Preparation and performances of nanosized Ta2O5 powder photocatalyst

Nanosized-Ta₂O₅ powder photocatalyst was successfully synthesized by using sol-gel method via TaCl₅ butanol solution as a precursor. Ta₂O₅ species can be formed under 500 °C via the decomposition of the precursor. The crystalline phase of Ta₂O₅ powder photocatalyst can be obtained after being calcined above 600 °C for 4 h. The crystal size and particle size of Ta₂O₅ powder photocatalyst was about 50 nm. A good photocatalytic performance for the degradation of gaseous formaldehyde was obtained for the nanosized-Ta₂O₅ powder. The Ta₂O₅ powder formed at 700 °C for 4 h and at 650 °C for 12 h showed the best performance. The calcination temperature and time play an important role in the crystallization and photocatalytical performance of nanosized-Ta₂O₅ powder.     

四角星形BiVO4/Bi2O3催化剂的制备及性能

采用水热法合成具有四角星形貌的钒酸铋,再将钒酸铋浸渍在碱溶液里二次水热,制备出BiVO_4/Bi_2O_3催化剂。采用X射线粉末衍射(XRD)、扫描电子显微镜(SEM),紫外-可见漫反射(UV-Vis DRS)等方法对样品进行表征。可见光下,BiVO_4/Bi_2O_3复合物的光催化降解罗丹明B性能及光电流响应均优于纯BiVO_4。这是由于BiVO_4/Bi_2O_3复合材料形成了异质结构,有效抑制了光生电子与空穴的复合效率。     

四角星形BiVO4/Bi2O3催化剂的制备及性能研究

采用水热法合成具有四角星形貌的钒酸铋,再将钒酸铋浸渍在碱溶液里二次水热,制备出BiVO₄/Bi₂O₃催化剂。采用X射线粉末衍射(XRD)、扫描电子显微镜(SEM),紫外-射(UV-Vis DRS)等方法征。可见光下,BiVO₄/Bi₂O₃复合物的光催化降解丹明B性能及光电优于纯BiVO₄。BiVO₄/Bi₂O₃复合材料形成了异质结构,有效抑制了光电子与空穴的复合效率。     

Bi/BiVO4&Bi4V2O11复合催化剂的制备及其光催化性能

经由溶剂热反应、光辅助还原过程制备Bi/Bi VO_4Bi_4V_2O_(11)纳米复合光催化材料。通过X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、高分辨率透射电子显微镜(HRTEM)、X射线光电子能谱(XPS)、紫外-可见漫反射光谱(UV-Vis DRS)、N_2吸附-脱附等温线和光致发光(PL)等手段对该复合物进行表征。实验结果表明当金属Bi与BiVO_4Bi_4V_2O_(11)的质量比值为0.8,可见光照射30 min时,Bi/BiVO_4Bi_4V_2O_(11)复合催化剂对罗丹明B(RhB)的降解率可达95.6%。此外,Bi/BiVO_4Bi_4V_2O_(11)对四环素(TC)的降解也表现出增强的光催化性能。Bi/BiVO_4Bi_4V_2O_(11)复合材料提升的光催化性能可能归因于金属Bi的表面等离子体共振(SPR)效应、拓宽的可见光吸收范围和增大的比表面积。此外,提出了复合光催化剂可能的光催化机理。     

纳米钒酸铋的微波快速合成及光催化性能研究

采用微波辅助加热法以NaVO₃溶液和Bi(NO₃)₃·5H₂O的硝酸溶液为反应物,在10～40 min内合成了纳米钒酸铋粉末。利用XRD、FTIR、TEM、UV-Vis等手段研究了反应时间对产物结构及形貌的影响。经测定反应10 min时,得到纯的四方相BiVO₄,随着反应时间的延长,逐渐出现单斜相的衍射峰,当反应40 min时,获得纯的单斜相BiVO₄。同时XRD和IR结果证明了相转变的过程。TEM分析表明不同的反应时间条件下样品呈现不同的形貌。不同反应时间下获得样品的光催化性能的结果表明,微波反应时间对BiVO₄结构的转变及光催化性能的改变起到了重要的作用。     

