Effective synthesis of nanoscale anatase TiO2 single crystals using activated carbon template to enhance the photodegradation of crystal violet

Nanoscale anatase TiO₂ single crystals were successfully synthesized using three kinds of activated carbon (AC) templates through a simple sol–gel method. The optimal photocatalyst (T‐WOAC) was obtained using wood‐based AC template. X‐ray diffraction, transmission electron microscopy and Brunauer–Emmett–Teller analyses revealed that T‐WOAC possessed a small crystallite size of 8.7 nm and a clear mesoporous structure. The photocatalytic properties of samples were then evaluated through photodegradation of crystal violet (CV). Results implied that the photocatalysts prepared using the AC templates exhibited superior photocatalytic activity to that of the original TiO₂. This enhancement may be due to the small crystallite size, large specific surface area and pore volume of the catalysts prepared with ACs. T‐WOAC showed high photocatalytic activity, CV degradation of 99.01% after 120 min of irradiation and k = 0.03914 min^?1, which is 3.9 times higher than that of the original TiO₂ (k = 0.00994 min^?1). This result can be mainly attributed to the application of WOAC with moderate specific surface area and pore volume to produce T‐WOAC. Alkaline conditions benefitted the photodegradation of CV over photocatalysts. This work proposes a possible degradation mechanism of CV and indicates that the fabricated photocatalysts can be used to effectively remove CV from aqueous solutions.     

Synthesis and characterization of ternary nanocomposites of TiO2/rGO/CdS as an efficient catalyst for photo-degradation of methyl orange

Novel ternary composite photocatalysts have been successfully prepared by TiO₂ nanofibers, reduced graphene oxide, and CdS nanoparticles (TiO₂/rGO/CdS) by using electrospinning technique with easy chemical methods. The structures and their properties are examined by X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and field-emission scanning electron microscope (FESEM). The structural characterization of the composite reveals that pure TiO₂ NFs and CdS NPs crystalline very well and the reduced graphene oxide is tightly composed with TiO₂ NFs and CdS Nps. The photodegradation of methyl orange (MO) under UV light illumination is significantly enhanced compared with that of bare materials. This ternary composite degrades methyl orange within 75 min. The enhanced photocatalytic degradation performance resulted from effective separation of e–h pairs with rGO sheets and also contributed for high rate degradation efficiency. This novel ternary composite has a potential application of wastewater purification and utilization for energy conversions.     

Synthesis and photocatalytic activity of TiO2/conjugated polymer complex nanoparticles

A photocatalyst of nanometer TiO2/conjugated polymer complex was successfully synthesized and characterized by spectroscopic methods and photocatalytic experiments. The complex photocatalyst could be activated by absorbing both ultraviolet and visible light （λ = 190-800 nm）. Methylene blue （MB） could be degraded more efficiently on the complex photocatalyst than on the TiO2 under natural light. The conjugated polymer played a promoting role in the photocatalytic degradation of MB. The calcination temperature had an important effect in degradation of dye and could be summarized as 260℃ 〉 300 ℃ 〉 340 ℃ 〉 220 ℃ 〉 180 ℃.     

ZnTPP/TiO_2纳米复合催化剂的合成及其光催化活性的测定

<正>TiO2是一种环保型多相半导体光催化剂,对一些毒性大、生物难降解的有机污染物,用TiO2光催化剂催化生成的强氧化剂,在常温、常压下可以彻底地将有机物氧化为H2 O、CO2等小分子[1-3]。目前,TiO2主要用于中低浓度废水处理、小空间空气净化、材料表面自清洁、重金属回收、固体废物处理等领域。与传统除污工艺相比,具有无毒、安全、稳定性好、催化活性高、见效快、能耗低、可重     

树叶为模版制备网状TiO2和Fex/TiO2及光催化活性研究

以梧桐树叶为模板制备了具有网状结构的TiO2和Fex/TiO2光催化材料.通过扫描电镜(SEM)、X-射线衍射(XRD)、X-射线光电子能谱(XPS)、荧光发射光谱(PL)、紫外-可见吸收光谱(UV-Vis)等对这两类光催化材料的结构和物理性能进行了表征.结果表明,以树叶为模板制得的Fe0.005/TiO2呈网状结构.在600～800℃范围内,随煅烧温度的升高,网状TiO2和Fe0.005/TiO2中锐钛型TiO2的含量减少,Fe3+的掺杂能促进锐钛型向金红石型的转变.与Degussa P25相比,网状TiO2和Fex/TiO2的荧光光谱强度明显减弱,光生电子-空穴对的复合情况得到改善;吸收光谱范围明显红移,禁带宽度有不同程度的缩小.孔雀石绿的光催化降解实验表明,网状TiO2和Fex/TiO2具有比Degussa P25更强的催化活性.光催化活性的稳定性研究表明,网状Fe0.005/TiO2具有良好的稳定性,能多次重复使用.     

