Sonocatalytic degradation of some dyestuffs and comparison of catalytic activities of nano-sized TiO2, nano-sized ZnO and composite TiO2/ZnO powders under ultrasonic irradiation

Here, a novel sonocatalyst, composite TiO2/ZnO powder, was prepared through the combination of nano-sized TiO2 and ZnO powders. Because of the appropriate adsorbability to organic pollutants and special crystal interphase between TiO2 and ZnO particles, the composite TiO2/ZnO powder exhibits a high sonocatalytic activity under ultrasonic irradiation during the degradation of acid red B. Especially, the sonocatalytic activity of composite TiO2/ZnO powder with 4:1 molar proportion treated at 500 degrees C for 50 min showed obvious improvement compared with pure nano-sized TiO2 and ZnO powders. When the experimental conditions such as 10mg/L acid red B concentration, 1.0 g/L catalyst addition amount, pH=7.0, 20 degrees C system temperature, 100 min ultrasonic time and 50 mL total volume were adopted, the satisfactory degradation ratio and rate were obtained. All experiments indicate that the sonocatalytic method using composite TiO2/ZnO powder may be a more advisable choice for the treatments of non- or low-transparent organic wastewaters in future.     

Ultrasonic-assisted sol-gel method of preparation of TiO2 nano-particles: characterization, properties and 4-chlorophenol removal application

Nano-size TiO2 photocatalysts were prepared by sol-gel and ultrasonic-assisted sol-gel methods using two different sources of ultrasonicator, i.e., a bath type and tip type. The physicochemical characteristics of the catalysts were investigated by BET, XRD and TEM analyses and the photocatalytic properties of the TiO2 catalysts prepared by three different methods were compared. The intrinsic and extrinsic properties of TiO2, such as the particle size, surface area, pore-volume, pore-diameter, crystallinity as well as anatase, rutile and brookite phase ratios, could be controlled by the ultrasonic-assisted sol-gel method. During this preparation method, the effect of such important operating variables as the ultrasonic irradiation time, power density, the ultrasonic sources (bath-type and tip-type), magnetic stirring during synthesis, initial temperatures and size of the reactors are discussed here. It was found that each of the parameters played a significant role in controlling the properties of the TiO2 nano-particles. Among the three different methods, TiO2 photocatalysts prepared by ultrasonic (tip-US) assisted sol-gel possessed the smallest particle size, highest surface area and highest pore-volume than the catalysts prepared by the other two methods. 4-Chlorophenol was used as a pollutant to observe the photocatalytic degradation ability of the prepared photocatalysts and the TiO2 catalysts prepared by the bath-US ultrasonic-assisted sol-gel method were shown to be the most highly active. This is due to their high surface area and high pore-diameter. This study clearly demonstrates the importance and advantages of ultrasonication in the modification and improvement of the photocatalytic properties of mesoporous nano-size TiO2 particles.     

(Fe,N)共掺杂TiO2红外光谱的电负性原理研究

采用电负性原理,构建合理的红外光谱模型,对TiO2红外光谱的振动频率与元素电负性之间的各种经验关系进行探究.采用溶胶-凝胶法制备(Fe,N)共掺杂TiO2,利用X-射线衍射(XRD)、傅里叶红外光谱(FTIR)对样品的物相和红外光谱进行了表征.XRD物相分析表明当煅烧温度为600 ℃时,TiO2样品中的无定形结构己基本转化为锐钛矿型结构.随着煅烧温度升高,TiO2的X射线衍射峰逐渐由宽变窄,衍射强度由弱变强.当煅烧温度为700 ℃时,锐钛矿型的衍射峰基本消失,取而代之的是金红石相的衍射峰,但TiO2的主晶相并没有发生改变.红外光谱分析表明(Fe,N)共掺杂TiO2在650~500 cm-1区间有一个较宽的吸收峰.电负性模拟计算了(Fe,N)共掺杂TiO2红外光谱的伸缩振动频率,获得了Fe、N掺杂的位置、分子结构和键价特征:首先计算出约化质量μ,然后按照经典力学伸缩力常数k与频率V之间满足的关系,结合力常数与电负性关系、键级的计算方法,计算了基本单元都是氧八面体的掺杂金红石、锐钛矿TiO2的分子振动频率.结果表明:通过电负性理论计算的(Fe,N)共掺杂的TiO2的红外光谱与实验测量的红外光谱的伸缩振动频率比较吻合.     