Nano size crystals of goethite, α-FeOOH: Synthesis and thermal transformation

An aqueous suspension of amorphous iron(III) hydroxide was kept at room temperature (298 K) for 23 years. During this period of time the pH of the liquid phase changed from 4.3 to 2.85, and nano size crystals of goethite, α-FeOOH crystallised from the amorphous iron(III) hydroxide. Transmission electron microscopy (TEM) investigations, Mössbauer spectra, and powder X-ray diffraction using Co Kα radiation showed that the only iron containing crystalline phase present in the recovered product was α-FeOOH. The size of these nano particles range from 10 to 100 nm measured by TEM. The thermal decomposition of α-FeOOH was investigated by time-resolved in situ synchrotron radiation powder X-ray diffraction and the data showed that the sample of α-FeOOH transformed to α-Fe₂O₃ in the temperature range 444-584 K. A quantitative phase analysis shows the increase in scattered X-ray intensity from α-Fe₂O₃ to follow the decrease of intensity from α-FeOOH in agreement with the topotactic phase transition.     

Photoluminescence properties of BaMoO4 amorphous thin films

BaMoO₄ amorphous and crystalline thin films were prepared from polymeric precursors. The BaMoO₄ was deposited onto Si wafers by means of the spinning technique. The structure and optical properties of the resulting films were characterized by FTIR reflectance spectra, X-ray diffraction (XRD), atomic force microscopy (AFM) and optical reflectance. The bond Mo-O present in BaMoO₄ was confirmed by FTIR reflectance spectra. XRD characterization showed that thin films heat-treated at 600 and 200 °C presented the scheelite-type crystalline phase and amorphous, respectively. AFM analyses showed a considerable variation in surface morphology by comparing samples heat-treated at 200 and 600 °C. The reflectivity spectra showed two bands, positioned at 3.38 and 4.37 eV that were attributed to the excitonic state of Ba²⁺ and electronic transitions within MoO²⁻₄, respectively. The optical band gaps of BaMoO₄ were 3.38 and 2.19 eV, for crystalline (600 °C/2 h) and amorphous (200 °C/8 h) films, respectively. The room-temperature luminescence spectra revealed an intense single-emission band in the visible region. The PL intensity of these materials was increased upon heat-treatment. The excellent optical properties observed for BaMoO₄ amorphous thin films suggested that this material is a highly promising candidate for photoluminescent applications.     

Ion-beam irradiation of lanthanum compounds in the systems La2O3-Al2O3 and La2O3-TiO2

Thin crystals of La₂O₃, LaAlO₃, La_2/3TiO₃, La₂TiO₅, and La₂Ti₂O₇ have been irradiated in situ using 1 MeV Kr²⁺ ions at the Intermediate Voltage Electron Microscope-Tandem User Facility (IVEM-Tandem), Argonne National Laboratory (ANL). We observed that La₂O₃ remained crystalline to a fluence greater than 3.1×10¹⁶ ions cm⁻² at a temperature of 50 K. The four binary oxide compounds in the two systems were observed through the crystalline-amorphous transition as a function of ion fluence and temperature. Results from the ion irradiations give critical temperatures for amorphisation (T_c) of 647 K for LaAlO₃, 840 K for La₂Ti₂O₇, 865 K for La_2/3TiO₃, and 1027 K for La₂TiO₅. The T_c values observed in this study, together with previous data for Al₂O₃ and TiO₂, are discussed with reference to the melting points for the La₂O₃-Al₂O₃ and La₂O₃-TiO₂ systems and the different local environments within the four crystal structures. Results suggest that there is an observable inverse correlation between T_c and melting temperature (T_m) in the two systems. More complex relationships exist between T_c and crystal structure, with the stoichiometric perovskite LaAlO₃ being the most resistant to amorphisation.     

Low temperature synthesis of Mn3O4 polyhedral nanocrystals and magnetic study

Manganese oxide (hausmannite) polyhedral nanocrystals were prepared by a microwave-assisted solution-based method using Mn(CH₃COO)₂ and (CH₂)₆N₄ at 80 °C. The as-prepared Mn₃O₄ nanocrystals were characterized by means of X-ray diffraction, field-emission transmission electron microscopy, field-emission scanning electron microscopy and Raman spectrum. Mn₃O₄ polyhedral nanocrystals prepared by microwave heating at 80 °C for 60 min were of cubic and rhombohedral shapes with the edge lengths in the range of 15-40 nm. Mn₃O₄ nanocrystals grew following the Ostwald ripening mechanism with increasing reaction time. High-resolution transmission electron microscopy and selected area electron diffraction confirm that the as-obtained polyhedral nanocrystals were single-crystalline. The magnetic behavior of Mn₃O₄ nanocrystals was studied. Mn₃O₄ nanocrystals show an obvious ferromagnetic behavior at low temperatures. The magnetic behavior of Mn₃O₄ nanocrystals was sensitive to crystal size. Ferromagnetic onset temperatures (T_c) of samples 1 and 3 are 40.6 and 41.1 K, respectively, lower than that observed for bulk Mn₃O₄ (42 K).     

