Transition of TiO_2 in TiO_2/Vermiculite Nanocomposites

The TiO2/vermiculite composites were prepared by in-situ hydrolyzing reaction and in-situ dehydrating reaction of tetrabutyl titanate-hexadecyl trimethyl ammonium bromide intercalated vermiculite. The structural phase transition of TiO2 in TiO2/vermiculite composites calcined at different temperatures was characterized by using XRD and Raman. The results show that at calcination temperature of 800℃ appeared the anatase phase of TiO2 in TiO2/vermiculite nanocomposites, while pure TiO2 is all converted to rutile at the same temperature. The average crystal size of TiO2 in TiO2/vermiculite nanocomposites and pure TiO2 both increase with the calcination temperature. The average grain size of TiO2 in TiO2/vermiculite nanocomposites is less than that of pure TiO2 at the same calcination temperature. The results also show that the silicon-oxygen structure in layered vermiculite structure can effectively depress the phase transformation from anatase to rutile, thus enhancing the transition temperature and inhibitting the growth of anatase crystals.     

微波处理TiO2柱撑蒙脱石的光催化性能

采用微波处理方法合成了TiO2结晶体柱撑蒙脱石光催化材料,采用XRD、BET吸附和降解甲基橙实验分析了柱撑蒙脱石的结构、锐钛矿金红石晶相比例、比表面积和光催化性能。结果证实,微波功率与辐照时间等条件将影响材料的结构与性能;与传统加热方式比较,微波处理可获得锐钛矿相含量高的混晶TiO2;该TiO2柱撑蒙脱石具备优异的光催化性能。     

金刚石表面沉积二氧化钛薄膜研究

用均一沉淀法在金刚石表面沉积二氧化钛 ,探讨了沉积工艺条件。覆层在高温和真空条件下被还原为单质金属钛 ,X射线衍射分析表明金刚石表面有钛和碳化钛生成。     

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.     

利用天然矿物承载TiO2制备光催化功能材料的研究

利用天然沸石、膨润土作载体制备的TiO2 /矿物复合体光催化材料 ,在阳光照射下对有机染料罗丹明 -B具分解脱色性能。实验证实未经高温处理的样品光催化性能优于经高温处理的 ,沸石的脱色率 6小时达 10 0 %,膨润土的脱色率达 94 %。晶相分析和热分析证实锐钛矿在有沸石、膨润土存在的水相体系中可直接在矿物表面生成 ,结合牢固 ,同时引起矿物结构的调整。     

蒙脱石热处理产物的微结构变化研究

本文对广东和平蒙脱石及其热处理产物进行了化学分析、差热和热重分析、X射线粉末衍射分析、红外吸收光谱分析、扫描电镜、原子力显微镜及魔角旋转核磁共振等研究。结果表明,蒙脱石在热处理温度为126℃-148℃时,主要脱出吸附水和层间水,这一脱水过程是可逆的。当热处理温度达到659℃时,蒙脱石八面体片中的羟基开始脱失,但层状结构仍然保持,这种羟基的脱失过程对应着八面体片中Al^Ⅵ向Al^Ⅳ的转变。当温度达到900℃时,蒙脱石的层状结构完全被破坏,并有新的矿物相μ-堇青石产生。当温度为1200℃时,则出现方英石及莫来石相。当热处理温度达到1350℃时,方英石及莫来石的含量略有减少,并出现较多的含铁堇青石相。     

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。     

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.     

制备方法对纳米TiO2介孔柱撑蒙脱石结构和性能的影响

分别通过离子交换方法和离子交换-水热法制备纳米TiO2介孔柱撑蒙脱石,利用XRD、DSC-TG、N2吸附-脱附等方法对材料进行结构特征与性能的表征。实验结果表明,传统的离子交换方法可使制备的钛柱撑蒙脱石比表面积、孔体积增大;离子交换-水热法可使TiO2介孔柱撑蒙脱石中锐钛矿晶型更好,晶粒变大,柱撑蒙脱石结构更稳定,而且水热的温度越高,所需反应时间越短,锐钛矿的晶型更好,发育更完善。     

掺铜TiO2/膨润土光催化剂的制备及其光催化性能研究

以天然钠基膨润土为载体,利用四氯化钛水解法制备了掺铜TiO₂/膨润土复合光催化剂;比较了不同量Cu²⁺对TiO₂/钠基膨润土的修饰作用及不同光照条件对光催化性能的影响。采用分光光度计、XRD、IR及TG-DTA等测试手段对试验结果进行表征。结果表明,铜的掺入对TiO₂/膨润土光催化活性有显著提高:当掺铜量为原土阳离子交换量的10.9%时,紫外光下催化效果最好;16.4%时太阳光下催化效果最好。复合后样品热处理温度为500 ℃,获得较理想的光催化活性。     