聚(2-甲氧基-5-辛氧基)对苯乙炔/TiO2纳米复合材料的光物理性能研究

通过原位强碱诱导下的脱氯化氢缩合聚合法制备了一系列不同纳米TiO2含量的聚(2-甲氧基-5-辛氧基)对苯乙炔/纳米二氧化钛(PMOCOPV/TiO2)光电复合材料。红外光谱和拉曼光谱证实了在纳米TiO2表面的包覆层为PMOCOPV。紫外-可见吸收光谱表明随着TiO2含量的增加PMOCOPV/TiO2纳米复合材料的吸收强度提高。高分辨透射电镜观察发现PMOCOPV/TiO2是具有核-壳结构的纳米复合粒子,直径约30 nm,其中PMOCOPV包覆层的厚度约为8~10 nm。荧光光谱研究表明,PMOCOPV/TiO2纳米复合材料的最大发射波长随着TiO2含量的增加发生红移,荧光寿命约为1 ns,且随着TiO2含量的增加荧光强度和荧光寿命得到显著提高,并通过PMOCOPV/TiO2纳米复合材料中的激子离化和电荷传输过程以及复合材料中的电势能级探讨了PMOCOPV/TiO2的荧光量子效率和荧光强度增加的机理。     

反胶束软模板法合成PANI/TiO2纳米棒复合材料及其性能研究

以阳离子表面活性剂十六烷基三甲基溴化胺(CTAB)形成的反胶束为模板,制备了一系列不同纳米TiO2含量的PANI/TiI2纳米复合材料.利用FTIR,UV-Vis,TG,TEM和荧光光谱等方法对产物进行了结构表征和性能研究.探讨了反胶束体系中PANI/TiO2复合纳米棒形成的自组装机理.结果表明:复合材料主要为直径30～40 nm,长约400 nm的PANI/TiO2复合纳米棒,二氧化钛纳米粒子与聚苯胺大分子之间存在强的相互作用,并对复合材料的热稳定性起到提高作用,PANI/TiO2纳米复合材料在紫外和可见光区域均有吸收,并在416 nm处激发产生荧光,荧光强度随着掺杂TiO2含量的提高得到了较大的增强.通过PANI/TiO2纳米棒复合材料中的激子离化和电荷传输过程探讨了PANI/TiO2的荧光量子效率和荧光强度增加的机理.     

Mn-N共掺杂TiO2电子结构和光学性质的第一性原理计算

本文采用第一性原理研究了Mn、N掺杂TiO2和Mn-N共掺杂TiO2的能带结构、态密度和Mn-N共掺TiO2对体系介电函数与吸收谱的影响.研究结果表明,Mn掺杂TiO2的能带结构的禁带内出现的杂质能级是由Mn 的3d轨道贡献;N掺杂TiO2在费米能级处的杂质能级则由O 2p, Ti 3d和N 2p轨道杂化形成; Mn-N共掺的TiO2能带在费米能级处的杂质能级则由O 2p, Ti 和Mn的3d以及N 2p轨道杂化形成; 对于介电函数,在低能区间(<2.5 eV),理想TiO2无介电峰, Mn-N共掺体系则出现了两个介电峰,原因在于Mn 3d态和N 2p态使介电峰值向低能区移动;同时,与理想TiO2的吸收谱相比,最大的变化是在可见光区出现了一个吸收峰,且在可见光区的响应的范围变宽.     

Mn-N共掺杂TiO_2电子结构和光学性质的第一性原理计算

本文采用第一性原理研究了Mn、N掺杂TiO_2和Mn-N共掺杂TiO_2的能带结构、态密度和Mn-N共掺TiO_2对体系介电函数与吸收谱的影响.研究结果表明,Mn掺杂TiO_2的能带结构的禁带内出现的杂质能级是由Mn的3d轨道贡献;N掺杂TiO_2在费米能级处的杂质能级则由O 2p,Ti 3d和N 2p轨道杂化形成;Mn-N共掺的TiO_2能带在费米能级处的杂质能级则由O 2p,Ti和Mn的3d以及N 2p轨道杂化形成;对于介电函数,在低能区间(2.5 e V),理想TiO_2无介电峰,Mn-N共掺体系则出现了两个介电峰,原因在于Mn 3d态和N 2p态使介电峰值向低能区移动;同时,与理想TiO_2的吸收谱相比,最大的变化是在可见光区出现了一个吸收峰,且在可见光区的响应的范围变宽.     

