧化物La3NbS2O5,并通过X射线衍射(XRD)、紫外?可见漫反射(DRS)、场发射扫描电镜(FE-SEM)等技术对其进行表征和分析,研究硫化条件与光催化分解水产氢活性的关系。结果表明：与传统固相法比较,硫化法使La3NbS2O5在更低的温度和更短的反应时间(1 h)合成;合成的La3NbS2O5粒子呈规则的盘子状,粒径为0.1?0.6μm,粒子表面光滑;在1073 K硫化1 h制得的La3NbS2O5具有极高的产氢活性,大约为固相法制得La3NbS2O5的产氢活性的1.83倍。     

Optical properties and photocatalytic activity of Nd-doped ZnO powders

To improve the photocatalytic activity of zinc oxides, ZnO powders doped with different neodymium (Nd) concentrations were prepared via hydrothermal method. X-ray diffraction (XRD) together with X-ray photoelectron spectroscopy (XPS) patterns revealed that Nd atoms were successfully incorporated into the ZnO lattice. XRD pattern also showed some anisotropy of the powders. The photoluminescence (PL) spectrum demonstrated a strong and broad peak in the visible light region, and the intensity of visible light emission was enhanced by Nd-doping. The photocatalytic activity was evaluated by the degradation of methyl orange solution. It is shown that doping of Nd into ZnO induces an increase of the photocatalytic activity and it attains to optimum at 3% (mole fraction) doping concentration. The intense visible light emission and the enhanced photocatalytic activity were explained by the increase in electron hole pairs and induced defects like antisite oxygen O_Zn and interstitial oxygen O_i, due to the doping of Nd.     

Novel AgCl/Ag<Subscript>2</Subscript>CO<Subscript>3</Subscript> heterostructured photocatalysts with enhanced photocatalytic performance

A series of novel AgCl/Ag₂CO₃ heterostructured photocatalysts with different AgCl contents (5 wt%, 10 wt%, 20 wt%, and 30 wt%) were prepared by facile coprecipitation method at room temperature. The resulting products were characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and ultraviolet–visible diffuse reflectance spectroscopy (UV–Vis DRS), respectively. The photocatalytic activity of the samples was evaluated by photocatalytic degradation of methyl orange (MO) under UV light irradiation. With the optimal AgCl content of 20 wt%, the AgCl/Ag₂CO₃ composite exhibits the greatest enhancement in photocatalytic degradation efficiency. Its first-order reaction rate constant (0.67 h^?1) is 5.2 times faster than that of Ag₂CO₃ (0.13 h^?1), and 16.8 times faster than that of AgCl (0.04 h^?1). The formation of AgCl/Ag₂CO₃ heterostructure could effectively suppress the recombination of the photo-generated electron and hole, resulting in an increase in photocatalytic activity.     

Fast fabrication of Co3O4 and CuO/BiVO4 composite photocatalysts with high crystallinity and enhanced photocatalytic activity via ultrasound irradiation

A facile and efficient approach for the fabrication of Co₃O₄ and CuO/BiVO₄ composite photocatalysts was developed by intense ultrasound irradiation at room temperature. The as-synthesized samples were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), photoluminescence (PL) spectroscopy, UV-vis diffuse reflectance spectra (UV-vis DRS), and Brunauer-Emmett-Teller (BET) surface areas. The photocatalytic activity of the composite catalysts was evaluated by photocatalytic degradation of acid orange II under visible light (λ > 420 nm) irradiation. Results showed that under intense ultrasonic irradiation, the precursors of copper acetate and cobaltous acetate could transform into CuO and Co₃O₄, respectively and the amorphous BiVO₄ can easily crystallize to highly crystalline BiVO₄. The composite photocatalysts exhibited much higher photocatalytic activity than that of pure BiVO₄. The enhanced photocatalytic performance could be attributed to the high crystallinity of BiVO₄ and the formed p-n heterojunction of Co₃O₄/BiVO₄ or CuO/BiVO₄. These two factors can effectively suppress the recombination of photogenerated hole-electron pairs.     

