Characterization and activity of Pd-modified TiO2 catalysts for photocatalytic oxidation of NO in gas phase

Pd-modified TiO(2) prepared by thermal impregnation method was used in this study for photocatalytic oxidation of NO in gas phase. The physico-chemical properties of Pd/TiO(2) catalysts were characterized by X-ray diffraction analysis (XRD), Brunauer-Emmett-Teller measurements (BET), X-ray photoelectron spectrum analysis (XPS), transmission electron microscopy (TEM), high resolution-transmission electron microscopy (HR-TEM), UV-vis diffuse reflectance spectra (UV-vis DRS) and photoluminescence spectra (PL). It was found that Pd dopant existed as PdO particles in as-prepared photocatalysts. The results of PL spectra indicated that the photogenerated electrons and holes were efficiently separated after Pd doping. During in situ XPS study, it was found that the content of hydroxyl groups on the surface of Pd/TiO(2) increased when the catalyst was irradiated by UV light, which could result in the improvement of photocatalytic activity. The activity test showed that the optimum Pd dopant content was 0.05 wt.%. And the maximum conversion of NO was about 72% higher than that of P25 when the initial concentration of NO was 200 ppm, which showed that Pd/TiO(2) photocatalysts could be potentially applied to oxidize higher concentration of NO.     

The electronic and optical properties of Eu/Si-codoped anatase TiO(2) photocatalyst

The electronic and optical properties of Eu/Si-codoped anatase TiO(2) are investigated using the density functional theory. The calculated results show that the synergistic effects of Eu/Si codoping can effectively extend the optical absorption edge, which can lead to higher visible-light photocatalytic activities than pure anatase TiO(2). To verify the reliability of our calculated results, nanocrystalline Eu/Si-codoped TiO(2) is prepared by a sol-gel-solvothermal method, and the experimental results also indicate that the codoping sample exhibits better absorption performance and higher photocatalytic activities than pure TiO(2).     

Ce/ TiO2纳米复合粉体的制备及其性能评价

以锐钛矿型纳米TiO2和硫酸铈为主要原料，采用浸渍法制备了Ce／TiO2纳米复合材料。采用滴定法研究TiO2对Ce^4＋的吸附，结果表明，在pH值为2-7的范围内TiO2对铈离子的吸附量接近100％。采用X射线衍射（XRD）进行物相结构分析，发现在700℃下焙烧仍保持锐钛型结构，而在800℃下焙烧出现了金红石型TiO2和CeO2，说明铈离子的存在减缓了TiO2的晶型转变。最后以甲基橙为目标降解物评价了Ce^4＋／TiO2复合粉体的光催化反应活性。     

TiO_2-Pt/CuS光电材料的制备及性能研究

采用电化学沉积Pt和化学沉积CuS的方法对TiO2纳米管阵列电极进行复合修饰,获得了二元TiO2-Pt和三元TiO2-Pt/CuS纳米结构体系。用SEM和TEM-EDS对催化剂进行了表征,并用水和有机物作为目标物,评价所制备的催化剂的光电活性。结果表明,TiO2在电化学和化学沉积后都能够保持原有形貌;Pt在纳米管内和阵列表面都有沉积,部分CuS与Pt形成混相复合状态。水的分解和有机物的降解的结果表明,所制备的光电材料的光电活性顺序为TiO2-Pt/CuSTiO2-PtTiO2。     

电气石/La/TiO2光催化材料的合成与表征

以硝酸镧、天然电气石(Tourmaline,简称T)和钛酸丁酯为原料,采用溶胶-凝胶法制备掺杂电气石和稀土La的TiO2复合光催化薄膜样品。用正交试验方法对影响该薄膜样品光催化性能的制备工艺进行优化,并通过紫外可见光谱对复合薄膜样品的吸收光谱进行分析。结果表明,掺杂稀土元素La可使TiO2的光吸收范围发生红移,掺杂电气石将增强La/TiO2光吸收强度,T/La/TiO2复合光催化薄膜最佳制备工艺为:La3+掺杂量为1.2%(wt,下同)、电气石掺杂量为0.8%、焙烧温度为500℃、焙烧时间为1.5h、负载次数2次,样品的的甲醛降解率可达82.5%。     

Preparation and characterization of N-S-codoped TiO(2) photocatalyst and its photocatalytic activity

