SO_4~(2-)/ZrO_2型固体超强酸改性及其催化氧化脱除噻吩类硫化物

通过掺杂不同金属元素对SO_4~(2-)/ZrO_2型固体超强酸进行改性,应用共沉淀法制备了一系列固体酸催化剂SO_4~(2-)/ZrO_2、SO_4~(2-)/ZrO_2-ZnO、SO_4~(2-)/ZrO_2-Fe_2O_3、SO_4~(2-)/ZrO_2-CuO、SO_4~(2-)/ZrO_2-Al_2O_3,利用氧气作氧化剂进行催化氧化脱除噻吩硫化物动力学实验.研究结果表明,掺杂了Zn、Fe和Cu的SO_4~(2-)/ZrO_22型催化剂催化氧化效果较SO_4~(2-)/ZrO_2都有明显提高,其中添加了金属Zn的SO_4~(2-)/ZrO_2-ZnO催化氧化效果最好,在反应温度为50℃,能达到100%的脱硫率.对合成的系列固体酸进行了X射线衍射(XRD)、氨程序升温脱附(NH3-TPD)的表征,结果表明,催化剂样品中四方相ZrO_2的含量越高,表面酸含量越大,其催化氧化噻吩硫化物的活性越高.     

稀土固体超强酸SO_4~(2-)/TiO_2-Ce~(4 )直接法催化合成聚乳酸及其机理的研究

对稀土固体超强酸SO_4~(2-)/TiO_2-Ce~(4 )催化剂直接法催化合成聚乳酸反应机理进行了研究,实验结果表明:SO_4~(2-)/TiO_2-Ce~(4 )直接法催化剂合成聚乳酸的聚合机理是酸性聚合,酸性越强所合成聚乳酸的分子量越高。     

固体超强酸S2O82-/ZrO2-Fe2O3催化合成乙酸异戊酯

通过沉淀-浸渍法合成固体超强酸S2O82-/ZrO2-Fe2O3催化剂,并将其应用于催化合成乙酸异戊酯。用XRD、IR和化学分析等手段对催化剂进行了表征,研究了焙烧温度对其酸性、结构和催化性能的影响。实验结果表明:当n(Zr)∶n(Fe)=1∶0.1,焙烧温度为550℃时,酯化率最高。     

Ce-SO42-/TiO2固体超强酸光催化剂降解茜素红染料催化活性的研究

对SO24-/TiO2固体超强酸光催化剂进行了铈掺杂改性。在铈掺杂情况下,采用沉淀浸渍法,对不同浓度硫酸浸渍液和不同温度焙烧前驱体对催化剂的影响进行了分析。在最佳浓度和最适焙烧温度下,制备了不同铈掺杂量的催化剂,成功的用于10mg/L茜素红溶液降色处理。使其在超过SO24-/TiO2固体超强酸光催化剂降色效果的条件下重复使用,确定了使用次数在铈掺杂为2‰最多。     

第一性原理研究α-Al2O3的电子结构、力学性质和德拜温度

采用基于密度泛函理论的平面波超软赝势的第一性原理方法,利用CASTEP软件计算了α-Al_2O_3的电子结构、力学性质和德拜温度。计算结果显示优化后的晶格常数与实验数据基本一致。能带结构图表明α-Al_2O_3具有典型的离子化合物特征,禁带宽度为5.964eV。计算的态密度表明α-Al_2O_3的下价带在-19.426~-15.370eV之间,态密度主要由O的2s轨道电子贡献;上价带在-7.178~0.711eV之间,态密度主要由O的2p轨道电子贡献;导带在5.698~14.977eV之间,态密度主要由Al的3s和3p轨道电子贡献。差分电荷密度分布表明α-Al_2O_3中存在离子键和共价键。力学性质的计算结果表明α-Al_2O_3的体积模量为224.885GPa,剪切模量为144.687GPa,弹性模量为357.411GPa,泊松比为0.235,各向异性指数为0.220;α-Al_2O_3剪切模量与体积模量的比值为0.643,表明α-Al_2O_3具有脆性。α-Al_2O_3的德拜温度为974.834K。     

