Preparation, characterization and photocatalytic activity of metal-loaded NaNbO3

Fe-, Ni-, Co- and Ag- loaded NaNbO₃ catalysts were prepared and their activities have been investigated in the reaction of photocatalytic hydrogen generation. Me/NaNbO₃ were synthesized by impregnation of NaNbO₃ in an aqueous solution of metal nitrates and then by calcination at the temperature of 400 °C. The crystallographic phases and optical and vibronic properties were examined by X-ray diffraction (XRD) and diffuse reflectance (DR) UV-vis and resonance Raman spectroscopic methods, respectively. Morphology and chemical composition of the produced samples were studied using a high-resolution transmission electron microscope (HR-TEM) and an energy dispersive X-Ray spectrometer (EDX) as its mode. The detailed analysis has revealed that all the investigated catalysts exhibit high crystallinity and the presence of Fe₂O₃, NiO, Co₃O₄ and Ag₂O oxides on Me/NaNbO₃ was confirmed. Finally, the influence of different metal loadings (Fe, Ni, Co and Ag) on the photocatalytic activity of NaNbO₃ for photocatalytic hydrogen generation has been investigated. Here we report that among all the Me/NaNbO₃ photocatalysts Ag-loaded NaNbO₃ exhibited higher photocatalytic efficiency for photocatalytic hydrogen generation than NaNbO₃.     

Preparation and photocatalytic properties of platelike NaNbO3 based photocatalysts

Two kinds of plate-like NaNbO₃ were separately prepared by the one- and two-step molten salt processes via topochemical micro-crystal conversion methods. Meanwhile, the composite photocatalysts were obtained via heating the mixture of corresponding NaNbO₃ powders and urea. Their photocatalytic activities were evaluated from the photodegradation of Rhodamine B under full arc and visible light irradiation of Xe lamp. The sample containing NaNbO₃ prepared by the one-step molten salt process and carbon nitride displays the highest activity. The enhancement of photocatalytic activity was attributed to the surface properties and the state of the carbon nitride.     

2-Propanol photodegradation over nitrogen-doped NaNbO3 powders under visible-light irradiation

Nitrogen-doped perovskite-type materials, yellowish NaNbO_3−xN_x powders, had been developed as visible-light-sensitive photocatalysts for decomposition of gaseous 2-propanol. The NaNbO_3−xN_x samples were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), ultraviolet-visible (UV-vis) light diffuse reflectance spectroscopy, Brunauer-Emmett-Teller (BET) measurement, and scanning electron microscopy (SEM). The UV-vis spectra confirmed that the spectral response of the NaNbO₃ powders could be tuned to visible-light region by nitrogen doping technique. The photocatalytic activities of NaNbO_3−xN_x samples were evaluated by decomposing gaseous 2-propanol into acetone and CO₂ under visible-light irradiation (400 nm<λ<520 nm). The NaNbO_3−xN_x sample annealed at 833 K showed the highest visible-light photocatalytic activity among all the nitrogen-doped samples. The relationship between nitrogen doping amount and photocatalytic activity of NaNbO_3−xN_x samples was also investigated and discussed.     

Photocatalytic properties of lanthanide tungstates Ln2W2O9 (Ln=La,Pr, Nd,Sm, and Gd)

Lanthanide tungstates, Ln₂W₂O₉ (Ln=La, Pr, Nd, Sm, and Gd), were prepared via the polymerized complex method at 1273 K for 2 h, and their photocatalytic activities for hydrogen and oxygen evolution were investigated. Pt-loaded Gd₂W₂O₉ exhibited activity for H₂ evolution from an aqueous methanol solution under light irradiation (λ>300 nm). The remaining Ln₂W₂O₉ were inactive for H₂ evolution due to the influence of the Ln elements and their crystal structures. All Ln₂W₂O₉ were inactive for O₂ evolution from an aqueous AgNO₃ solution due to the lack of O₂ evolution sites on the surface.     