石墨烯/电气石/二氧化钛复合材料的制备及其光催化降解异丙醇性能

光催化是一种理想的应对全球能源短缺和环境污染问题的绿色化学技术,可以实现有机物降解、水分解和二氧化碳光还原等.光催化反应效率受诸多因素影响,其中光生载流子(电子和空穴)的分离和传输具有至关重要的作用.以往研究表明,构筑多元复合光催化材料体系有利于光生电子和空穴有效分离和传递,促进催化剂表面的还原和氧化反应,从而提高其光催化效率.基于以上考虑,我们提出了一种新型的石墨烯/电气石/TiO2三元复合光催化材料体系,其中TiO2因其价格低廉、无毒和抗光腐蚀等优点而被广泛用作光催化材料;石墨烯(G)拥有独特的二维结构、高的电子迁移率、大的比表面积,是一种优异的催化剂载体;电气石(T)的一个重要性质是表面存在自发极化的静电场,该静电场将会影响光激发载流子的分离、传递和光催化反应过程.利用水热法合成了不同成分的石墨烯/电气石/TiO2三元复合材料体系.为了对比研究石墨烯表面电荷性质的影响,其中一组的石墨烯(氧化石墨)为直接采用改良的Hummers法所制备,其表面带负电;另一组的石墨烯经聚二烯丙基二甲基氯化铵(PDDA)修饰,使其表面带正电.X射线衍射结果显示,三元复合材料中TiO2为锐钛矿相,其结晶性没有因为与石墨烯和电气石的复合而受到影响.扫描和透射电子显微分析表明,TiO2的平均颗粒大小为15 nm左右,并且与石墨烯和电气石均匀复合.傅里叶变换红外光谱和zeta电位表征分析证实,PDDA可以有效地对石墨烯进行功能化改性,使其表面带正电.紫外-可见分光光谱显示,石墨烯/电气石/TiO2三元复合材料与TiO2的吸收带边一致,复合材料中石墨烯和电气石并没有改变TiO2的光吸收特征.光催化降解异丙醇实验表明,石墨烯/电气石/TiO2三元复合材料优于单纯的TiO2、石墨烯/TiO2以及电气石/TiO2二元复合材料,当石墨烯和电气石的质量百分比分别为0.5%和5%时,三元复合材料降解异丙醇产生丙酮的速率达到最高(223μmol/h).特别值得指出的是,由表面带负电的石墨烯组成的复合材料比由带正电荷的PDDA-石墨烯组成的复合材料具有更高的光催化性能,原因如下:在水溶液中显示正zeta电位值的TiO2与带负电的石墨烯/电气石复合物静电吸引而均匀紧密复合,有利于TiO2中光生电子和空穴的快速分离和传递,从而使得石墨烯/电气石/TiO2三元复合材料具有较高的光催化性能;而带正电的PDDA-石墨烯/电气石复合物和TiO2颗粒相互排斥而不宜复合,导致PDDA-石墨烯基复合材料的光催化活性降低.机理研究揭示,在三元复合材料光催化降解异丙醇的反应中起主要作用的是光生电子和空穴.基于以上研究结果,我们提出了三元复合材料光催化降解异丙醇的反应机理.     

