基于纳米ZnO/聚氯乙烯的复合材料光催化性能研究

本文采用纳米氧化锌与聚氯乙烯溶液共混制备了复合材料前驱体，运用TG-DTA联机分析得到了其分解温度及相关热分解数据；经适当温度煅烧后得到复合材料光催化剂，并用TEM、XRD、FTIR、UV-Vis、ESR对复合材料进行分析表征。在室内普通照明用荧光灯作用下，以甲基橙溶液为催化对象，对复合材料的光催化性能进行了检测，并在相同条件下，与纳米氧化锌、纳米氧化钛及聚氯乙烯直接煅烧产物的光催化性能进行了比对分析；同时研究了pH值对复合材料光催化性能的影响。研究结果表明，复合材料对甲基橙催化降解8 min后，甲基橙溶     

低共熔溶剂中纳米氧化锌的制备及形貌调控

分别以工业氧化锌、氯化锌和草酸锌为锌源,氯化胆碱-尿素低共熔溶剂为溶剂,通过沉淀法制备了不同结构和形貌的纳米氧化锌。通过X射线衍射仪(XRD)、扫描电子显微镜(SEM)和甲基橙光催化降解对样品进行了表征,分析了锌源变化对产物形貌的影响以及不同形貌氧化锌形成过程中前驱体的调控作用及反应机理。并将制备的不同形貌氧化锌应用于光催化降解甲基橙。结果表明制备的由纳米晶组装而成的厚块状Zn O纳米结构对甲基橙有良好的光催化性能。     

纳米ZnO/聚醋酸乙烯酯复合薄膜的光催化性能研究

采用溶胶-凝胶和浸渍-提拉而后煅烧的方法得到了在可见光作用下具有光催化性能的纳米ZnO/聚醋酸乙烯酯(PVAc)复合薄膜.通过正交设计实验,研究了PVAc的浓度、煅烧温度、煅烧时间、复合薄膜层数和附加ZnO膜层数等工艺因素对光催化性能的影响,并通过SEM,XRD和FT-IR对其进行了分析与表征.在室内普通照明用白炽灯作用下,以甲基橙溶液为催化对象,PVAc含量10%的、在250℃煅烧30min所得到的纳米ZnO/PVAe复合薄膜的光催化性能的实验结果表明,复合薄膜对甲基橙降解率达60%,而使用250℃煅烧30min所得到的纳米ZnO 4层薄膜或PVAc 4层薄膜催化的甲基橙溶液的浓度变化很小.     

不同形貌ZnO@PANI纳米复合材料的制备及光催化性质

采用直接沉淀法和水热合成法制备出形貌和尺寸比较均一的颗粒状、棒状和球形花状的纳米ZnO。使用硅烷偶联剂KH-42(苯胺甲基三乙氧基硅烷,C6H5-NH-CH2-Si(OCH3)3)对所得纳米ZnO进行表面化学修饰,修饰后的纳米ZnO(m-ZnO),经由皮克林乳液聚合法使苯胺单体在其表面聚合,形成聚苯胺(PANI)包覆的氧化锌纳米复合材料(m-ZnO@PANI),采用XRD、SEM、HRTEM、FTIR、UV-Vis、TG等对样品进行表征;研究了m-ZnO@PANI纳米复合材料对亚甲基蓝(MB)的光催化性能。结果表明,复合材料对可见光也有较强的吸收,在紫外、可见光照射下都有较好的光催化降解效率。其中,棒状ZnO纳米复合材料的光催化降解性能最好,它的紫外-可见光和可见光光催化降解率分别达到98.2%和97.1%,而且复合材料的光催化性能稳定,二次循环的紫外-可见光催化降解率仍达到96.0%。     

AuNPs@POMs/rGO复合材料的制备及光催化性能

以Keggin型多金属氧酸盐(多酸,POMs)为光催化还原剂、稳定剂和包覆剂,在光照下一步合成AuNPs@POMs/rGO复合纳米材料。采用透射电镜(TEM)、X射线衍射(XRD)和紫外-可见吸收光谱(UV-vis)等对所制得的材料进行了结构表征和性能测试。以光催化降解甲基橙为模型反应研究了AuNPs@POMs/rGO纳米复合材料的光催化活性。透射电子镜结果显示Au纳米微粒均匀的负载在rGO薄层上,无聚集和团聚现象。实验探究了pH、温度、催化剂投放量以及甲基橙初始浓度对光催化降解过程的影响。光催化降解结果表明:当溶液处于室温,pH=8.0,催化剂投放量为0.15 g·L~(-1),甲基橙溶液初始浓度为25.0 mg·L~(-1)时,效果达到最佳,降解率为94.5%。     

溴化银/二氧化钛复合材料的可见光催化性能

将硝酸银的乙醇溶液与溶胶凝胶TiO2混合得到前驱体,随后经共沉淀-煅烧制备得到AgBr/TiO2复合材料;采用扫描电镜、X射线衍射仪、X射线光电子能谱仪分析了复合材料的形貌、晶体结构、Ag元素的价态,采用紫外-可见漫反射光谱仪测定了其光吸收性能;进而以甲基橙(MO)的可见光降解为探针反应测定了AgBr/TiO2复合材料的可见光催化性能.结果表明,当前驱体在不同温度下煅烧后,无定形TiO2颗粒逐渐增大,并逐渐转变为锐钛矿结构;担载的AgBr可明显拓展TiO2的可见光吸收范围;Ag物种主要以Ag+形式存在.当煅烧温度为300℃时,复合材料的光催化活性最高,MO的降解率在60min内达到90%以上;随着煅烧温度的增加,催化活性逐渐降低.     