退火对TiO2薄膜形貌、结构及光学特性影响

利用射频磁控溅射技术在熔融石英基片上制备TiO<,2>薄膜,采用X射线衍射、扫描电子显微镜(SEM)、拉曼光谱以及透过谱研究了退火温度和退火气氛对TiO<,2>薄膜的结构、形貌和光学特性的影响.实验结果表明:在大气环境下退火,退火温度越.高,薄膜晶化越好,晶粒明显长大,温度高于700℃退火的薄膜,金红石相已明显形成.实验还发现,退火气氛对金红石相的形成是非常重要的,拉曼光谱反应出Ar气氛退火,抑制了金红石晶相的发育,薄膜仍以锐钛矿相为主.Ar气氛退火的薄膜在可见光范围内的透过率比大气退火的要低,并且由透过率曲线推知:金红石的光学带隙约为2.8 eV,比锐钛矿的光学带隙小0.2 eV.     

金属离子掺杂对TiO2/白云母纳米复合材料中TiO2的颗粒形态及相组成的影响

采用化学液相沉积法制备了系列未掺杂和掺杂不同金属离子的TiO2白云母纳米复合材料.利用扫描电子显微镜(SEM),x射线衍射(XRD)对其TiO2薄膜的TiO2颗粒形态和相组成进行了详细研究.结果表明,TiO2颗粒在15—50nm之间;除球形颗粒外,掺杂Mn2+,Zn2+的样品中还出现有金红石柱状颗粒.TiO2薄膜中相组成以锐钛矿、金红石共存为特征;掺杂金属离子对TiO2相组成的影响取决于金属离子的离子半径、电荷及配位体特征. 关键词： 金属离子掺杂 TiO2 颗粒形态 相组成     

二氧化钛胶体及其自组装薄膜的光谱分析

水解钛酸四丁酯制备了二氧化钛胶体;采用静电自组装技术制备了聚电解质与二氧化钛胶体的复合薄膜;采用吸收光谱和荧光光谱对二氧化钛胶体及其复合薄膜进行了表征。吸收光谱显示,胶体的吸收带边蓝移,显示出量子尺寸效应,胶体的荧光光谱出现了多个发光带,最短发光波长位于371nm,发光主要集中在蓝光区域内;在252nm光源激发下。复合薄膜的发射谱带具有二氧化钛水溶胶的发射谱带的特征,荧光发射主要来源于二氧化钛,聚电解质的引入对复合薄膜的光致发光特性有一定影响。     

Sonocatalytic degradation of methyl orange in the presence of TiO2 catalysts and catalytic activity comparison of rutile and anatase

Rutile and anatase titanium dioxide (TiO(2)) powders were used as sonocatalysts for the degradation of methyl orange which was used as a model compound. Ultrasound was used as an irradiation source. It was found that the sonocatalytic degradation ratios of methyl orange in the presence of TiO(2) powder were much better than ones without any TiO(2), but the sonocatalytic activity of rutile TiO(2) particles was obviously higher than that of anatase TiO(2) particles. Although there are many factors influencing sonocatalytic degradation of methyl orange, the experimental results show that the best degradation ratio of methyl orange can be obtained when the experimental conditions of the initial methyl orange concentration of 10 mg/l, rutile TiO(2) added amount of 500 mg/l, ultrasonic frequency of 40 kHz, output power of 50 W, pH=3.0 and 40 degrees C within 150 min were adopted. In addition, the catalytic activity of reused rutile TiO(2) catalyst was also studied and found to be better than new rutile TiO(2) catalyst sometimes. All experimental results indicated that the method of the sonocatalytic degradation of organic pollutants in the presence of TiO(2) powder was an advisable choice for treating non- or low-transparent organic wastewaters.     