N-S-codoped anatase nanosized TiO(2) photocatalyst (NSTO) was successfully prepared by one-step hydrothermal method from a mixed aqueous solution of Ti(SO(4))(2) and thiourea. The samples were characterized by XRD, UV-vis, XPS, FT-IR and EA. From results of UV-vis, a red shift of the absorption edge was brought out owing to N and S codoping, and the extension for photoabsorption range of NSTO occurred. XRD, XPS, EA and FT-IR studies revealed that N and S were in situ codoped in the lattice of TiO(2) and N concentration decreased from the surface to the center of NSTO. Especially, the photocatalytic tests indicated that NSTO exhibited a high activity for decompositions of methyl orange both under UV-light and vis-light irradiation comparing to S-doped TiO(2) (STO) and undoped TiO(2) (TO). The high activity of NSTO can be related to the results of the synergetic effects of strong absorption in the UV-vis region, red shift in adsorption edge, oxygen vacancies and the enhancement of surface acidity induced by N and S codoping.     

Characterization of TiO(2)-chitosan/glass photocatalyst for the removal of a monoazo dye via photodegradation-adsorption process

In this paper, the newly explored TiO(2)-Chitosan/Glass was suggested as a promising alternative material to conventional means of wastewater treatment. Characterization of TiO(2)-Chitosan/Glass photocatalyst was studied with SEM-EDX, XRD, and Fourier transform infrared spectroscopy (FTIR) analysis. The combination effect of photodegradation-adsorption process for the removal of methyl orange (MO), an acid dye of the monoazo series occur promisingly when four layers of TiO(2)-Chitosan/Glass photocatalyst was used for MO removal. Approximately, 87.0% of total MO removal was achieved. The reactive -NH(2), -OH, and metal oxide contents in the prepared photocatalyst responsible for the photodegradation-adsorption effect were confirmed by FTIR study. Similarly, MO removal behavior was well supported by SEM-EDX and XRD analysis. Significant dependence of MO removal on the TiO(2)-Chitosan loading can be explained in terms of relationship between quantum yield of photocatalytic reactions and photocatalyst structure/activity. Hence, the research work done thus far suggests a new method, having both the advantages of photodegradation-adsorption process in the abatement of various wastewater pollutants.     

纳米二氧化钛/硅胶光催化剂的制备与性能研究

采用溶胶 凝胶法在硅胶载体上制备了纳米二氧化钛 ,研究载体表面负载二氧化钛的结构、表面形态及其光催化性能。实验发现 ,包覆在硅胶表面的二氧化钛大小为 2 0～ 30nm ,且分布均匀 ,晶型为锐钛矿相 ,以甲基橙作为降解对象研究所制备样品的光催化性能。     

Effects of SO2 on selective catalytic reduction of NO with NH3 over a TiO2 photocatalyst

The effect of SO₂ gas was investigated on the activity of the photo-assisted selective catalytic reduction of nitrogen monoxide (NO) with ammonia (NH₃) over a TiO₂ photocatalyst in the presence of excess oxygen (photo-SCR). The introduction of SO₂ (300 ppm) greatly decreased the activity of the photo-SCR at 373 K. The increment of the reaction temperature enhanced the resistance to SO₂ gas, and at 553 K the conversion of NO was stable for at least 300 min of the reaction. X-ray diffraction, FTIR spectroscopy, thermogravimetry and differential thermal analysis, x-ray photoelectron spectroscopy (XPS), elemental analysis and N₂ adsorption measurement revealed that the ammonium sulfate species were generated after the reaction. There was a strong negative correlation between the deposition amount of the ammonium sulfate species and the specific surface area. Based on the above relationship, we concluded that the deposition of the ammonium sulfate species decreased the specific surface area by plugging the pore structure of the catalyst, and the decrease of the specific surface area resulted in the deactivation of the catalyst.     

Kinetics of the decoloration of reactive dyes over visible light-irradiated TiO(2) semiconductor photocatalyst

Photocatalytic decoloration kinetics of triazine (Reactive Red 11, Reactive Red 2, and Reactive Orange 84) and vinylsulfone type (Reactive Orange 16 and Reactive Black 5) of reactive dyes have been studied spectrophotometrically by following the decrease in dye concentration with time. At ambient conditions, over 90-95% decoloration of above dyes have been observed upon prolonged illumination (15 h) of the reacting system with a 150 W xenon lamp. It was found that the decoloration reaction followed first-order kinetics. The values of observed rate constants were found to be dependent of the structure of dyes at low dye concentration, but independent at higher concentration. It also reports for the first time the decoloration of two different dyes together in a binary dye mixture using visible light-irradiated TiO(2) photocatalyst. Rate of decoloration of two different dyes together in a binary dye mixture using visible light-irradiated TiO(2) photocatalyst is governed by the adsorptivity of the particular dye onto the surface of the TiO(2) photocatalyst.     