板式纳米碳纤维负载二氧化钛光催化复合材料的制备及降解甲基橙的研究

以板式纳米碳纤维为载体,采用酸性氧化法对载体进行预处理之后,使用钛酸异丙酯为钛源,高温水热法制备了二氧化钛/纳米碳纤维复合光催化剂,并考察了其对甲基橙的光催化去除能力及循环反应性能.复合材料中二氧化钛含量通过改变前驱体组成进行调节.材料的结构性能通过氮气吸附、X射线衍射(XRD)、能谱分析仪(EDS)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、热重分析仪(TG-DSC)等测试技术进行了表征.结果表明,锐钛矿型的二氧化钛以纳米颗粒形式均匀分散在纳米碳纤维表面,从而形成了高度分散的二氧化钛/碳纤维纳米复合材料.另外,复合系统中中孔吸附作用的存在,与纳米二氧化钛的光催化产生协同作用,增强了复合材料在紫外光照射下对于水溶液中甲基橙的去除能力.在光照射下反应120 min时,不同担载量样品对甲基橙的去除率最高可达80.1%,不同煅烧温度样品最高可达79.2%.此外,光催化剂有着良好重复利用性能,3次循环反应后对甲基橙去除率仍可保持80.0%.     

太阳光活性的铁酸铝-二氧化钛纳米复合光催化剂

以共沉淀法制备的铁酸铝和溶胶-凝胶法制备的二氧化钛粉体作为前驱体, 合成了铁酸铝-二氧化钛纳米复合材料, 通过曙红染料和甲基橙的光催化降解来评价该纳米复合材料的光催化活性, 并与单一二氧化钛的光催化性能进行了比较. 实验结果表明: 无论是紫外光还是太阳光的激发下, 铁酸铝-二氧化钛纳米复合材料的光催化活性均优于同样条件下所制备的单一二氧化钛纳米材料, 理想的铁酸铝掺杂浓度分别是1.0%(紫外光)和9.0%(太阳光). 由于在二氧化钛基体中掺入铁酸铝纳米粒子, 既可以促进光生载流子的电荷分离, 又可以使二氧化钛的光响应波长向可见光区域拓展, 提高了太阳能利用率, 从而使其在太阳光下具有更优越的光催化活性.     

微波助离子液体中纳米TiO2／PMMA复合材料的制备及光催化性能

微波加热法合成离子液体[Bmim]BF4,并以该离子液体为反应介质,在微波辐射条件下制备纳米TiO2/PMMA复合材料.用XRD,IR和TG对该复合材料进行测试和表征;并在高压汞灯下用甲基橙溶液对其进行光催化降解性能测试.结果表明,制备TiO2/PMMA复合材料的最佳条件是:离子液体1.7mL,钛酸丁酯与MMA的体积比为3.4∶1.0,微波辐射功率600W、反应温度70℃、反应时间35min.并且用[Bmim]BF4作为反应介质,能够显著提高TiO2/PMMA复合材料的光催化活性,所制备的TiO2/PMMA复合材料不需要经过高温煅烧,就表现出极高的光催化活性;TiO2负载PMMA后,复合材料的光催化活性得到了进一步的改善.该复合材料对甲基橙的降解率在1.5h就可达到98.4%,其活性明显优于未负载的纳米TiO2催化剂.     

ZnTiO3-TiO2纳米复合材料的光催化性能

通过溶胶 凝胶（Sol-Gel）法制备了ZnTiO3-TiO2纳米复合光催化剂,利用透射电子显微镜、X射线衍射、紫外-可见吸收光谱和ζ电位等测试技术对其形貌、晶体结构及其光谱响应特性进行了表征。 以亚甲基蓝（MB）溶液的脱色降解为模型反应,考察了光源和焙烧温度对该纳米复合材料光催化性能的影响。 结果表明,所得纳米复合材料的催化性能与材料的尺寸、在介质中的分散性能、表面荷电性质等有关。 600 ℃下焙烧3 h所得的ZnTiO3-TiO2纳米复合材料尺寸小（约60 nm）、分散性能好、表面荷负电荷量最高、催化性能最好,且在太阳光下的活性高于紫外光下的。 如太阳光下7 h可使亚甲基蓝（MB）溶液的脱色降解率达到93%,而在紫外光下只有82%;并且其催化活性高于纯TiO2和ZnO的。 该纳米复合催化剂重复使用4次仍能使亚甲基蓝（MB）溶液的脱色降解率在80%以上。 因此,具有较好的光催化稳定性能。     