Structure and photocatalytic properties of copper-doped rutile TiO2 prepared by a low-temperature process

Copper-doped titania with variable Cu/Ti ratios have been prepared via a simple aqueous-phase method at 85 °C. The obtained products were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD) and UV-vis absorption spectra analysis. The photocatalytic properties of the products were tested by photocatalytic degradation of aqueous brilliant red X-3B solution. The results showed that the sample with 2% copper doping has the best photocatalytic activity, which is 3 times that of undoped rutile titania. The effect of the doped copper on the structure and property of TiO₂ has also been discussed.     

Photocatalytic H2 evolution under visible light irradiation on AgIn5S8 photocatalyst

A new visible-light-driven photocatalyst AgIn₅S₈ was prepared by a simple two-step process, which involves the first co-precipitation process at room temperature and subsequently heat-treatment process at 750 °C under pure argon flow protection. The obtained AgIn₅S₈ sample showed high activity for the evolution of hydrogen under visible light irradiation (λ?420 nm) from aqueous solution containing S²⁻ and SO₃²⁻ ions as sacrificial electron donors. It was found that several experimental parameters, such as the concentration of sacrificial reagents and the loading of Pt co-catalyst, play important roles on the evolution rate of H₂ under visible light irradiation.     

Template-free preparation and characterization of nanocrystalline ZnO in aqueous solution of [EMIM][EtSO4] as a low-cost ionic liquid using ultrasonic irradiation and photocatalytic activity

A fast, template-free, and environmentally benign green route for the preparation of nanocrystalline ZnO in aqueous solution of 1-ethyl-3-methylimidazolium ethyl sulfate, [EMIM][EtSO₄], room-temperature ionic liquid (RTIL), via ultrasonic irradiation is proposed. The X-ray diffraction (XRD) studies display that the products are excellently crystallized in the form of wurtzite hexagonal. Energy-dispersive X-ray spectroscopy (EDX) investigations reveal the products are extremely pure. The morphology of as-prepared nanocrystalline ZnO was characterized by scanning electron microscopy (SEM). Diffuse reflectance spectra (DRS) of the products with absorption maxima at 359 nm show blue shift relative to the bulk ZnO with absorption at 384 nm that can be attributed to quantum confinement effect of nanocrystalline ZnO. A possible formation mechanism of the nanocrystalline ZnO using ultrasonic irradiation in aqueous solution of the RTIL is presented. The results demonstrate that photocatalytic activity of the nanocrystalline ZnO prepared in the presence of the RTIL is higher than the prepared sample in water.     

Synthesis of a magnetically separable composite photocatalyst with high photocatalytic activity under sunlight

A novel magnetically separable composite photocatalyst (N-doped titania-coated γ-Fe₂O₃ magnetic activated carbon) was prepared. It consists of N-doped titania, activated carbon and γ-Fe₂O₃. The whole processes were carried out under low temperature. The prepared sample was characterized by XRD, DRS, SEM, BET and vibrating sample magnetometer (VSM). The photocatalytic activity was determined by degradation of Reactive Brilliant Red X-3B in an aqueous solution under solar irradiation. Results showed that this as-prepared composite photocatalyst exhibited much higher photocatalytic activity than Degussa P25. Furthermore, the photocatalyst can be separated easily by an external magnetic field. Thus, the photocatalyst can be recycled without mass losing, and the degradation percent of X-3B decreased less than 2% after six cycles.     