Heterojunction semiconductor SnO2/SrNb2O6 with an enhanced photocatalytic activity: The significance of chemically bonded interface

Heterojunction photocatalysts SnO₂/SrNb₂O₆ were synthesized by a milling–annealing technique. The powders were characterized by X-ray diffraction (XRD), Brunauer–Emmett–Teller (BET) method, transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDS) and UV–vis diffuse reflection spectroscopy (DRS). Their UV-induced photocatalytic activities were evaluated by the degradation of methyl orange and methylene blue. The results generally show that the binary semiconductors SnO₂/SrNb₂O₆, with matching band potentials, exhibit better photocatalytic properties than the single phase SrNb₂O₆ or SnO₂. The effective electron–hole separation both at the chemically bonded interface and in the two semiconductors is believed to be mainly responsible for the increased photocatalytic performance of composites. The formation of chemically bonded interfaces between SnO₂ and SrNb₂O₆ particles makes the interparticle charge transfer more spatially available and smoother, which is significant to enhance the photocatalytic activity.     

Preparation of nanometric CeO2–ZrO2–Nd2O3 solid solution and its catalytic performances

A kind of nanometric CeO₂–ZrO₂–Nd₂O₃ (CZN) solid solution for a carrier in the automotive three-way catalysts was synthesized by a coprecipitation method and characterized by means of X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), nitrogen adsorption–desorption (BET), scanning electron microscopy (SEM) and oxygen storage capacity (OSC). For the purpose of comparison, an unincorporated CeO₂–ZrO₂ (CZ) was also synthesized. The XRD measurements disclose the prepared CeO₂–ZrO₂–Nd₂O₃ have a face-centered cubic fluorite structure and nanoparticle sizes. According to the results of XPS, Nd³⁺ ions can enter the CZ lattice and form a homogenous solid solution. Oxygen storage capacity measurements reveal that CeO₂–ZrO₂–Nd₂O₃ display high oxygen mobility at a low temperature. The results of the activity tests show that the catalyst exhibits good three-way catalytic activity and fairly wide range of air-to-fuel ratios.     

Preparation, characterization and photocatalytic activity of sulfuric acid-modified titanium-bearing blast furnace slag

The feasibility of reducing Cr(VI)from the aqueous solution by sulfuric acid-modified titanium-bearing blast furnace slag(SATBBFS)as a photocatalyst was investigated.The photocatalysts were examined by X-ray diffraction(XRD),UV-vis diffuse reflectance spectra,thermogravimetric analysis(TG)and Fourier transform infrared spectroscopy(FTIR).The photocatalytic activities of the different catalysts were evaluated by the photocatalytic reduction of Cr(VI)under UV-vis light irradiation.The results show that the photocatalytic activities of SATBBFS catalysts are strongly dependent on CaTiO3-to-TiO2 mass ratio,adsorption capacity and surface acidity,and SATBBFS calcined at 400°C shows a higher photocatalytic activity compared with other catalysts.     

Bismuth tungstate nano/microstructures: Controllable morphologies, growth mechanism and photocatalytic properties

A facile hydrothermal process was utilized to synthesize bismuth tungstate (Bi₂WO₆) hierarchical nano/microstructures, by which various morphologies could be achieved, including caddice clew-like, nest-like, flower-like and plate-like nanostructures. From the scanning electron microscopy (SEM) and X-ray diffraction (XRD) analysis, the morphologies and phases of the as-synthesized Bi₂WO₆ exhibited a strong dependence on the pH value of the precursor solutions. Moreover, the formation mechanisms of the controllable assembly of these Bi₂WO₆ nano/microstructures under different pH values were investigated. The photocatalytic performances of Bi₂WO₆ with different morphologies were also discussed, and the nest-like Bi₂WO₆ displayed the best photocatalytic activity due to the effective visible absorption and the large surface areas.     

