Iron and chromium doped titanium dioxide nanotubes for the degradation of environmental and industrial pollutants

Pure titanate nanotubes and titanate nanotubes doped with iron (III) and chromium (III) were fabricated by the hydrothermal treatment in methanol and sodium hydroxide mixture. The fabricated nano tubes have high surface area, high aspect ratio, consisted of very good surface morphology and high metals dispersion. The morphology, crysralline phase, composition were characterized by powdered X-ray diffraction, scanning electron microscopy, transmission electron microscopy, Barrett-Joyner-Halenda methods and X-ray photoelectron spectroscopy. The results showed that nanotubes possess anatase phase and are composed up of 8–12 nm in diameter and 360–400 nm in length. The band gap of the titanium dioxide nanotubes was determined using transformed diffuse reflectance spectroscopy according to the Kubelka-Munk theory, showed pronounced band gap decrease on doped titanium dioxide nanotubes. The photocatalytic activity of doped nanotubes were evaluated in terms of degradation of phenol and photoreduction of carbon dioxide into methanol and ethanol under Ultra violet and Infra red irradiation. It was found that with iron (III) and chromium (III) doped titanium dioxide nanotubes exhibited much higher photocatalytic activity than undoped titanate nanotubes.     

制备多孔镍负载TiO2薄膜光催化降解喹啉和化工废水

为了获得具有高光催化活性和稳定性的TiO2薄膜,采用浸渍涂布法不加黏结剂将Deguessa P-25TiO2固定在泡沫镍基片上,制备成泡沫镍基负载TiO2薄膜,并以Ti-10薄膜为光催化组件制备了一种新型连续流内循环光催化反应器。表征结果显示:P-25薄膜呈混晶相,增大负载浓度会增加基片上结晶质(如锐钛矿相(101))数量、团聚颗粒数量、表面微裂痕以及比表面积;高温煅烧下泡沫镍基片上Ni元素以金属Ni和NiO形式扩散到薄膜表面,形成NiO-Ni体系,有助于提高薄膜的光催化活性;当负载P-25质量分数为10%时,薄膜表层Ni原子比为12.29%,此时薄膜具有最佳光催化活性。以Ti-10样品为光催化薄膜组件制备了一种连续流光催化反应装置,该装置降解化工废水的实验结果显示反应装置连续运行一周,出水可达到一级排放标准。     

非离子表面活性剂修饰纳米钛柱撑粘土材料的合成与应用

本文采用非离子表面活性剂聚乙烯醇(PVA)对粘土进行改性修饰,并以钛酸丁酯和盐酸分别为前驱物和酸催化剂,采用溶胶-凝胶法制备了PVA修饰疏水型纳米钛柱撑粘土材料,对其进行了比表面积(BET)、热重分析(TGA)、X射线粉末衍射(XRD)和扫描电子显微镜(SEM)表征。实验结果表明,TiO2成功地插入了粘土层间,并以锐钛矿型的晶型存在,制备的柱撑粘土复合材料仍有较好的层状结构,其比表面积较原土有明显的增加,经过PVA修饰后柱撑粘土表面的疏水性得到了提高。以甲基橙的吸附和降解为模型反应,考察了柱撑粘土的吸附性能和光催化活性,实验结果发现PVA修饰疏水型纳米钛柱撑粘土材料对甲基橙表现出了良好的吸附能力和较好的光催化活性。     

Transition metals (Mn,Ni, Co) doping in TiO<Subscript>2</Subscript> nanoparticles and their effect on degradation of diethyl phthalate

Transition metal-doped TiO₂ nanoparticles are synthesized by sol–gel method. The as-prepared samples are characterized by various techniques to correlate structural and optical properties with chemical nature of dopants and their effect on photocatalytic degradation of diethyl phthalate esters. X-ray diffraction (XRD) reveals that all the samples are crystalline and exhibit anatase as a major phase. Chemical nature of dopants could not affect the formation of anatase and its volume fraction. The crystallite size of undoped and doped TiO₂ nanoparticles varies between 10 and 12 nm as confirmed by XRD and transmission electron microscope. The lowest optical band gap observed is 2.47 eV in Mn-doped TiO₂. Among all the samples, Ni-doped TiO₂ sample shows better photocatalytic activity and degradation of diethyl phthalate due to its lower crystallite size and higher surface area than those of Mn- and Co-doped TiO₂ samples.     