Calorimetric, optical and catalytic activity studies of europium chloride-polyvinyl alcohol composite system

Polyvinyl alcohol (PVA) films doped with europium chloride (EuCl₃) have been prepared by casting from their aqueous solutions. The phase transitions and thermal decomposition behavior of the prepared samples were investigated by thermal analysis and the interactions between the host PVA and Eu³⁺ were examined by FTIR spectroscopy. The optical absorption was recorded at room temperature in the range of 190-1000 nm. From the absorption edge studies, the values of the Urbach energy (E_e) were found to be 0.56 eV in case of the pure polymer; however, its value increased to be in the range of 1.21-1.75 eV. These energy values indicate that the model based on electronic transitions between localized states is not preferable and transitions are made between band tails. Optical parameters such as refractive index and complex dielectric constant have been determined. The dispersion of the refractive index is discussed in terms of the single-oscillator Wemple-DiDomenico model. Color properties of the prepared samples are discussed in the framework of CIE L?u*v* color space. The prepared samples have been used as catalysts in the photocatalytic degradation of p-nitrophenol (PNP) in aqueous solution under UV light irradiation using H₂O₂ as oxidizing agent. The catalytic activity of the Eu-polymer towards the photodegradation of PNP greatly increased after doping with Eu³⁺ ions. The highest catalytic activity was noticed at the optimum pH value of 5.5.     

Band structure and photocatalytic properties of perovskite-type compound Ca2NiWO6 for water splitting

An oxide semiconductor Ca₂NiWO₆, with double-perovskite crystal structure, was synthesized by solid-state reaction method. The compound Ca₂NiWO₆ was characterized by X-ray diffraction, UV-visible diffuse reflectance, and photoluminescence. The photocatalytic properties of the compound for water splitting were investigated under UV and visible light irradiation. The results showed H₂ evolution was not observed over the compound under visible light irradiation (λ>420 nm) with a 300 W xenon arc lamp when using methanol (CH₃OH) as electron donor, although the compound was responsive to visible light region. Based on the experimental results, a possible band structure was proposed through theoretical calculation of the electronic structure by using the full potential-linearized augmented plane wave (F-LAPW). The band structure and photocatalytic properties were attributed to the special crystal and electronic structures. Due to the oxygen vacancies in the compound, which worked as electron-hole recombination centers, the photocatalytic activity of the compound was low.     

Preparation of Ru-loaded CdS/Al-HMS nanocomposites and production of hydrogen by photocatalytic degradation of formic acid

The composite of aluminum-substituted mesoporous silica (Al-HMS) molecular sieve coupled with CdS (CdS/Al-HMS) was prepared by template, ion exchange and sulfurization reactions. The result of low angle XRD patterns showed that the low content of 2.5 wt% CdS is incorporated inside Al-HMS channels. The results of diffuse reflectance UV-visible spectra and fluorescence emission spectra exhibited that the absorption edge and photoluminescence peak for CdS/Al-HMS are blue-shifted about 75 nm and 40 nm in comparison to bulk CdS, respectively. The activities of hydrogen production by photocatalytic degradation of formic acid were evaluated under visible light irradiation (λ ≥ 420 nm) and the CdS/Al-HMS loaded 0.07 wt% Ru showed the highest H₂ evolution at a rate of 3.7 mL h⁻¹ with an apparent quantum yield of 1.2% at 420 nm.     

Composition dependence of AgSbO3/NaNbO3 composite on surface photovoltaic and visible-light photocatalytic properties

The visible-light-active xAgSbO₃/NaNbO₃ (x=0.5, 1, 2, 4, 6) composite photocatalysts were prepared by a conventional solid-state reaction method. Composition dependences on the structure, optical, surface photoelectronic and photocatalytic properties were investigated. The absorption edge of the composites could be red-shifted increasing the amount of AgSbO₃ in comparison with that of NaNbO₃. The surface photovoltage response shows the selectivity for the amount of AgSbO₃ in the samples. The photocatalytic activities for Rhodamine B degradation exhibit a parabola-like behavior with the amount of AgSbO₃. The highest photocatalytic activity is observed on the AgSbO₃/NaNbO₃ composite due to the better dispersiveness, electron transfer and surface photoelectric properties.     