Synthesis, characterization and photocatalytic activity of NaNbO3/ZnO heterojunction photocatalysts

A series of NaNbO₃/ZnO heteronanostructures were synthesized with the hydrothermal method. Various characterization methods such as X-ray powder diffraction (XRD), scanning electronic microscope (SEM) and energy dispersive X-ray spectrometer (EDS), transmission electron microscope (TEM), X-ray photoelectron spectra (XPS) and diffuse reflectance spectra (DRS) were employed to investigate the structure, morphology and photocatalytic properties. The photocatalytic activity of the catalysts was evaluated by the degradation of methylene blue dye and the highest photocatalytic efficiency was observed when the content of NaNbO₃ was 10 wt.%. The photocatalytic mechanism of the heterojunction was also discussed. The effective transformation of the photoexcited electron and holes restricted the recombination of charges, which was regarded as the main reason of the high photocatalytic activity.     

Catalytic reduction of SO2 by CO over CeO2–TiO2 mixed oxides

The structure and catalytic desulfurization characteristics of CeO₂–TiO₂ mixed oxides were investigated by means of X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and catalytic activity tests. According to the results, a CeO₂–TiO₂ solid solution is formed when the mole ratio of cerium to titanium n(Ce):n(Ti) is 5:5 or greater, and the most suitable n(Ce):n(Ti) is determined as 7:3, over which the conversion rate of SO₂ and the yield of sulfur at 500 °C reach 93% and 99%, respectively. According to the activity testing curve, Ce_0.7Ti_0.3O₂ (n(Ce):n(Ti)=7:3) without any pretreatment can be gradually activated by reagent gas after about 10 min, and reaches a steady activation status 60 min later. The XPS results of Ce_0.7Ti_0.3O₂ after different time of SO₂+CO reaction show that CeO₂ is the active component that offers the redox couple Ce⁴⁺/Ce³⁺ and the labile oxygen vacancies, and TiO₂ only functions as a catalyst structure stabilizer during the catalytic reaction process. After 48 h of catalytic reaction at 500 °C, Ce_0.7Ti_0.3O₂ still maintains a stable structure without being vulcanized, demonstrating its good anti-sulfur poisoning performance.     

Electrodeposition, characterization and long term stability of NiW and NiWZn coatings on copper substrate in alkaline solution

This paper describes the electrodeposition of Ni, NiW and NiWZn coatings onto copper surfaces from electrolyte solutions containing Na₃C₆H₅O₇, Na₂WO₄, NiSO₄ and ZnSO₄. The electrocatalytic effects of electrodeposited coatings were investigated for hydrogen evolution reactions in 1 M NaOH solution. Surface characterization studies were carried out by energy dispersive X-ray spectroscopy, scanning electron microscopy, atomic force microscopy and cross-section analysis. The effect of operating conditions on the chemical composition, microstructure and electrocatalytic properties of Ni-W coatings was studied. The Zn ions were used to improve the active surface area and catalytic activity of the electrodeposited surface. The electrocatalytic activity of NiW and NiWZn coated electrodes for the hydrogen evolution reaction in alkaline solution was compared with that of an electrodeposited Ni electrode and copper substrate by using cathodic polarization curves and electrochemical impedance spectroscopy techniques over 96 h of electrolysis. The results proved that the NiWZn coated electrode showed better electrocatalytic activity and durability than bare Cu, Ni and NiW coatings.     