激光熔覆法制备Al2O3-TiO2涂层的显微组织与性能研究

采用预置粉末式激光熔覆法在钛合金(Ti-6Al-4V)表面开展了Al_2O_3-13%(质量分数)TiO_2涂层的研究。利用光学显微镜(OM)、扫描电子显微镜(SEM)、X射线衍射分析仪(XRD)和显微硬度计研究了激光熔覆熔池的特征和涂层的显微结构,分析了涂层的成分分布、相组成和显微硬度分布情况。预置粉末激光熔覆制备的Al_2O_3-13%(质量分数)TiO_2涂层界面结合良好,涂层组织均匀,没有明显的裂纹和气孔。激光熔覆涂层表现出明显流线型特征,熔覆层截面分为热影响区、扩散结合区和涂层区。涂层由Ti、AlTi_3、α-Al_2O_3和γ-Al_2O_3等相组成。涂层的显微硬度达到1000~1300HV_(0.3),比基体硬度360~390HV_(0.3)高2倍。     

SO42-/ZrO2固体酸的超声快速制备及表征

在沉淀和浸渍过程中都分别施加超声波快速制备了SO42-/ZrO2固体酸。利用XRD、FT-IR、TG-DTA、BET和NH3-TPD等方法对样品进行分析表征,探讨超声作用对固体酸中ZrO2晶粒粒径、样品比表面积、热稳定性和酸性等的影响。结果表明,超声制备SO42-/ZrO2形成超强酸结构的适宜焙烧温度为550℃。与常规法相比,超声波的引入能获得较小晶粒的ZrO2,并强化了浸渍过程中与高价硫的结合,所得样品比表面积增大,并可以提高催化剂的酸强度以及改变催化剂酸量分布。     

La改性固体超强酸S_2O_8~(2-)/ZrO_2-Al_2O_3的制备及催化性能研究

采用共沉淀-浸渍法制备了固体超强酸S2O82-/ZrO2-Al2O3催化剂,并加入La对催化剂进行改性。以柠檬酸三丁酯的合成为探针反应评价催化剂的活性,并通过红外光谱、X射线衍射、NH3程序升温脱附等方法对催化剂进行表征,考察制备条件及La的引入对催化剂结构和性能的影响。结果表明:(NH4)2S2O8溶液浸渍浓度为0.5mol/L,锆铝氧化物物质的量比为1∶1,600℃焙烧4h后于1%(质量分数)的La(NO3)3溶液浸渍所得的催化剂活性较好,柠檬酸的转化率可达93.69%。La的引入可以提高催化剂对S2O82-的结合能力,抑制活性组分的分解,增加催化剂的酸强度和酸总量,提高催化剂的活性。     

MxOy-Al2O3复合氧化物在生物质油催化裂化中的催化性能

采用共沉淀法制备复合氧化物MxOy-Al2O3(MxOy=CeO_2,ZrO_2,SiO_2,TiO_2)催化剂,同时用XRD、SEM、TPD和FT-IR等对复合氧化物的晶相结构、酸种类、酸量以及热稳定性等进行了表征。结果表明,复合氧化物MxOy-Al2O3对生物质油具有较好的催化裂化的反应活性,其中ZrO_2-Al_2O_3有较好的裂化反应活性和选择性,裂化反应产物分布中相对分子量小于100的占70.72%;SiO2-Al2O3表现出较好的脱氧率,裂解油中含氧率为17.72%,比原料油下降了24.29%,而CeO_2-Al_2O_3催化剂具有较好的抗结焦能力。     

单分散γ-Al_2O_3纳米颗粒制备工艺参数的调控

采用均相沉淀法,在950℃煅烧碱式硫酸铝(Al(SO_4)_x(OH)_y)纳米颗粒2h,制备出单分散的γ-Al_2O_3纳米颗粒。研究了阴离子、浓度和沉淀剂/铝盐摩尔比对Al(SO_4)_x(OH)_y颗粒的形貌、尺寸和分散性的影响。结果表明,Al(SO_4)_x(OH)_y颗粒的最佳制备条件为:二甲胺硼烷(DMAB)作沉淀剂、Al_2(SO_4)_3.18H_2O作铝源、[Al~(3+)]=0.0005mol/L、n(DMAB)/n(Al_2(SO_4)_3·18H_2O)=40。制备出的Al(SO_4)_x(OH)_y具有球形、平均颗粒尺寸为98nm、粒径分布为75~130nm、单分散性的特点;获得了球形、平均颗粒尺寸为90nm、粒径分布范围为50~105nm、单分散的γ-Al_2O_3颗粒。     