TiO2 thick films supported on reticulated macroporous Al2O3 foams and their photoactivity in phenol mineralization

TiO₂ thick films deposited on macroporous reticulated Al₂O₃ foams with pore size of 10 ppi and 15 ppi were prepared using dip coating from slurries of Aeroxide^® P25 nanopowder and precipitated titania. All prepared films have sufficiently good adhesion to the surface of the substrate also in case of strongly cracked films. No measurable release of deposited TiO₂ after repeated photocatalytic cycles was observed. The photocatalytic activity was characterized as the rate of mineralization of aqueous phenol solution under irradiation of UVA light by TOC technique. The best activity was obtained with Aeroxide^® P25 coated Al₂O₃ foam with the pore size of 10 ppi, annealed at 600 °C. The optimal annealing temperature for preparation of films from precipitated titania could be determined at 700 °C. Films prepared by sol-gel deposition technique were considerably thinner compared to coatings made of suspensions and their photocatalytic activity was significantly smaller.     

纳米ZnO的制备及其在不同牺牲试剂下的光催化产氢性能

采用沉淀法与异相共沸蒸馏技术相结合制备了ZnO纳米粉体,并利用X射线粉末衍射、扫描电镜、透射电镜和液氮吸-脱附等技术对制备的样品进行了分析与表征．考察了Pt的负载量、煅烧温度以及牺牲试剂的种类和浓度对制备的纳米ZnO的光催化产氢效率的影响．结果表明：与其他温度下煅烧获得的产物相比,400 oC煅烧产物表现出最佳的光催化产氢效率,且以甲醇为牺牲试剂时纳米ZnO悬浮体系的光催化产氢效率远高于以三乙醇胺为牺牲试剂时的产氢效率．其原因在于光催化过程中甲醇氧化也对体系的产氢有贡献．此外,探讨了基于实验结果对含甲醇的     

Immobilization of RuS2 Nanoparticles Prepared in Reverse Micellar System onto Thiol-Modified Polystyrene Particles and their Photocatalytic Properties

RuS₂ nanoparticles, smaller than 3 nm in diameter, were prepared by H₂S gas injection into the AOT/isooctane reverse micellar solution containing RuCl₃ aqueous solution. The nanoparticle size was found to be independent of the W_o (water content) value of the reverse micellar system, as shown by TEM observation. The recovery and immobilization of the RuS₂ nanoparticles from reverse micelles onto thiol-modified polystyrene particles (PSt-SH) were successfully carried out, by the addition of PSt-SH into the reverse micellar solution under conditions of mild stirring. The resulting composites, PSt-RuS₂, showed photocatalytic activity for H₂ generation form aqueous solution containing 2-propanol and Na₂SO₃ as sacrificial electron donors.     

Preparation and characterization of Tb and Tb(sal)3·nH2O doped PC:PMMA blend

Tb doped polycarbonate:poly(methyl methacrylate) (Tb-PC:PMMA) blend was prepared with varying proportions of PC and PMMA. Thermal and spectroscopic properties of the doped polymer have been investigated employing Fourier Transform Infrared (FTIR) absorption and differential scanning calorimetric (DSC) techniques. PC:PMMA blend (with 10 wt% PC and 90 wt% PMMA) shows better miscibility. Optical properties of the dopant Tb³⁺ ions have been investigated using UV-vis absorption and fluorescence excited by 355 nm radiation. It is seen that luminescence intensity of Tb³⁺ ion depends on PC:PMMA ratio and on Tb³⁺ ion concentration. Concentration quenching is seen for TbCl₃·6H₂O concentration larger than 4 wt%. Addition of salicylic acid to the polymer blend increases the luminescence from Tb³⁺ ions. Luminescence decay curve analysis affirms the non-radiative energy transfer from salicylic acid to Tb³⁺ ions, which is identified as the reason behind this enhancement.     