Synthesis of mesoporous TiO2/BMMs via hydrothermal method and its potential application toward adsorption and photocatalytic degradation of crystal violet from aqueous solution

The novel mesoporous TiO₂/BMMs nanocomposites using bimodal mesoporous silica (BMMs) as support and rutile-anatase mixed phase as active species were successfully synthesized via hydrothermal and subsequent calcination method. Their structural and physiochemical properties were characterized by X-ray diffraction, scanning/transmission electron microscopy, BET-isotherms, inductive coupled plasma optical emission spectroscopy, zeta potential, Fourier transform infrared and UV–visible spectroscopy. The results demonstrated that the photocatalytic degradation activity of the synthesized catalysts were extensively enhanced as compare to bare TiO₂, due to the highly uniform dispersion of mixed phases (Anatase and Rutile) TiO₂ on the bimodal mesoporous surfaces. Particularly, the catalytic efficiency became increased as increasing the calcination temperature, showing the highest (98%) overall removal of CV dye using TBH5d as catalyst calcinated at 800 °C. Its most interesting finding is that the % adsorption of TBH5d was 46 %, more than that (26%) of TBH5c calcinated at 600 ℃, however, its % degradation was 21 %, lower than that (39 %) of TBH5c for dye concentration of 20 ppm in 50 min. Meanwhile, the kinetic adsorption and degradation performances were followed the pseudo second and first order models, respectively, further proving the high degradation efficiency of TBH5c with high rate constant than that of TBH5d. Thermodynamic parameters (ΔG_ads, ΔH_ads, and ΔS_ads) were calculated, suggesting the spontaneous and exothermic procedure with high entropy, while the adsorption equilibrium data was fitted to Dubinin-Radushkevich model. Both TBH5c and TBH5d showed an excellent stability and reactivity 71.2 and 61 %, respectively, even after 5th cycles. Thus, these results suggested that that TBH5c may be one of the suitable candidates in wastewater treatments.     

BiVO4/TiO2复合光催化剂的制备及可见光降解腐殖酸

首先以P123为模板剂利用溶胶-凝胶法制备TiO2载体,然后采用沉淀法制得介孔BiVO4/TiO2复合光催化剂.采用X射线衍射仪、漫反射吸收光谱仪、比表面分析仪对所制得的光催化剂进行了表征.结果表明,催化剂样品中的TiO2主要以锐钛矿型存在,BiVO4为四方相和单斜相共存的混晶,与单纯的BiVO4、TiO2光催化剂相比,BiVO4/TiO2复合光催化剂具有更高的可见光吸收性能、较好的比表面积和均一的介孔结构.腐殖酸的可见光降解试验表明,随着腐殖酸初始浓度的增大,其光降解率逐渐降低,ln(C/C0)对t呈线性关系.试验同步研究了腐殖酸光催化降解过程中荧光光谱、红外光谱和GC-MS谱图的变化情况.     

双醇诱导自组装制备多级蛋壳结构TiO2材料及其光催化性能研究

采用双醇诱导自组装的方法可控合成了纳米片、实心球、核壳球、蛋壳球和空心球Ti02．利用SEM、TEM、XRD、UV-Vis等表征手段,探索了一元醇羟基的活泼性及丙三醇的三羟基结构在形成多级结构TiO2中的作用．丙三醇和一元醇的比例及醇热时间可控制TiO2的自组装过程而影响材料的形貌结构．同时光催化降解苯酚实验表明,具有多级结构的蛋壳球TiO2显示高活性,归因于光吸收增强．     

三维有序介孔/大孔TiO2微球的制备、表征及光催化性能

以聚甲基丙烯酸甲酯微球为模板,分别以钛酸四丁酯和四异丙醇钛为钛源,通过溶胶-凝胶法辅助模板法制得TiO2纳米微球前驱体,并用程序升温控制其焙烧温度,最终成功制得了具有三维有序介孔/大孔复合结构的TiO2微球.以罗丹明B(RhB)为模型污染物,探索了以不同钛源制备得到的介孔/大孔复合TiO2微球的光催化性能;并采用XRD、SEM、TEM、UV-vis DRS、比表面积测试、光催化性能测试等对样品的晶粒尺寸、物相、形貌、光吸收、比表面积及性能等进行了分析.结果表明,运用溶胶凝胶法辅助模板法能够合成结晶度高、形貌规整、比表面积大、光催化活性良好的锐钛矿相TiO2微球.     

异质结型AgI/AgBr/TiO2催化剂的制备及其光催化性能

首先以沉积-沉淀法制备AgBr/TiO₂复合催化剂,然后采用离子交换法制备出新型的异质结型AgI/AgBr/TiO₂光催化剂.利用XRD和UV-Vis对AgI/AgBr/TiO₂光催化剂进行了表征.以甲基橙为染料模型,在可见光条件下(500 W、λ>420 nm)研究了AgI的含量对AgI/AgBr/TiO₂催化活性的影响.结果表明,AgI拓展了催化剂的吸收光谱范围;AgI生成量为AgBr的5%时,AgI/AgBr/TiO₂的催化活性最高.AgI/AgBr异质结的形成有利于光生电子和空穴的分离,提高AgI/AgBr/TiO₂的催化活性.     