坡缕石/磁性铁氧化物/TiO2复合光催化剂性能实验研究

用醇盐水解法、硫酸亚铁-硝酸钾氧化法制备TiO2光催化剂、坡缕石/TiO2复合光催化剂和坡缕石/磁性铁氧化物/TiO2复合光催化剂.通过XRD、TEM、UV-Vis和MS分析光催化剂的物相组成、形貌特征、对紫外可见光的漫反射以及磁化率,并以甲基橙为处理对象,对比研究了TiO2光催化剂、坡缕石/TiO2复合光催化剂和坡缕石/磁性铁氧化物/TiO2复合光催化剂的光催化效果.结果表明:坡缕石/磁性铁氧化物的复合能降低复合光催化剂中锐钛矿的平均粒径,提高锐钛矿的分散性.铁的复合是否提高光催化剂的光催化效率与催化剂的煅烧温度有关.坡缕石的复合对光催化剂的最佳煅烧温度有影响.     

Visible light N-TiO<Subscript>2</Subscript>-induced photodegradation of Congo red: characterization,kinetics and mechanistic study

In this study, the photocatalytic degradation of Congo red has been investigated in N-doped TiO₂ (N-TiO₂) aqueous suspensions under visible light irradiation. Visible light-active N-TiO₂ was successfully prepared at three different weight contents (2.5, 5, and 7%) employing sol–gel method. It was able to harvest the visible irradiation with wavelength suitable for activation. X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray spectrometer, diffused reflectance UV–Vis spectroscopy, nitrogen adsorption Brunauer–Emmert–Teller, Raman spectroscopy, photoluminescence and X-ray photoelectron spectrometer were used to characterize the doped catalyst. The samples had a relatively large specific Brunauer–Emmert–Teller surface areas of about 42 m² g^?1 with average X-ray diffraction crystalline size of 52 nm and showed visible light photocatalytic activity at about 408 nm. The impacts of several operating parameters on the Congo red photodegradation process were examined. Langmuir–Hinshelwood model exhibited pseudo-first-order degradation kinetics. N-TiO₂-assisted plausible photodegradation mechanism has been suggested based on the qualitatively detected intermediate compounds.     

溶胶-凝胶法制备掺铈纳米TiO2光催化剂降解NO2-的研究

利用X射线粉晶衍射、扫描电镜、透射电镜等方法分析煅烧温度、保温时间等因素对以溶胶-凝胶法制备的纳米TiO2及掺铈纳米TiO2光催化剂的相组成、晶粒大小的影响,煅烧温度升高使晶粒粒径增大并使物相组成发生改变,保温时间增加使晶粒粒径增大以及结晶度增高;利用所制备样品对亚硝酸盐进行光催化降解试验研究,结果表明样品的制备条件、光催化剂的晶粒大小、光催化时间对亚硝酸盐的降解率有重要影响,铈的掺入有利于提高亚硝酸盐的降解率,掺铈量在1％～3％范围内,亚硝酸盐的光催化降解率随掺铈量的增加而提高。     

Photodegradation of amaranth in aqueous solution catalyzed by immobilized nanoparticles of titanium dioxide

The use of suspensions of nanoparticles of titanium dioxide in photocatalytic degradation of dye solution has disadvantages of inconvenient separation of fine particles for reuse and limited penetration of light for effective degradation. These problems can be minimized by supporting titanium dioxide on various inert supports. The present study involves the preparation of immobilized titanium dioxide films by three different techniques and characterization of the prepared films. The immobilized films of nanocrystals of titanium dioxide were prepared using sol?Cgel technique, polyvinyl alcohol?Cformaldehyde binder and acrylic emulsion. The photocatalytic performance of the prepared films for degradation of amaranth dye has also been evaluated and compared. Combination of photodegradation and adsorption processes induces strong beneficial effects on removal of dyes. Addition of high adsorption capacity activated carbon to photoactive titanium dioxide in photodegradation of dyes improves the efficiency of dye mineralization. The activated carbon has also been immobilized along with titanium dioxide in the present work to examine the dual effect of photodegradation and adsorption in the removal of amaranth. The films formed with the help of polyvinyl alcohol?Cformaldehyde binder showed better dye degradation capabilities.     