TiO2/电气石复合物的光催化性能

采用溶胶-凝胶法制备TiO2/电气石复合光催化剂,通过光降解甲基橙实验考察复合光催化剂的活性,发现复合物中2%电气石的制备比例就可以显著提升TiO2降解有机物活性,降解率(0.5h)达99.87%,明显优于纯TiO2(0.5h)83.64%,提高了约20%。经XRD、BET、SEM等手段对样品进行分析得知:经800℃以下长时间热处理,电气石的结晶构造不变;900℃热处理使电气石结构破坏。SEM分析显示复合物中TiO2颗粒呈球簇状,均匀包覆在电气石表面形成颗粒膜层。     

蒙脱石层电荷与有机改性蒙脱石凝胶性能关系研究

利用自然沉降法提取了山东两不同产地膨润土中的钙基蒙脱石矿物M1和M2,利用结构式推算法计算了两提纯蒙脱石的层电荷:M1单位半晶胞的层电荷为0.38,M2单位半晶胞的层电荷为0.59;利用十八烷基三甲基氯化铵对蒙脱石进行有机改性,并对有机蒙脱石凝胶性能和层电荷的相关关系进行研究。研究发现:蒙脱石单位半晶胞的层电荷越低,在水中的分散性越好,越有利于十八烷基三甲基铵阳离子的插层,相应有机改性蒙脱石在二甲苯和乙醇体系中的凝胶性能越好(如M1);蒙脱石单位半晶胞的层电荷越高,在水中的分散性越差,越不利于十八烷基三甲基铵阳离子的插层,相应有机改性蒙脱石产品的凝胶性能较差(如M2)。     

热液条件下锐钛矿晶体生长的实验

为了解金属离子生长成为热液矿石矿物的过程和机理,使用氟钛酸钾稀溶液在100 MPa和200~400℃条件下开展了一系列等温不等时和等时变温实验.结果显示该热液条件下形成了不同形貌的锐钛矿.随着反应时间和温度的增加,锐钛矿由几十纳米生长至十几微米;10 h以内的晶体生长速度远高于10 h以后,相对高温下的晶体生长速度则高于低温,表明锐钛矿的热液生长与温度、过饱和程度密切相关.综合来看,粒子成核生长、定向附着和奥氏熟化先后控制了热液锐钛矿的生长,而金属在流体中的过饱和程度和溶解-沉淀过程则决定了其生长速度.因而锐钛矿的形态特征可用于指示其形成的温度、世代关系甚至含氟流体的演化历史.      

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。     

H_2O_2增效TiO_2/凹凸棒石光催化体系降解亚甲基蓝

以钛酸四丁酯为前驱体,天然凹凸棒石为载体,采用溶胶凝胶法制备了TiO_2/凹凸棒石复合光催化剂,并用XRD、TEM对其进行表征.以亚甲基蓝染料为模拟污染物,采用300 W汞灯为紫外光源,以光催化实验来评价该催化剂的活性,并研究了H_2O_2的引入对光催化活性的影响.实验结果表明,H_2O_2能显著提高染料的脱色效率:亚甲基蓝的初始浓度为50 mg/L,催化体系为2 mmol/L H_2O_2+0.5 g/L TiO_2/凹凸棒石+UV(紫外线),光催化10 min后其脱色率为95%,相对于单独的0.5 g/L TiO_2/凹凸棒石+UV催化体系,其脱色率提高了约50%.全波段扫描显示,加入H_2O_2后,亚甲基蓝在290 nm对应的苯环吸收蜂急剧下降,665 nm对应的最大吸收峰则近乎消失,且没有新的吸收峰产生.     