Mn2+/H2O2光催化体系对染料甲基橙、茜素红、结晶紫的降解研究

研究了锰与过氧化氢组成的催化体系在二氧化钛、光的作用下与染料甲基橙、茜素红、结晶紫的脱色和降解反应，结果表明，Mn^2 /H2O2体系在pH8-9,二氧化钛存在下，用日光和紫外光分别照射时对三种染料的脱色和降解作用明显，脱色率达到80％以上。还研究了Mn^2 /TiO2/H2O2/UV（紫外光）体系的动力学，为动力学一级反应。     

基于FTIR与UV-Vis的Ce-La/TiO_2光-湿-热复合材料制备机理

为获得具有调温调湿且能够进行光催化降解有害物质的多功能复合材料,利用溶胶-凝胶法制备Ce-La/TiO_2空心微球,以Ce-La/TiO_2空心微球为载体材料,采用真空吸附法将相变材料——癸酸-棕榈酸填充在Ce-La/TiO_2空心微球的空腔中制备具有光-湿-热协同性能的Ce-La/TiO_2复合材料。采用傅里叶红外光谱仪(FTIR)对制备过程中主要阶段的产物进行测试,研究SiO2模板的构建作用,表面活性剂聚乙烯吡咯烷酮(PVP)的衔接作用,癸酸-棕榈酸的嵌入对Ce-La/TiO_2空心微球的影响,利用紫外-可见分光光谱仪(UV-Vis)对Ce-La/TiO_2复合材料的光响应范围进行测试,研究Ce-La共掺杂对TiO_2空心微球光响应能力的影响,采用扫描电镜(SEM)对Ce-La/TiO_2复合材料的微观形貌进行表征分析,进一步阐明Ce-La/TiO_2复合材料制备机理。结果表明,氨水提供的碱环境有利于正硅酸乙酯缩合反应,在780.00cm-1处生成Si—O—Si基团,搭建SiO2网络骨架,形成内核,作为支撑TiO_2壁材的模板,构建TiO_2的空腔结构;表面活性剂PVP的添加,在1 035.00cm-1处形成—C—N—基团,有利于TiO_2附着在SiO2的表面;高温煅烧能够有效去除PVP避免杂质离子引入到Ce-La/TiO_2复合材料体系中。Ce-La共掺杂使Ce-La/TiO_2复合材料的吸收边带发生红移,提高在可见光下的催化降解能力,同时在1 630.00cm-1处出现—OH基团能够提高CeLa/TiO_2复合材料的亲水性。癸酸-棕榈酸较好的填充于Ce-La/TiO_2空心微球的空腔中,各组分的特征吸收峰没有发生明显变化,能够保持各组分的基本性能不变。     

镍锰共掺杂TiO2的制备及其光催化性能研究

采用溶胶-凝胶的方法,镍、锰离子在钛酸丁酯[Ti(OBu)4]水解的条件下掺杂到TiO2中,合成了不同摩尔比的镍、锰离子共掺杂的TiO2光催化剂.通过光催化降解甲基橙实验,对所制备光催化剂的光催化活性进行了考察.结果表明掺杂后的TiO2光催化剂在可见光下对甲基橙能有效地降解,表现出了较好的光催化活性,当镍、锰离子掺杂量...     

制备温度对TiO2基膜表面非晶态ZnO薄膜发光特性影响的研究

利用电子束热蒸发镀膜的方式，以高纯度的ZnO和TiO₂颗粒为原料，以Si为基底在有氧的气氛中制备ZnO/TiO₂复合薄膜。研究制备温度对ZnO/TiO₂薄膜的结构以及发光性能的影响。通过拉曼(Raman)谱和X射线衍射(XRD)谱分析了ZnO/TiO₂薄膜的结构，表明所制备的ZnO薄膜为非晶态。用光致发光 (PL) 谱表征了它的发光特性，数据表明在250℃时制备的非晶态ZnO薄膜在波长389nm处具有极强的紫外光发射，在波长431nm处发出很强的紫光，在波长519nm处发出较强的黄绿光。     

二氧化钛薄膜的制备及退火对其形貌、结构的影响

利用磁控溅射技术,在石英基片上沉积Ti膜,分别在400、600、700、900℃的大气中退火获得TiO2薄膜。采用这种制备方式获得的TiO2薄膜呈现不同的颜色,退火温度为400℃的样品为暗紫红色,600℃时为黑色,而在700℃和900℃时均为黄色。采用X射线衍射、扫描电子显微镜（SEM）以及Raman光谱等手段研究了退火温度对TiO2薄膜的结构和形貌的影响。结果表明：退火温度为400℃时,TiO2薄膜为锐钛矿相,温度升高至600℃时,几乎转变为金红石晶相,但仍存在微量锐钛矿相,温度升高至700℃以上,则完全转变为金红石晶相。由XRD衍射图可知退火温度为700℃和900℃时,薄膜的金红石相沿（101）晶面择优取向。     