纳米TiO2光催化降解亚甲基蓝

在以钛酸丁酯为钛源,采用溶胶-凝胶法合成制备纳米TiO2催化剂样品的基础上,将其用于在紫外光照射和无光照射条件下进行亚甲基蓝降解的实验研究,并与P-25纳米TiO2进行光催化降解对比研究。对在不同条件下合成制备样品的光催化降解率的差异,通过X射线粉晶衍射、扫描电镜等从物相组成、微观结构等因素上进行了分析和探讨。结果表明,采用溶胶-凝胶法在450℃焙烧2 h所得到的纳米TiO2具有很好的光催化降解亚甲基蓝的能力,当催化剂样品质量浓度为2.5 g/L,亚甲基蓝初始浓度为5.0 mg/L时,室温下光催化反应3 h,其降解率达98%以上,其光催化降解率比P-25纳米TiO2高;光催化降解率与催化剂样品的制备条件、物相组成、颗粒尺寸等因素有关。     

不同产地矿物对有机-钛柱撑蒙脱石复合材料光催化活性的影响

以钛酸丁酯为前驱体,采用醋酸为酸催化剂制备TiO2溶胶,将制备的溶胶分别加入经表面活性剂十六烷基三甲基溴化铵改性的河北、临安、安吉、内蒙古膨润土中,制备有机-钛柱撑膨润土复合光催化剂,并对其进行XRD、SEM、BET表征。结果表明,TiO2插入了膨润土层间,并以锐钛矿型的晶形存在,制备的复合光催化剂仍有较好的层状结构,其比表面积均比相对应的不同产地的膨润土的比表面积大。以甲基橙为目标污染物,考察了有机-钛柱撑膨润土复合光催化剂的吸附性能和光催化活性,发现所制备的复合光催化剂具有较好的光催化活性,而且用不同的膨润土合成的催化剂的光催化活性差别很大。膨润土的化学组成和层状结构上的差异是复合催化剂吸附性能和光催化活性差别的主要原因。其中有机-钛柱撑临安膨润土复合光催化剂的光催化活性最好。     

氮配位的磁性高分子复合微球P（GMA—MMA—AA）／Fe3O4负载钯催化水相Suzuki反应的研究

以可控自由基聚合技术制备的磁性高分子复合微球P（GMA—MMA．AA）／Fe3O4为载体,三乙烯四胺为配体制备了一种新型的负载型钯催化剂。采用透射电镜、振动样品磁强计、x射线光电子能谱仪和x射线衍射分析仪等手段对催化剂进行了表征,并评价了催化剂对水相Suzuki反应的催化活性。结果表明,催化剂的平均粒径为800nm左右,钯在载体表面呈高度分散状态,整个催化剂呈超顺磁性。该催化剂在空气氛围中就能较好的催化水相中芳基卤代物与苯硼酸的Suzuki反应,较高产率且立体选择性地生成取代的联苯产物,反应过程中催化剂可稳定分散于反应体系中,并可在外磁场作用下快速与从体系分离。催化剂重复使用5次后,仍具有较高的活性。     

Synthesis of novel potassium peroxodisulfate-modified titanium dioxide for photocatalytic oxidation of acetaminophen under visible light irradiation

In recent years, traces of acetaminophen, a widely used analgesic and anti-inflammatory and known to be an over-the-counter drug, have been detected unaltered in effluents of conventional wastewater treatment facilities. About 58–68% released through excretion during patient’s therapeutic treatment, and only about 80–86% were removed by the wastewater treatment facility. This study investigated the improved performance of photocatalysis in degrading or removing acetaminophen. The visible light active potassium peroxodisulfate-doped titanium dioxide photocatalysts synthesized via sol–gel method was used to eliminate acetaminophen from aqueous solutions through photocatalytic oxidation. The effects of the amount of dopant, calcination temperature and calcination time on the properties and visible light photocatalytic activity of potassium peroxodisulfate-doped titanium dioxide were also investigated. Increasing the amount of the dopant and calcination temperature up to a certain extent increases removal efficiency while further decreased the removal rate. Potassium peroxodisulfate-doped titanium dioxide photocatalysts were characterized by X-ray diffraction, ultraviolet–visible light diffuse reflectance spectroscopy, Brunauer–Emmett–Teller method and X-ray photoelectron spectroscopy. Potassium peroxodisulfate-doped titanium dioxide with 0.5%_w dopant and calcined at 300 °C for 3 h degrades about 100% acetaminophen in aqueous solution within 540 min. The reaction of acetaminophen with the photocatalyst has an apparent rate constant of 8.39 × 10^?3 min^?1.     