In-situ Synthesis of Ti3AlC2/TiC-Al2O3 Composite from TiO2-Al-C System

Ti3AlC2/TiC-Al2O3 composite was synthesized by a combustion reaction in TiO2-Al-C system. The effect of the compositions in raw materials on the products was investigated. Ti3AlC2/TiC-Al2O3 composite was obtained at the molar ratio of TiO2:Al:C=3.0:5.0～5.1:1.8～2.0. The reaction path for the 3TiO2-5Al-2C system was proposed. Al3Ti, Ti2O3, TiO, and δ-Al2O3 are found to be transitional phases. Finally,Ti3AlC2/TiC-Al2O3 composite forms at ～900℃ of furnace temperature. The measured Vickers hardness,fracture toughness, and flexural strength of the nearly dense sample from 3TiO2-5Al-2C are 13.3±1.1 GPa,5.8±0.3 MPa.m1/2, and 466±39 MPa, respectively.     

TiO_2-Al_2O_3负载型催化剂的制备及其光催化性能

以钛酸四丁酯和氢氧化钠为反应物,采用两步水热法制备TiO2纳米线,并将其原位负载于Al2O3载体上,研究它们对甲基橙的光催化降解性能。结果表明,锐钛矿相TiO2主要呈纳米线和八面体状负载在Al2O3载体上,当TiO2负载质量分数为30%,焙烧温度为400℃,催化剂用量为1.332 0 g/L时,TiO2-Al2O3负载型催化剂光催化降解甲基橙的性能最佳,光照5 h后,甲基橙在紫外和太阳光下的降解率分别达到58.9%和55.6%。相同实验条件下,TiO2-Al2O3负载型催化剂对甲基橙的降解率比单纯TiO2提高了35.1%。     

SO_4~(2-)/TiO_2-SiO_2固体超强酸失活原因及再生方法研究

以SO42-/TiO2-SiO2固体超强酸催化剂为例,选择松香与甘油酯化这一高粘度有机反应体系,通过IR、TPD、XRD和BET等检测方法,研究了SO42-/TiO2-SiO2的失活原因。研究表明,催化剂表面吸附有机物、酸中心减少、酸量下降是导致该催化剂失活的主要原因。在此基础上研究了再生方法,优化了再生条件:在500℃焙烧脱去吸附物,再用H2SO4浸渍对失活催化剂进行再生。再生催化剂的催化性能与新鲜催化剂性能基本相同。     

纳米氧化铝粉体的绿色合成及其物相转变控制研究

以氯化铝、碳酸钠为原料,采用直接沉淀法,并于500～1,200℃煅烧,制备纳米Al2O3粉体。然后用TiO2、BaO对纳米Al2O3粉体掺杂,控制其物相转变过程。通过X射线衍射仪、差式扫描量热仪和透射电子显微镜分析纯净和掺杂后的纳米Al2O3的物相转变过程。结果表明,直接沉淀法所得水合Al2O3,经500℃煅烧后可转变为纳米活性Al2O3,粒径约为10 nm;纯净和掺杂Al2O3样品经1,200℃煅烧2 h后均为纳米粉体,其粒径为40～50 nm;在较高温度下,掺杂氧化钡对Al2O3的物相转变具有强烈抑制作用,粉体直至1,200℃仍未转变为结晶良好的α-Al2O3物相;而氧化钛则对其物相转变有显著促进作用,在1,000℃时粉体的主要物相即为α-Al2O3,1,100℃之后粉体已完全转变为α-Al2O3。     

Study on the Phase Transformation Behavior of Nanosized Amorphous TiO2

Nanosized amorphous TiO2 powders with a specific surface area of 501 m^2.g^-1 were prepared by hydrolysis. After calcined at 400℃ for 2 h, the prepared amorphous TiO2 powders were fully transformed into anatase crystallites with a specific surface area of 141 m^2.g^-1. Differential scanning calorimetric (DSC) experiments were performed on the samples of nanosized amorphous TiO2 mixed with microsized anatase, nanosized anatase, or nanosized α-Al2O3 respectively. Effects of sample packing, anatase addition, or α-Al2O3 addition on the crystallization behavior of nanosized amorphous TiO2 were analyzed.     