Effects of SO2 on selective catalytic reduction of NO with NH3 over a TiO2 photocatalyst

Abstract

The effect of SO₂ gas was investigated on the activity of the photo-assisted selective catalytic reduction of nitrogen monoxide (NO) with ammonia (NH₃) over a TiO₂ photocatalyst in the presence of excess oxygen (photo-SCR). The introduction of SO₂ (300 ppm) greatly decreased the activity of the photo-SCR at 373 K. The increment of the reaction temperature enhanced the resistance to SO₂ gas, and at 553 K the conversion of NO was stable for at least 300 min of the reaction. X-ray diffraction, FTIR spectroscopy, thermogravimetry and differential thermal analysis, x-ray photoelectron spectroscopy (XPS), elemental analysis and N₂ adsorption measurement revealed that the ammonium sulfate species were generated after the reaction. There was a strong negative correlation between the deposition amount of the ammonium sulfate species and the specific surface area. Based on the above relationship, we concluded that the deposition of the ammonium sulfate species decreased the specific surface area by plugging the pore structure of the catalyst, and the decrease of the specific surface area resulted in the deactivation of the catalyst.     

Sustainable engineering of TiO2-based advanced oxidation technologies:From photocatalyst to application devices

In recent years,photocatalysis(PC)and photoelectrocatalysis(PEC)technologies have shown great promise as low-cost,environmentally friendly,and sustainable strategies in addressing the issues of energy shortages and environmental pollution,which has become a research hotspot.Titanium dioxide(TiO2)-based PC and PEC are the most promising sustainable technologies for advanced oxidation appli-cations.Due to its inherent characteristics,including high oxidation ability,low price,and stability,TiO2 photocatalyst has been widely studied and used in different scales for numerous decades.For practical applications in these areas,the engineering of the photocatalysts and the design of the PC and PEC devices must be both environmentally and economically sustainable.On the one hand,for the engineering of the photocatalysts,the photocatalyst shall be able to deliver the following characteristics,including large specific surface area,high absorption of light,rapid and low-cost separation and regeneration,and high stability.On the other hand,the design of the PC and PEC devices shall facilitate high in energy utilization and catalytic efficiency,and low in building and operational cost.This work covers the reaction mecha-nism ofTiO2-based PC and PEC technologies,sustainable design,and preparation of TiO2 photocatalysts as well as sustainable design in PC and PEC devices for wastewater treatment,sensing,and water split-ting.Finally,we provide some critical perspectives on the future development of TiO2-based PC and PEC technology.     

炭与TiO2光催化剂的复合及协同作用研究进展

通过论述炭与TiO2光催化剂的复合方式，系统总结了复合光催化剂的各种制备方法，指出炭与TiO2的复合呈现多样化的特征，炭不仅作为载体，还可以用作涂层、造孔剂以及助剂。同时，炭在复合体中也展现出多方面的作用，不仅可以富集目标污染物，捕获中间产物，还可以抑制水蒸气和其他组分对光催化降解的影响，并且可以抑制热处理时TiO2相变和晶粒长大。可见，炭与TiO2光催化剂的复合将为推动光催化技术的实用化产生积极影响。     

Surface structure of the TiO2 thin film photocatalyst

Control of the surface structure of titanium dioxide thin film photocatalysts was successfully carried out by a polymer-doped dip-coating process. The thin films prepared were either transparent or opaque, depending on the molecular weight of the polymer doped. All the thin film photocatalysts had anatase form with similar crystallinity. The surface of the transparent thin films looked plain consisting of uniformly aggregated nanometer-size TiO2 particles, while the opaque thin films were formed of cubic crystalline TiO2 at the micrometer level. Both the transparent and opaque films showed catalytic activity for the elimination of NOx in air. The specific surface area and photocatalytic activity of the transparent thin film was almost the same as that of the opaque one. The activity of the thin films was almost equal to the commercial photocatalyst P25. Decrease in the film thickness led to a decrease of the elimination of NO in air by the thin films. The thin films were porous and the surface area was dependent on the film thickness. Adsorbed NO was photooxidized to NO2 by the thin films, while the NO2 formed was re-photooxidized to HNO3 before the desorption of NO2 from the film surface.     