Exfoliation of kaolinite by urea-intercalation precursor and microwave irradiation assistance process

A type of exfoliated kaolinite was produced by urea-intercalation and original microwave irradiation assisted method. The product was investigated by Fourier transformation infrared (FT-IR) spectroscopy, X-ray diffraction (XRD), scanning electronic microscopy (SEM), Brunauer-Emmett-Teller (BET) and laser particle analysis techniques. FT-IR spectra show that NHCO molecule exists in the intercalated kaolinite. XRD analyses indicate that the kaolinite sheet-like structure was disordered after microwave irradiation. The urea decomposition process and explosion effect between the sheet-like structures of kaolinite under microwave irradiation were discussed. The SEM and BET analyses reveal that the end product is exfoliated kaolinite with thin particles and increased surface area. Size and zeta potential analyses show that the particle size distribution is between 250 nm and 550 nm with normal distribution and the particle is negatively charged. In comparison with the conventional grind method, the process adopted appears to be economic and the exfoliated kaolinite end product may display a significantly enhanced performance in industrial applications.     

Structure and chemistry of grain boundaries in deformed, olivine + basalt and partially molten lherzolite aggregates: evidence of melt-free grain boundaries

Olivine grain boundaries in deformed aggregates of olivine + basalt and partially molten lherzolite were analyzed with various electron microscopy techniques to test for the presence of thin (0.5-10 nm) intergranular melt films. High-resolution transmission electron microscopy (HREM) observations reveal that most of the boundaries do not contain a thin amorphous phase, although a small fraction of grains are separated by relatively thick (~1 µm) layers of melt. However, due to the anisotropy of the olivine-melt interfacial energy, melt often tapers from a triple junction into an adjoining grain boundary over a length of 1 to 2 µm, giving an effective dihedral angle of only ~2°. The chemistry of olivine-olivine grain boundaries was analyzed using energy dispersive X-ray (EDX) profiling by scanning transmission electron microscopy (STEM) with a probe size of <1.5 nm. Ca, Al and Ti segregate to grain boundaries forming enriched regions of <7 nm width. Although these elements are concentrated in the glass phases, the presence of glass films with the same chemical composition as the bulk glass phases cannot explain concentrations of other elements such as Si and Al at the boundaries. Combined with the HREM results, the STEM/EDX profiling demonstrates the existence of chemical segregation between solid grains but the absence of thin, grain boundary melt films. Additionally, if melt films exist along all of the grain boundaries, as reported for similar samples by other groups, the rock should be substantially weakened. Creep experiments on the partially molten rocks analyzed in this study reveal little weakening at small melt contents, consistent with our observations of melt-free grain boundaries.     

不同表面活性剂修饰TiO2柱撑粘土的制备及其光催化活性研究

本文分别采用阴离子、非离子、阳离子三种不同类型的表面活性剂对河北蒙脱石进行改性修饰,并以酞酸丁酯和盐酸分别为前驱物和酸催化剂,采用溶胶-凝胶法（Sol-gel）制备了不同表面活性剂修饰TiO2柱撑粘土催化剂.用X射线粉末衍射（XRD）和场发射扫描电子显微镜（SEM）等手段表征了催化剂的微观结构,以2,4,6-三氯苯酚（2,4,6-trichlorophenol, TCP）和甲基橙染料的吸附、降解为模型反应,考察了改变溶胶和表面活性剂的不同添加顺序对阳离子表面活性剂所修饰的催化剂性质的影响,以及不同类型的表面活性剂修饰所得的催化剂的光催化活性.实验结果表明,通过添加不同的表面活性剂能够不同程度地改变柱撑粘土的BET比表面积,并使其对不同目标污染物具有不同的吸附能力和光催化活性.阴离子表面活性剂十二烷基苯磺酸钠（DBS）修饰的TiO2柱撑粘土具有较好的光催化活性,其次是非离子表面活性剂聚乙烯醇（PVA）修饰的TiO2柱撑粘土,而阳离子表面活性剂十六烷基三甲基溴化铵（CTMAB）修饰的柱撑粘土光催化活性较差.     

Study of photocatalytic degradation of environmentally harmful phthalate esters using Ni-doped TiO<Subscript>2</Subscript> nanoparticles

Undoped and Ni-doped TiO₂ nanoparticles are synthesized using sol–gel technique. The physical, structural, optical and thermal properties of the samples are investigated using X-ray powder diffraction, Fourier transform infrared spectroscopy, transmittance electron microscopy, UV–visible diffuse reflectance and thermogravimetric analysis. The photocatalytic activity of the samples is investigated by the photocatalytic degradation of phthalate esters. Phthalate esters have been considered as endocrine disrupting compounds. Ni-doped TiO₂ samples show better photocatalytic activity as compared to undoped TiO₂ sample. The greater photocatalytic activity of doped samples as compared to undoped TiO₂ can be attributed to the production of more number of electron–hole pairs in doped samples.     