Mercury removal from aqueous solution and flue gas by adsorption on activated carbon fibres

The use of two activated carbon fibres, one laboratorial sample prepared from a commercial acrylic textile fibre and one commercial sample of Kynol^®, as prepared/received and modified by reaction with powdered sulfur and H₂S gas in order to increase the sulfur content were studied for the removal of mercury from aqueous solution and from flue gases from a fluidized bed combustor. The sulfur introduced ranged from 1 to 6 wt.% depending on the method used. The most important parameter for the mercury uptake is the type of sulfur introduced rather than the total amount and it was found that the H₂S treatment of ACF leads to samples with the highest mercury uptake, despite the lower sulfur amount introduced. The modified samples by both methods can remove HgCl₂ from aqueous solutions at pH 6 within the range 290-710 mg/g (ACF) which can be favourably compared with other studies already published. The use of a filter made with an activated carbon fibre modified by powdered sulfur totally removed the mercury species present in the flue gases produced by combustion of fossil fuel.     

Preparation, characterization and photocatalytic activity of polycrystalline Bi2O3/SrTiO3 composite powders

Bi₂O₃/SrTiO₃ composite powders have been prepared and their photocatalytic activities were investigated by photooxidation of methanol. These powders were characterized by UV-Visible diffuse reflectance spectra, SEM and X-ray diffraction (XRD). The results revealed that all the Bi₂O₃/SrTiO₃ composite powders exhibited higher photocatalytic activity than pure SrTiO₃, Bi₂O₃ and TiO₂ (P25) under visible light irradiation (λ>440 nm). The effects of the Bi₂O₃ contents on the photocatalytic activities of the composite powders were examined, the photocatalytic activities increased with the content of Bi₂O₃ increasing to a maximum of 83% and then decreased under visible light irradiation. The effects of the calcination temperatures on the photocatalytic activities of the composite powders were also investigated.     

Intricate photocatalytic decomposition behavior of gaseous methanol with nanocrystalline tungsten trioxide films in high vacuum

Gas phase photocatalytic decomposition of methanol with nanocrystalline tungsten trioxide (WO₃) thin films in high vacuum was investigated. WO₃ thin films were prepared from a novel precursor prepared using peroxo-tungstic acid and polyethylene glycol (PEG300) in water. Uniform thin films of WO₃ with different morphologies such as micro-sheets, platelets, nanorods and nanoparticles were fabricated by varying the concentration of PEG300 in the precursor solution and by optimizing other preparative parameters. Nanocrystalline thin films were obtained with 20% of PEG300 in the precursor solution and at a calcination temperature of 350 °C, followed by post annealing in air at 500 °C. Photocatalytic decomposition of gaseous methanol in high vacuum was examined with nanocrystalline WO₃ thin films using a quadrupole mass spectrometer at a real-time scale under visible (400-700 nm) and UVA (300-400 nm) illumination. Methanol was first decomposed to formaldehyde via direct hole transfer mechanism. Subsequently formaldehyde was decomposed to CO and finally to CO₂. As a result, the partial pressures of CH₂O, CO and CO₂ showed a switching phenomenon according to the ON/OFF of light illumination. A rapid decrease in the photocatalytic activity was observed due to photo-induced desorption of methanol during the initial light pulse and gradual decrease at longer times was observed because of formation of tungsten bronze. Thus, the overall process of methanol decomposition over WO₃ films is complex convolution of elementary steps that involve several intermediates.     

Preparation and characterization of lithium niobate as a novel photocatalyst in hydrogen generation

Several chemical compounds based lithium niobate have been tested in the reaction for the photocatalytic hydrogen generation. The photocatalysts have been prepared by impregnation of Nb₂O₅ in the aqueous solution of lithium hydroxide and then the calcination at the temperature range of 400-650 °C. In this report, we present the interesting study showing that the most active catalyst for the photocatalytic generation of hydrogen is the one containing two lithium niobate phases such as LiNbO₃ and LiNb₃O₈. It means that the lithium niobates based catalyst without any further modification or doping can be applied as a novel material for this process.