氧化铝-氧化钛纳米粉末的形貌、微结构和晶型转变

用溶胶-凝胶法合成了含氧化钛质量分数为10wt.%、30wt.%和50wt.%的氧化铝-氧化钛纳米复合粉末和单纯氧化铝纳米粉末,用溶胶-凝胶法合成的氢氧化物前驱体在700-1200℃锻烧2h转变为相应的氧化物,用XRD和TEM对氧化铝-氧化钛纳米复合粉末的形貌、微结构和晶相进行表征,结果表明,二氧化钛质量含量每增加约20wt.%,复合氧化物中氧化铝的α相转变温度就降低100℃,随着氧化钛加入量的增加,复合氧化物的晶粒迅速减小。第二相的加入有效地抑制了氧化铝基体晶粒的快速长大。添加质量分数为30wt.%氧化钛且在1000℃下煅烧的样品拥有25-32nm的最小晶粒。     

Role of Y4Al2O9 in High Temperature Oxidation Resistance of NiCoCrAlY-ZrO2.Y2O3 Coatings

NiCoCrAlY-ZrO2·Y2O3 coatings were deposited on the substrates by using a technology of combining electron,atom and ion beams （three beams）. Isothermal oxidation for these samples was performed at 1100℃ for 100-300 h. The results show that a thermally grown oxide （TGO） layer was formed between NiCoCrAlY layer and oxidation. The TGO contains α-Al2O3 and Y4Al2O9 etc. oxides. The intensity ratio of α-Al2O3/Y4Al2O9 was monotonously decreased with increasing oxidation time based on XRD （X-ray diffraction） analysis. The Y4Al2O9 phase plays the most important role in high temperature oxidation resistance at 1100℃. The related mechanism was also discussed.     

不同载体Mn-Ce催化剂的制备及其脱硝性能

以TiO_2、SiO_2及Al_2O_3为载体,采用分步共混法制备了三种均质整体式Mn-Ce负载型催化剂,探究了不同载体对催化剂脱硝活性、N2选择性及机械强度的影响。结果表明,以TiO_2和SiO_2为载体的催化剂80℃的脱硝率接近90%,而以Al2O3为载体的催化剂仅达46%。催化剂的表征发现这与Mn-Ce/TiO2和Mn-Ce/SiO2催化剂的比表面积和表面酸量较Mn-Ce/Al2O3更大、更多有关。而三种催化剂的N2选择性在80~200℃之间均接近100%,然而Mn-Ce/SiO2催化剂200℃以上N2选择性比其余两种催化剂差。三种催化剂的机械强度为Mn-Ce/TiO2Mn-Ce/SiO2Mn-Ce/Al2O3,其微观形貌显示这与催化剂体相结构的密实状况有关,各催化剂的活性组分氧化物均以无定形态存在。     

Preparation of mesoporous titania solid superacid and its catalytic property

Mesoporous titania (TiO(2)) was synthesized by hydrothermal method using cetyltrimethyl ammonium bromide (CTAB) as a template and using anhydrous ethanol and tetra-n-butyl titanate (TBOT) as raw materials. Mesoporous titania solid superacid and nanosized titania solid superacid catalysts were prepared by wet impregnation method. The structure and property of as-prepared samples were characterized by means of XRD, FT-IR and N(2) physical adsorption. The esterification of salicylic acid with isoamyl alcohol and the condensation of cyclohexanone with ethylene were used as model reactions to test the catalytic activities of the catalysts. On the other hand, the comparison of catalytic activities of the prepared solid superacid catalysts and the conventional liquid acid H(2)SO(4) was also carried out under the same experimental conditions. The results show that the catalytic activities of the prepared solid superacid catalysts were higher than that of the conventional liquid acid H(2)SO(4), and that the catalytic activity of mesoporous TiO(2) solid superacid is the highest among the three catalysts. Mesoporous TiO(2) solid superacid is a good catalyst for the synthesis of isoamyl salicylate or cyclohexanone ethylene ketal.     

Photocatalytic degradation of Direct Red 23 dye using UV/TiO2: Effect of operational parameters

In this study, the photocatalytic degradation of Direct Red 23 (Scarlet F-4BS) was investigated in UV/TiO2 system. The effect of catalyst loading and pH on the reaction rate was ascertained and optimum conditions for maximum degradation were determined. The results obtained showed that acidic pH is proper for the photocatalytic removal of Direct Red 23. In addition, the effects of several cations (Cu2+, Al3+, Cr3+, and Sn4+) and anions (BiO3(-), SO4(2-), and CN(-)) and C2H5OH were examined in this photocatalytic process. On the order hand, three types of catalysts (Fe2O3, SnO2, and ZnO) were compared with TiO2. After 90 min reaction, the relative decomposition order established was UV/TiO2>UV/SnO2>UV/Fe2O3>UV/ZnO.