叶腊石微结构及其晶体结构缺陷的高分辨透射电镜分析

采用场发射扫描电镜（FE-SEM）、高分辨透射电镜（HRTEM）结合选区电子衍射（SAED）、X射线粉晶衍射（XRD）及X射线荧光光谱（XRF）等对浙江青田叶腊石的微结构特征进行较系统的研究。结果表明：①粉晶X射线衍射证实青田叶腊石具有典型的单斜晶系特征,该结论与叶腊石粉体选区电子衍射结果吻合,且其伴生矿为石英。②叶腊石微晶体呈＂复式板片＂构型,且＂复式＂板片中薄片厚度约为8±2 nm。③在高能电子束辐照下,叶腊石矿物颗粒形貌及晶格结构发生明显的改变,且由此产生晶格膨胀,并最终形成非晶态。     

Preparation and Phase Transformation Behavior of Boehmite via Heat Treatment in Water Vapor

Boehmite was prepared under heat treatment in water vapour, and the phase transformation of gibbsite heat-treated at various temperatures was investigated. The sample was characterized by scanning electron microscopy(SEM), X-ray diffraction (XRD), thermogravimetry and differential thermalanalysis (TG-DTA), fourier transform infrared (FTIR),and BET surface area.Effect of temperature on preparation was studied in the range of 155°–195°.With the increase in temperature, transformation of gibbsite into crystalline boehmites took place as indicated by the X-ray diffraction (XRD). The shape of the grains in the prepared sample was cube-like morphology.In water vapour gibbsite transform into boehmite by a dissolution - precipitation mechanism.     

TiO<Subscript>2</Subscript>-based shaped catalyst for the recovery of elemental sulfur from H<Subscript>2</Subscript>S and SO<Subscript>2</Subscript> gas streams

The Claus process has been used for the conversion of H₂S and SO₂ to elemental sulfur. These two sulfur compounds need special attention because they are very poisonous with negative impact on both the environment and human health. Here, highly active Fe–Ni/TiO₂ catalyst has been prepared and shaped by three different binders (bentonite, polyethylene glycol and carboxymethyl cellulose) into extrudes. Comparing the mechanical strength and surface area of prepared extrudes, the optimal shaped catalyst was selected with 20% of bentonite, 2% of PEG and 2% of CMC. The optimal catalyst was characterized by X-ray powder diffraction, temperature-programmed reduction, Brunauer–Emmett–Teller specific surface area, Barrett–Joyner–Halenda, scanning electron microscopy and energy-dispersive X-ray techniques and used for sulfur recovery process. The performance of this product for sulfur recovery via Claus process was excellent with the conversion of hydrogen sulfide of 76.77% and sulfur dioxide of 97.83%. The catalyst also provides high hydrolysis activity of CS₂ (83.06%). Therefore, a highly active TiO₂-supported shaped catalyst with 85.62% of conversion efficiency has been prepared successfully to convert the small amounts of H₂S, SO₂ and CS₂ to elemental sulfur.     

Response surface methodology (RSM) optimization approach for degradation of Direct Blue 71 dye using CuO–ZnO nanocomposite

The present study highlights the synthesis of CuO–ZnO nanocomposite via facile hydrothermal method at 150 °C and autogenous pressure. The structural and textural features of prepared composite material was characterized by several characterization techniques such as X-ray powder diffraction, Fourier transform infrared spectroscopy, Scanning electron microscopy, and energy-dispersive X-ray spectroscopy. The optimized prepared nanocomposite was utilized for photocatalytic degradation of aromatic Direct Blue 71 dye (DB71) under natural sunlight conditions. The catalytic activity results by CuO–ZnO nanocomposite were observed to be higher than the reagent-grade zinc oxide under visible light conditions. The response surface methodology protocol (RSM) with central composite design was optimized by different photodegradation operational parameters such as pH, dye concentration, catalyst amount, and reaction time. The optimized RSM results demonstrated that a quadratic polynomial model was found suitable to define the relation between the photocatalytic activity and operational parameters. Moreover, the observed high R ² value (0.9786) confirms a strong evaluation of experimental data. To achieve maximum DB71 degradation, optimized condition was found at 177.13 min of contact time, 3.93 solution pH, and 24.34 mg/L of dye concentration with 1.85 g/L of catalyst dose The identical optimum conditions resulted maximum 89.58% DB71 degradation.