Catalytic performance and kinetics of Au/γ-Al_2O_3 catalysts for low-temperature combustion of light alcohols

Au/γ-Al2O3 catalysts were prepared by deposition-precipitation method for the catalytic combustion of low concentration alcohol streams(methanol,ethanol,iso-propanol and n-propanol).The catalysts were characterized by X-ray photoelectron spectroscopy(XPS),X-ray diffractometry(XRD) and energy dispersive X-ray micro analysis(EDS) techniques.The XPS results showed that there was only Au0 on the surface of catalysts.The XRD patterns showed that Au was presumably highly dispersed over γ-Al2O3.The temperatures for complete conversion of methanol,ethanol,iso-propanol and n-propanol with concentration of 2.0 g/m3 were 60,155,170 and 137 ℃,respectively,but they were completely mineralized into CO2 and H2O at 60,220,260 and 217 ℃ respectively over the optimized catalyst.The activity of the catalyst was stable in 130 h.The kinetics for the catalytic methanol elimination followed quasi-first order reaction expressed as r=0.652 8c0+0.084 2.The value of apparent activation energy is 54.7 kJ/mol in the range of reaction temperature.     

XPS and AES studies of the high temperature corrosion mechanism of Fe-30Cr alloy

Fe-30Cr alloy specimens were pre-oxidized at two different oxygen partial pressures (10^?16 and 10^?19 atm) at 900°C and subsequently exposed to environments containing both oxygen and sulfur. The sulfur and oxygen partial pressures were maintained such that Cr₂O₃ was the stable phase. The Cr₂O₃ scales formed during pre-oxidation became rapidly unstable when exposed to an environment whose composition approached the chromium sulfide-chromium oxide phase boundary; but when exposed to a higher oxygen partial pressure with the same sulfur partial pressure, the preformed scales remained intact. For elucidating the sulfidation mechanisms, the reaction products on the surface were analyzed at different stages of sulfidation by X-ray photo-electron spectroscopy and Auger electron spectroscopy. Correlation of the reaction mechanisms with thermodynamic and transport parameters are discussed.     

W18O49@Cu2O纳微米复合材料的制备及其光催化性能研究

本文首先用热蒸发方法制备得到了W₁₈O₄₉纳微米棒,然后经醋酸铜饱和溶液浸泡后再热处理的办法成功在W₁₈O₄₉纳微米棒表面负载Cu₂O制得得到了W₁₈O₄₉@Cu₂O纳微米复合材料;采用X-射线衍射仪、扫描电子显微镜、X-射线能谱分析及透射电子显微镜对样品进行分析表征;最后选用亚甲基蓝溶液作为目标降解物模拟污水处理测试材料的光催化性能。实验结果表明,W₁₈O₄₉纳微米棒在饱和醋酸铜溶液中浸泡时间越长,所得到的催化剂中Cu₂O的负载量越多,且所制备的W₁₈O₄₉@Cu₂O的纳微米复合材料相对于纯W₁₈O₄₉纳微米棒,其光催化效率得到了显著提高。     

Preparation and photocatalytic activity of immobilized composite photocatalyst (titania nanoparticle/activated carbon)

An immobilized composite photocatalyst, titania (TiO₂) nanoparticle/activated carbon (AC), was prepared and its photocatalytic activity on the degradation of textile dyes was tested. AC was prepared using Canola hull. Basic Red 18 (BR18) and Basic Red 46 (BR46) were used as model dyes. Fourier transform infrared (FTIR), wavelength dispersive X-ray spectroscopy (WDX), scanning electron microscopy (SEM), UV-vis spectrophotometry, chemical oxygen demand (COD) and ion chromatography (IC) analyses were employed. The effects of reaction parameters such as weight percent (wt.%) of activated carbon, pH, dye concentration and anions (NO₃⁻, Cl⁻, SO₄²⁻, HCO₃⁻ and CO₃²⁻) were investigated on dye degradation. Data showed that dyes were decolorized and degraded using novel immobilized composite photocatalyst. Formate, acetate and oxalate anions were detected as dominant aliphatic intermediates where, they were further oxidized slowly to CO₂. Nitrate, chloride and sulfate anions were detected as the photocatalytic mineralization products of dyes. Results show that novel immobilized composite photocatalyst with 2 wt.% of AC is the most effective novel immobilized composite photocatalyst to degrade of textile dyes.