Ag/TiO2纳米材料的制备和光致变色性能研究

 采用光催化还原法在不同温度热处理的TiO2薄膜表面沉积Ag纳米颗粒,制备了Ag/TiO2纳米薄膜材料。通过UV-Vis吸收光谱表征对比了不同温度热处理的TiO2对Ag粒子光催化沉积的影响,发现500℃退火处理TiO2薄膜较利于Ag纳米粒子的光催化沉积;在650 nm红色激光照射下,500℃退火处理的Ag/TiO2样品具有明显的光致变色现象,对此变色过程中涉及的机理进行了讨论,且发现随着Ag纳米颗粒光催化沉积时间的增长,Ag/TiO2薄膜光致变色的响应速率提高,但Ag纳米颗粒过多会抑制Ag/TiO2薄膜的变色响应速率。     

Investigation on the sonocatalytic degradation of acid red B in the presence of nanometer TiO2 catalysts and comparison of catalytic activities of anatase and rutile TiO2 powders

Here, the nanometer anatase and rutile titanium dioxide (TiO(2)) powders were introduced to act as the sonocatalysts during the ultrasonic degradation of azo dye-acid red B which was chosen as model compound. The ultrasound of low power was used as an irradiation source to induce TiO(2) particles performing catalytic activity. It was found that the processes of sonocatalytic degradation were different between nanometer anatase TiO(2) and nanometer rutile TiO(2). For nanometer anatase TiO(2) catalyst, the acid red B was mainly oxidated by the holes on the surface of nanometer anatase TiO(2) particles, so that the decolorization and degradation happened at the same time. For the nanometer rutile TiO(2) catalyst, the acid red B was mainly oxidated by the *OH radicals from the ultrasonic cavitation, so that the decolorization of azo bond takes place primarily, and then the degradation of naphthyl ring does. The intermediates of acid red B in the presence of nanometer anatase and rutile TiO(2) powders have been monitored by UV-vis spectra and high performance liquid chromatography (HPLC), respectively. All experiments indicated that the degradation effect of acid red B in the presence of nanometer anatase TiO(2) powder was obviously better than that in the presence of nanometer rutile TiO(2) powder. Hence, the method of sonocatalytic degradation for organic pollutants in the presence of nanometer anatase TiO(2) powder is expected to be promising as an advisable choice for the treatment of organic wastewaters in future.     

Ag负载WO3/TiO2光催化剂的合成及其催化性能

以钛酸丁酯、无水乙醇、钨酸铵为原料,采用溶胶-凝胶法合成了WO3/TiO2复合光催化剂;采用光还原技术制备了Ag负载WO3/TiO2光催化剂,借助X射线粉末衍射(XRD)和UV-Vis光谱等技术对样品的组成和光吸收性能进行了表征,并以罗丹明B为模型污染物考察样品的光催化活性。XRD分析表明,所得粉体均为锐钛矿型纳米TiO2,且与WO3复合后,纳米TiO2特征衍射峰宽化,强度降低;UV-Vis光谱分析表明,载银使得催化剂在400—700nm的可见光区域对光响应,且在紫外光区吸收显著增强,对光具有更高的利用率;以罗丹明B为降解物的光催化实验表明,WO3复合对纳米TiO2光催化活性有显著的影响,而载Ag后其光催化活性进一步提高,将该光催化剂用于炼油厂废水的处理,效果较好。     

TiO2/SnO2复合氧化物的制备和光谱特性

为了研究TiO2/SnO2复合氧化物的光学特性,用胶体化学方法制备了以SnO2为内核的TiO2/SnO2复合氧化物,并且用紫外-可见光吸收光谱、X射线衍射和红外光谱对TiO2/SnO2复合氧化物的特性进行了分析.结果显示TiO2和TiO2/SnO2的能带宽度分别为4.13和3.86 eV,表现出量子尺寸效应;TiO2/SnO2在紫外区域具有宽的强吸收带.X射线衍射中TiO2的(110)衍射峰的位置移动了1.6°,强度也发生了变化;与TiO2红外光谱相比,TiO2/SnO2中Ti-O键的伸缩振动由500cm-1移到了656 cm-1,并有560 cm-1的肩峰,与吸附水相应的1650 cm-1附近的吸收峰和3420 cm-1的吸收峰均有所增加.