TiO2/polyaniline composites： An efficient photocatalyst for the degradation of methylene blue under natural light

Polyaniline (PAn) sensitized nanocrystalline TiO_2 composites (TiO_2/PAn) were successfully prepared and used as an efficient photocatalyst for the degradation of dye methylene blue (MB).The results showed that PAn was able to sensitize TiO_2 efficiently and the composite photocatalyst could be activated by absorbing both the ultraviolet and visible light (λ:190～800nm),whereas pure TiO_2 absorbed ultraviolet light only (λ<380nm).Under the irradiation of natural light,MB could be degraded more efficiently on the TiO_2/PAn composites than on the TiO_2.Furthermore,it could be easily separated from the solution by simple sedimentation.     

超临界流体干燥法制备TiO2／C纳米粒子及光催化性能

以TiCl4为原料,采用溶胶凝胶法结合超临界流体干燥法(SCFD)制备了纳米级TiO2/C复合光催化剂.以苯酚的光催化降解对所得催化剂的催化活性进行了评价.结果表明,纳米TiO2/C复合粒子与单组分TiO2比较,复合粒子光催化活性高于单组分的TiO2,h苯酚降解率高达975 ％,COD为957%.并用XRD、TEM、 UV-Vis和XPS等手段进行了表征,iO2以锐钛矿型形式存在.比较了不同制备方法制得的TiO2/C复合催化剂,得出超临界干燥法制备的光催化剂具有粒径小,比表面积大,分散性好,光催化活性高等特点.     

TiO2‐nanoparticles as efficient catalysts for the synthesis of pyridine dicarbonitriles

The catalytic effects of two forms of nano‐TiO₂, which are prepared via an ordinary or a magnetized process, are investigated in the synthesis of pyridine dicarbonitriles by one‐pot multicomponent reaction of 4‐methyl thiophenol, malononitrile, and aryl aldehydes. The results have shown that both prepared nano‐TiO₂ exhibited high catalytic activities toward the synthesis of pyridine dicarbonitrile derivatives but the nano‐TiO₂, which is prepared via a magnetized process, has shown better catalytic activity. Furthermore, this new catalytic method for the synthesis of pyridine dicarbonitriles provides rapid access to the desired compounds in high yields and so a simple work‐up procedure in the presence of water at room temperature. Therefore, this method represents a significant improvement incompatible of the other methods that are available for the synthesis of pyridine dicarbonitriles.     

磁性纳米TiO_2/SiO_2/NiFe_2O_4的制备及其催化性能

采用溶胶凝胶法制备了核壳结构磁性纳米TiO2/SiO2/NiFe2O4催化剂.利用XRD、TEM、VSM等手段对样品的粒径、晶体结构、磁性和光催化性能进行了研究.结果表明:SiO2/NiFe2O4的加入抑制了TiO2纳米粒子的生长,使晶粒尺寸减小,促进了锐钛矿相向金红石相的转变,催化剂的回收率和光催化性能均得到提高.光催化实验结果表明,当SiO2/NiFe2O4的负载量为15%时,焙烧温度为500℃时对亚甲基兰的脱色率最高.     

二氧化钛纳米管的制备与光催化活性

用阳极氧化法,室温条件下在含NH4F和H2O的电解液(丙三醇+NH4F+H2O;乙二醇+NH4F+H2O)中制备了TiO2纳米管阵列。用环境扫描电子显微镜(SEM)、X射线衍射仪(XRD)表征二氧化钛纳米管阵列的微观形貌和物相结构。在丙三醇电解液中,电压为60 V,65 V,70 V,75 V制备的纳米管直径依次为160、170、190、220 nm。对甲基橙(10 mg/L)降解测试TiO2纳米管阵列的光催化性能。研究结果表明:在100 V阳极电压制备经过500℃退火处理后的TiO2纳米管阵列的光催化效果最好,其光催化降解率在光照时间120 min时达到89.2%。     