硅烷偶联剂改性TiO2/膨胀石墨复合材料的制备及其光催化性能研究

以硅烷偶联剂黏结剂,利用溶胶-凝胶法将TiO2（P25）负载在膨胀石墨上,利用XRD、EDS以及SEM等分析技术对TiO2/膨胀石墨复合材料进行表征;以橙黄Ⅱ为目标降解物,考察了TiO2/膨胀石墨复合材料光催化性能以及重复使用性能。结果表明：随着TiO2含量的增加,TiO2/膨胀石墨复合材料的光催化效率随之增加,对橙黄Ⅱ的光催化降解符合一级反应动力学方程,TiO2负载量为15%时,反应速率常数为0.387 h-1,高于P25的反应速率常数。TiO2/膨胀石墨复合物使用4次仍保持较高的光催化活性。     

Synthesis and Photocatalytic Activity of Ti-pillared Bentonite

Ti-pillared bentonite has been successfully prepared using a modified method that can induce the transformation of TiO2 pillar from amorphous to anatase phase at a low temperature （150℃）. The value of d0.01 =1.94 nm obtained by Ti-pillared bentonite is larger than that of corresponding raw clay （1.56 nm）. Due to large numbers of Ti-pillars formed, the Ti-pillared bentonite shows an excellent ability in adsorbing Rhodamine B （RB）. The photocatalytic activity and kinetic equation are investigated by decomposing RB solution under the UV irradiation. It is found that the Ti- pillared bentonite shows super photocatalytic activity for the degradation of RB solution compared with the untreated bentonite and pure TiO2, and the kinetic equation of the degradation of RB solution is a 1.5-oder equation.     

Discrimination of TiO<Subscript>2</Subscript> polymorphs in sedimentary and metamorphic rocks

Investigation by Raman spectroscopy of samples from different geological settings shows that the occurrence of TiO₂ polymorphs other than rutile can hardly be predicted, and furthermore, the occurrence of anatase is more widespread than previously thought. Metamorphic pressure and temperature, together with whole rock chemistry, control the occurrence of anatase, whereas variation of mineral assemblage characteristics and/or fluid occurrence or composition takes influence on anatase trace element characteristics and re-equilibration of relict rutiles. Evaluation of trace element contents obtained by electron microprobe in anatase, brookite, and rutile shows that these vary significantly between the three TiO₂ phases. Therefore, on the one hand, an appropriation to source rock type according to Nb and Cr contents, but as well application of thermometry on the basis of Zr contents, would lead to erroneous results if no phase specification is done beforehand. For the elements Cr, V, Fe, and Nb, variation between the polymorphs is systematic and can be used for discrimination on the basis of a linear discriminant analysis. Using phase group means and coefficients of linear discriminants obtained from a compilation of analyses from samples with well-defined phase information together with prior probabilities of groupings from a natural sample compilation, one is able to calculate phase grouping probabilities of any TiO₂ analysis containing at least the critical elements Cr, V, Fe, and Nb. An application of this calculation shows that for the appropriation to the phase rutile, a correct-classification rate of 99.5% is obtained. Hence, phase specification by trace elements proves to be a valuable tool besides Raman spectroscopy.     

Absorption and Photocatalytic Degradation of Machine Oil by Exfoliated Graphite-Supported Nanometer TiO2 Material

By loading nanometer anatase onto exfoliated graphite with the sol-gel method, exfoliated graphite-TiO2 composite （EG-TiO2） can be prepared, which can adsorb oil and can also degrade oil. In a technologic condition for preparing EG-TiO2, the impregnated number of times is the most important factor to influence oil-adsorbing capability, that is, when the impregnated number of times increases, the amount of saturation-adsorbed oil decreases. The study of EG-TiO2 photocatalytic degradation of machine oil based on the weight-loss method and infrared spectrum method indicates that EG-TiO2 has obvious effect of photocatalytic degradation for machine oil. Its performance is superior to pure nanometer TiO2 powder because nanometer TiO2 in EG-TiO2 has three-dimension laminar structure and comparatively high adsorption capability.     

水热法合成黄铁矿微观形貌和结构的观测与表征

模拟热液型金矿床中黄铁矿生成的地质条件,采用硫酸亚铁(FeSO4)和硫代乙酰胺(CH3CSNH2)为铁源和硫源,在Fe/S比为1∶3、温度180~200 ℃、加热时间24 h条件下考察黄铁矿的结晶情况。用SEM扫描电镜观察在不同水热条件下合成黄铁矿的形态及成分;用多晶X射线衍射仪(XRD)确定了产物物相组成;用透射电子显微镜(TEM)观测表征了黄铁矿晶体的形态和结构。结果表明：在200 ℃时黄铁矿为粒状,粒度较均匀,粒径1 μm左右。在180 ℃时黄铁矿除有尺寸在1 μm左右粒状黄铁矿外,还有不规则带状黄铁矿晶体,带宽为200 nm左右。认为水热条件中,随着结晶温度的逐步升高,黄铁矿的形貌逐步由不规则形状向规则形状的转变。所以在实验温度较高阶段,形成规则的粒状形貌;在低温阶段,则会出现不规则带状形貌。