TiO2光催化剂的掺N过程研究

以饱和尿素溶液水解沉淀钛酸四丁酯制备水合TiO2，再于温度400-700℃的空气气氛下煅烧2h，制得淡黄色的掺氮TiO2光催化剂。对样品的物相、粒径、比表面积及吸光性能进行了测试和表征，表明样品的粒径10-30nm，比表面积30-70m^2／g，有明显的可见光吸收效应；通过TG-DTA、FT-IR及XPS等测试结果，分析了氮的掺杂过程，表明掺杂氮源主要以形成配合物分子形式均匀存在于煅烧前驱体中，并在TiO2从无定形转为锐态矿型的过程中以Ti-N化学键的形式进入TiO2晶格。     

微等离子体氧化法TiO2、TiO2(W)薄膜的制备及性能

利用微等离子体氧化方法,在纯Ti金属表面制备TiO2、TiO2(W)薄膜,并用X射线衍射(XRD)、扫描电镜(SEM)初步研究了薄膜的组织结构和表面形貌.在不同的条件下,得到3种不同类型结构组成的薄膜:单一TiO2的锐钛型结构、单一TiO2金红石结构及TiO2(W)薄膜;同时对薄膜的催化特性进行了初步的研究.     

Preparation and activity evaluation of p-n junction photocatalyst NiO/TiO2

p–n Junction photocatalyst NiO/TiO₂ was prepared by sol–gel method using Ni(NO₃)₂·6H₂O and tetrabutyl titanate [Ti(OC₄H₉)₄] as the raw materials. The p–n junction photocatalyst NiO/TiO₂ was characterized by UV–vis diffuse reflection spectrum, X-ray powder diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The photocatalytic activity of the photocatalyst was evaluated by photocatalytic reduction of Cr₂O₇²⁻ and photocatalytic oxidation of rhodamine B. The results show that, for photocatalytic reduction of Cr₂O₇²⁻, the optimum percentage of doped-NiO is 0.5% (mole ratio of Ni/Ti). The photocatalytic activity of the p–n junction NiO/TiO₂ is much higher than that of TiO₂ on the photocatalytic reduction of Cr₂O₇²⁻. However, the photocatalytic activity of the p–n junction photocatalyst NiO/TiO₂ is much lower than that of TiO₂ on the photocatalytic oxidation of rhodamine B. Namely, the p–n junction photocatalyst NiO/TiO₂ has higher photocatalytic reduction activity, but lower photocatalytic oxidation activity. Effects of heat treatment on the photocatalytic activity of p–n junction photocatalyst NiO/TiO₂ were investigated. The mechanisms of influence on the photocatalytic activity were also discussed by the p–n junction principle.     

Ni2O3/TiO2-xNx可见光催化剂的制备及表征

用溶胶-凝胶法制备了一种新型可见光催化剂Ni2O3/TiO2-xNx,用热分析、X射线光电子能谱及X射线衍射等进行了分析表征,并以偶氮染料阳离子红为目标污染物,分析了催化剂可见光下的催化活性.结果表明,Ni2O3/TiO2-xNx催化剂样品450℃处理后呈锐钛矿型.N元素进入TiO2晶格,Ni元素以Ni2O3的形式游离于TiO2晶格之外.相对于无掺杂TiO2,Ni2O3/TiO2-xNx催化体系由于N元素的掺杂使其在可见光区域的吸收大大增强, Ni2O3掺入加快了光生电子-空穴的分离和转移,因此可见光下的催化活性和光电化学活性大大提高.     

Microwave assisted rapid and complete degradation of atrazine using TiO(2) nanotube photocatalyst suspensions

A technology, microwave-assisted photocatalysis on TiO(2) nanotubes, which can be applied to degrade atrazine rapidly and completely, was investigated. TiO(2) nanotubes were prepared, and confirmed by XRD, TEM and ESR. Microwave-assisted photocatalytic degradation of atrazine in aqueous solution was investigated. The result indicates that atrazine is completely degraded in 5min and the mineralization efficiency is 98.5% in 20min, which is obviously more efficient than that by the traditional photocatalytic degradation methods. It may be attributed to the intense UV radiation generated by electrodeless discharge lamps under microwave irradiation, the increased number of OH, additional defect sites on TiO(2) under the irradiation of microwave and larger specific surface area of TiO(2) nanotubes which could adsorb more organic substances to degrade than TiO(2) nanoparticles. Along with the degradation of atrazine, the concentrations of Cl(-) and NO(3)(-) increase gradually. In 20min [Cl(-)] and [NO(3)(-)] are 3, 27.8mg/L, respectively, which are close to their stoichiometric values. The major intermediates of atrazine were identified by HPLC/MS and possible degradation pathways of atrazine in microwave-assisted photocatalysis on TiO(2) nanotubes were proposed.