Synthesis and characterization of PEGylated iron and graphene oxide magnetic composite for curcumin delivery

Nowadays, nanostructures have been given significant attention in medical and biological fields. Among these nanostructures, graphene oxide (GO) has been widely used in drug delivery systems, because of its unique properties, and the ability to connect to other nanostructures such as magnetic nanoparticles (NPs) as well as polymers by its functional groups. In this research, first, GO was prepared by exfoliating graphite according to the modified Hummer’s method, and then the Fe₃O₄ NPs were synthesized by a simple co-precipitation method on GO nanosheets. In the next step, with the help of the ethyl-3-(3-dimethylaminopropyl) carbodiimide/N-hydroxysuccinimide coupling reagents, the polyethylene glycol (PEG) polymer was bonded to the GO-Fe₃O₄ nanocomposite. Finally, anti-cancer drug, curcumin (Cur) was loaded onto the nanocomposite and the Cur loading ratio was measured at about 8%. The samples were evaluated using Fourier transform-infrared, differential scanning calorimtery, vibrating-sample magnetometry, atomic force microscopy and dynamic light scattering techniques. The results show that the prepared nanocomposite is an appropriate candidate for biomedical applications.     

SO_4~(2-)/TiO_2、PO_4~(3-)/TiO_2、BO_3~(3-)/TiO_2系列固体酸的酸性、结构和晶相的研究

制备了ＳＯ４２－／ＴｉＯ２（Ⅰ）、ＰＯ４３－／ＴｉＯ２（Ⅱ）、ＢＯ３３－／ＴｉＯ２（Ⅲ）系列固体酸。用ＩＲ、Ｒａｍａｎ光谱对该系列固体酸进行结构表征,结果表明ＳＯ４２－与ＴｉＯ２表面的结合为螯合式双配位结构和共价硫酸盐共存,ＰＯ４３－与ＴｉＯ２表面的结合为桥式三配位结构,ＢＯ３３－与ＴｉＯ２表面的结合为单齿单配位结构和螯桥混合式三配位结构共存。用由溶液中正丁胺的吸附等温线测定固体表面酸度的方法测定了样品的酸量,结果表明酸量大小为Ⅰ＞Ⅱ＞Ⅲ。用ＸＲＤ技术对该系列固体酸进行考察,衍射图分析提示该系列固体酸主要都为锐钛矿型晶型,但Ⅰ、Ⅱ、Ⅲ中又各自夹杂其它不同的晶型     

Emerging polymorphism in nanostructured TiO2: Quantum chemical comparison of anatase,rutile, and brookite clusters

Density functional theory (DFT) and time‐dependent DFT calculations have been performed on a set of 34 titanium dioxide clusters ((TiO2)_n with n ≤ 125) to investigate structural and electronic properties of nanostructured TiO₂ (nano‐TiO₂) materials. The investigated clusters include models of the three low‐energy polymorphic forms of TiO₂ anatase, rutile, and brookite. A systematic comparison of clusters of increasing size show clear trends for emerging bulk properties in the investigated systems as the surface‐to‐bulk ratio changes from small clusters dominated by undercoordinated surface atoms to more realistic model nanocrystals with significant bulk components. Differences and similarities in terms of atomic coordination, structural stability, and electronic properties for the three different polymorphic forms of nano‐TiO₂ are discussed. The calculations provide evidence for emerging polymorphism with increasing cluster sizes so that the different TiO₂ forms can be clearly distinguished based on structural characteristics associated with the local bonding environment of the constituent atoms. © 2013 Wiley Periodicals, Inc.     

YFeO3/TiO2异质结材料的制备及其光催化性能研究

通过研磨-焙烧法制备了YFeO3/TiO2异质结材料,考察了焙烧温度和组分质量含量变化对合成异质结材料的影响;进行了X射线衍射(XRD)、傅里叶红外(FRIR)、紫外-可见漫反射(UV-vis/DRS)、光电子能谱(XPS)等表征并测试了不同样品光催化降解橙黄Ⅱ的活性.结果表明,YFeO3/TiO2复合氧化物不仅具有明显的可见光光响应,而且表现出比单组分相对较高的光催化降解活性.最佳的复合样品为600℃焙烧下,w(TiO2)=0.9的复合样品.复合材料光催化活性的提高可归因于p-YFeO3与n-TiO2间存在的p-n结.