Hydrothermal synthesis of cobalt carbonates using different counter ions: An efficient precursor to nano-sized cobalt oxide (Co3O4)

Synthesis of submicrometer crystalline particles of cobalt carbonate was achieved hydrothermally using different cobalt salts and urea with a molar ratio from 1:3 to 1:20 (cobalt salt:urea) in aqueous solutions at 160 °C for 24-36 h, in the presence of cetyltrimethylammonium bromide (CTAB) as a surfactant. Nanoparticles of Co₃O₄, with an average size from 30 to 39 nm, were obtained by thermal decomposition of CoCO₃ samples at 500 °C for 3 h in an electrical furnace. The as-synthesized products were characterized by powder X-ray diffraction (XRD), Fourier transform infrared spectra (FT-IR), transmission electron microscopy (TEM), scanning electron microscopy (SEM), UV-Vis spectra and thermal analysis. Studying the optical properties of the as-prepared cobalt oxide nanoparticles showed the presence of two band gaps, the values of which confirmed the semiconducting properties of the prepared Co₃O₄.     

CTAB-Mn3O4 nanocomposites: Synthesis,NMR and low temperature EPR studies

We are reporting on the synthesis of Mn₃O₄ nanoparticles and CTAB-Mn₃O₄ nanocomposites via a sonochemical route using MnCl₂, ethanol, NaOH and CTAB. The crystalline phase was identified as Mn₃O₄. The crystallite size of the CTAB-Mn₃O₄ nanocomposite was identified as 13 ± 5 nm from X-ray line profile fitting and the particle size from TEM was 107.5 ± 1.4 nm. The interaction between CTAB and the Mn₃O₄ nanoparticles was investigated by FTIR and ¹H NMR spectroscopies. Two different magnetic phase transitions were observed for both samples below the Curie temperature (43 °C) by using a low temperature Electron Paramagnetic Resonance (EPR) technique. Also we determined the effect of the capping with CTAB on the reduction in absorbed power.     

A sol-gel route for the development of rare-earth aluminum borate nanopowders and transparent thin films

A new sol-gel route was applied to obtain Y_0.9Er_0.1Al₃(BO₃)₄ crystalline powders and amorphous thin films by using Al(acac)₃, B(OPrⁱ)₃, Y(NO₃)₃·6H₂O, and Er(NO₃)₃·5H₂O as starting materials dissolved in propionic acid and ethyl alcohol mixtures. Our study shows that propionic acid acts as good chelant agent for yttrium and erbium ions while ethyl alcohol allows to dissolve Al(acac)₃. This process makes the resulting sols very stable to obtain homogeneous gels and transparent amorphous thin films. In addition, the propionic acid prevents the sol precipitation, making easy porous- and crack-free thin film depositions. Chemical reactions involved in the complexation were discussed. As-prepared powders and films are amorphous and present a good thermal stability due to their high glass transition (746 °C) and crystallization temperatures (830 °C). This new sol-gel route showed to be adequate to obtain dense and crack-free thin films free of organic and hydroxyl groups that can be considered as promising materials to be used in integrated optical systems.     

Photodegradation of 2,4-D over PdO/Al2O3-Nd2O3 photocatalysts prepared by the sol-gel method

The photocatalytic activity of 1.0 wt% PdO supported on Al₂O₃-Nd₂O₃ binary oxides prepared by the sol-gel method was studied in the photodegradation of 2,4-dichlorophenoxyacetic acid (2,4-D). The photocatalysts were characterized by N₂ physisorption, XRD and UV-vis spectroscopy. PdO supported on γ-Al₂O₃ photo-degrades the 2,4-D, however the addition of Nd₂O₃ to γ-Al₂O₃ notably improves the photocatalytic activity. As the concentration of Nd₂O₃ in the binary oxide increases from 2 to 10 wt%, the photodegradation of 2,4-D is highly enhanced. The catalytic test for PdO supported on pure Nd₂O₃ showed scarce photocatalytic activity. Total organic carbon (TOC) analysis showed that the 2,4-D has been completely destroyed on the PdO/Al₂O₃-Nd₂O₃ photocatalysts after 6 h under irradiation.     

The formation and physicochemical characterization of Al2O3-doped manganese ferrites

Mn/Fe mixed oxide solids doped with Al₂O₃ (0.32-1.27 wt.%) were prepared by impregnation of manganese nitrate with finely powdered ferric oxide, then treated with different amounts of aluminum nitrate. The obtained samples were calcined in air at 700-1000 °C for 6 h. The specific surface area (S_BET) and the catalytic activity of pure and doped precalcined at 700-1000 °C have been measured by using N₂ adsorption isotherms and CO oxidation by O₂. The structure and the phase changes were characterized by DTA and XRD techniques. The obtained results revealed that Mn₂O₃ interacted readily with Fe₂O₃ to produce well-crystallized manganese ferrite (MnFe₂O₄) at temperatures of 800 °C and above. The degree of propagation of this reaction increased by Al₂O₃-doping and also by increasing the heating temperature. The treatment with 1.27 wt.% Al₂O₃ followed by heating at 1000 °C resulted in complete conversion of Mn/Fe oxides into the corresponding ferrite phase. The catalytic activity and S_BET of pure and doped solids were found to decrease, by increasing both the calcination temperature and the amount of Al₂O₃ added, due to the enhanced formation of MnFe₂O₄ phase which is less reactive than the free oxides (Mn₂O₃ and Fe₂O₃). The activation energy of formation (ΔE) of MnFe₂O₄ was determined for pure and doped solids. The promotion effect of aluminum in formation of MnFe₂O₄ was attributed to an effective increase in the mobility of reacting cations.     

Effect of surface fluorination and conductive additives on the electrochemical behavior of lithium titanate (Li4/3Ti5/3O4) for lithium ion battery

Effect of surface fluorination and conductive additives on the charge/discharge behavior of lithium titanate (Li_4/3Ti_5/3O₄) has been investigated using F₂ gas and vapor grown carbon fiber (VGCF). Surface fluorination of Li_4/3Ti_5/3O₄ was made using F₂ gas (3 × 10⁴ Pa) at 25-150 °C for 2 min. Charge capacities of Li_4/3Ti_5/3O₄ samples fluorinated at 70 °C and 100 °C were larger than those for original sample at high current densities of 300 and 600 mA/g. Optimum fluorination temperatures of Li_4/3Ti_5/3O₄ were 70 °C and 100 °C. Fibrous VGCF with a large surface area (17.7 m²/g) increased the utilization of available capacity of Li_4/3Ti_5/3O₄ probably because it provided the better electrical contact than acetylene black (AB) between Li_4/3Ti_5/3O₄ particles and nickel current collector.     

Selective hydrothermal synthesis of BiOBr microflowers and Bi2O3 shuttles with concave surfaces

Through controlling the amount of NaOH added, BiOBr and Bi₂O₃ with different shapes were hydrothermally synthesized in the reaction system of Bi(NO₃)₃-hexadecyl trimethyl ammonium bromide (CTAB)-NaOH. As 8 mmol of NaOH was added, BiOBr microflowers constructed of nanoflakes were synthesized. The thickness of these single-crystal nanoflakes was about 20 nm. In the similar condition, when the amount of NaOH added was 28 mmol, Bi₂O₃ shuttles with concave surfaces were obtained. The length of these shuttles was 100 μm and the diameter at the middle of these shuttles was 50 μm. The photocatalytic activity of as-prepared BiOBr microflowers was evaluated by the degradation of methyl orange (MO) under visible-light irradiation (λ>420 nm), which was up to 96% within 90 min.     

Bi2MoO6/BiVO4异质结的水热合成和可见光催化活性

采用一步水热法制备Bi₂MoO₆/BiVO₄复合光催化剂. 利用X 射线衍射(XRD)、场发射扫描电子显微镜(FESEM)、高分辨透射电子显微镜(HRTEM)等手段对其晶体结构和微观结构进行了表征. 结果表明, Bi₂MoO₆纳米粒子沉积在BiVO₄纳米片表面从而形成异质结结构. 紫外-可见漫反射光谱(UV-Vis DRS)表明所制备的Bi₂MoO₆/BiVO₄异质结较纯相Bi₂MoO₆和BiVO₄对可见光吸收更强. 由于形成异质结结构及其光吸收性能使Bi₂MoO₆/BiVO₄ 光催化活性有较大提高. 可见光下(λ>420 nm)光催化降解罗丹明B (RhB)实验结果表明,Bi₂MoO₆/BiVO₄光催化活性较纯相Bi₂MoO₆和BiVO₄高. Bi₂MoO₆/BiVO₄样品光催化性能提高的原因是Bi₂MoO₆和BiVO₄形成异质结, 从而有效抑制光生电子-空穴对的复合, 增大了可见光吸收范围及比表面积.     

Photocatalytic Degradation of Palm Oil Mill Effluent (POME) Waste Using BiVO4 Based Catalysts

Disposal of palm oil mill effluent (POME), which is highly polluting from the palm oil industry, needs to be handled properly to minimize the harmful impact on the surrounding environment. Photocatalytic technology is one of the advanced technologies that can be developed due to its low operating costs, as well as being sustainable, renewable, and environmentally friendly. This paper reports on the photocatalytic degradation of palm oil mill effluent (POME) using a BiVO₄ photocatalyst under UV-visible light irradiation. BiVO₄ photocatalysts were synthesized via sol-gel method and their physical and chemical properties were characterized using several characterization tools including X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), surface area analysis using the BET method, Raman spectroscopy, electron paramagnetic resonance (EPR), and UV-Vis diffuse reflectance spectroscopy (UV-Vis DRS). The effect of calcination temperature on the properties and photocatalytic performance for POME degradation using BiVO₄ photocatalyst was also studied. XRD characterization data show a phase transformation of BiVO₄ from tetragonal to monoclinic phase at a temperature of 450 °C (BV-450). The defect site comprising of vanadium vacancy (V_v) was generated through calcination under air and maxima at the BV-450 sample and proposed as the origin of the highest reaction rate constant (k) of photocatalytic POME removal among various calcination temperature treatments with a k value of 1.04 × 10⁻³ min⁻¹. These findings provide design guidelines to develop efficient BiVO₄-based photocatalyst through defect engineering for potential scalable photocatalytic organic pollutant degradation.     

Synthesis, structure and magnetic properties of porous magnetic composite, based on MCM-41 molecular sieve with Fe3O4 nanoparticles

Porous magnetic composites were prepared by the synthesis of molecular sieve MCM-41 in the presence of Fe₃O₄ nanoparticles with average diameter of 15 nm. Nanoparticles were captured by porous silica matrix MCM-41, which resulted in their incorporation, as it was confirmed by TEM, SEM and X-ray diffraction. The materials possessed high surface area (392-666 m² g⁻¹), high pore volume (0.39-0.73 cm³ g⁻¹) along with high magnetic response (M_S up to 28.4 emu g⁻¹ at 300 K). Calcination of samples resulted in partial oxidation of Fe₃O₄ to α-Fe₂O₃. The influence of nanoparticles content on sorption and magnetic properties of the composites was shown. No hysteresis was found for the samples at 300 K; at 5 K, H_C was in the range 370-385 G for non-calcinated samples and 350-356 G for calcinated ones.     

The effect of B2O3 addition on the crystallization of amorphous TiO2-ZrO2 mixed oxide

The effect of B₂O₃ addition on the crystallization of amorphous TiO₂-ZrO₂ mixed oxide was investigated by X-ray diffraction (XRD), thermogravimetric and differential thermal analysis (TG/DTA). TiO₂-ZrO₂ mixed oxide was prepared by co-precipitation method with aqueous ammonia as the precipitation reagent. Boric acid was used as a source of boria, and boria contents varied from 2 to 20 wt%. The results indicate that the addition of small amount of boria (<8 wt%) hinders the crystallization of amorphous TiO₂-ZrO₂ into a crystalline ZrTiO₄ compound, while a larger amount of boria (?8 wt%) promotes the crystallization process. FT-IR spectroscopy and ¹¹B MAS NMR results show that tetrahedral borate species predominate at low boria loading, and trigonal borate species increase with increasing boria loading. Thus it is concluded that highly dispersed tetrahedral BO₄ units delay, while a build-up of trigonal BO₃ promote, the crystallization of amorphous TiO₂-ZrO₂ to form ZrTiO₄ crystals.