均相沉淀法合成纳米ZnO及其光催化性能研究

以ZnSO_4、尿素为原料,采用均相沉淀法在90 ℃合成出了纳米ZnO,并就反应 温度、反应时间、反应物浓度及物料配比等条件对产物的影响进行了探讨。XRD物 相分析,产物为六方晶系;TEM形貌观察,粒子基本为球形,平均粒径20 nm;并用 IR,TG-DTA等测试手段对其进行了表征。利用紫外-可见分光光度计测试了光吸收 性能,发现纳米氧化锌对200～380 nm波长范围的光有很强吸收性,在可见光范围 内,也有较强的吸收。利用纳米氧化锌作为光催化剂对有机染料溶液进行了降解实 验,发现在日光照射60 min后,对酸性大红4BE的降解率可达100%。     

Bi12 TiO20纳米粉体的制备及其光吸收特性研究

Nano-cystal Bi12 TiO20 powders have been prepared by the chemical solution decomposition（ CSD）method using bismuth nitrate and titanium butoxide as the starting precusors. The powders were characterized by the thermogravimetry and differential thermal analysis（TG-DTA）,X-ray diffractometry（XRD）and transmission electron microscopy（TEM）. The formation mechanism of Bi12TiO20 naocrystal has been analyzed. The UV-Vis diffuse reflectance spectra of the prepared Bi12TiO20 powders were measured to determine their optical absorption characteristic. The results showed that pure nano-crystal Bi12TiO20 powders could be easily prepared from stoichiometric precursor solutions at the annealing temperature 1550℃. A broad optical absorption band between 560-385 nm （about 2. 2-3. 22 eV）was observed for the prepared nano-crystal Bi12TiO20 powders.     

聚乳酸/氧化锌柱撑皂石纳米复合材料制备与性能及结构表征

通过微波水解法制备了ZnO柱撑皂石,并以其为加工助剂制备了聚乳酸(PLA)/ZnO柱撑皂石纳米复合材料.通过X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、对ZnO柱撑皂石及PLA/ZnO柱撑皂石纳米复合材料的结构进行了表征,并对其力学性能和热稳定性能进行了测试.微观结构分析表明,ZnO柱撑皂石呈现剥离状,并均匀分散在PLA基质中.力学性能研究表明0.3%ZnO柱撑皂石的加入有助于改善PLA复合材料的断裂伸长率.SEM分析表明PLA复合材料的断面发生明显改变,表现良好韧性;DSC结果显示纳米ZnO柱撑皂石可以降低复合材料的玻璃化转变温度、结晶温度,有助于提高PLA复合材料的结晶度,与XRD分析相吻合;热重分析表明ZnO柱撑皂石可以提高PLA复合材料的热稳定性.测试结果表明,ZnO柱撑皂石在PLA基质中起到了异相成核的作用,促进了PLA基质的结晶.     

钛酸锌的制备及其对高氯酸铵热分解的催化性能

ZnTiO₃ nanocrystals were prepared by sol-gel method, using Zn(NO₃)₂ and Ti(C₄H₉O)₄ in the topic. The as-prepared ZnTiO₃ nanocrystals were characterized by XRD, FTIR and TEM, and the catalytic performance of ZnTiO₃ nanocrystals of different contents for the ammonium perchlorate(AP)decomposition was investigated by thermal analysis. The results indicate that ZnTiO₃ with pure cube structure can be synthesized at 600 ℃ by this procedure,which was spheroid with particle size of about 60~100 nm. The results expressed that the low temperature decomposition peaks of AP is advanced by 17 ℃ and the high temperature decomposition peaks of AP is advanced by 24 ℃ when adding 5% nanoparticle ZnTiO₃ powder. The catalytic effects of ZnTiO₃ powders on the high temperature decomposition of AP are less than that of nanometer metal powders, but all the micron metal powders decrease the low decomposition temperature of AP.     

Preparation and characterization of nanocomposite ZnO–Ag thin film containing nano-sized Ag particles: influence of preheating,annealing temperature and silver content on characteristics

Nanocomposite ZnO–Ag thin film containing nano-sized Ag particles have been grown on glass substrate by spin-coating technique using zinc acetate dihydrate as starting precursor in 2-propanol as solvent and monoethanolamine as stabilizer. Silver nanoparticles were added in the ZnO sol using silver nitrate dissolved in ethanol-acetonitrile. Their structural, electrical, crystalline size and optical properties were investigated as a function of preheating, annealing temperature and silver content. The results indicated that the crystalline phase was increased with increase of annealing temperature up to 550 °C at optimum preheating temperature of 275 °C. Thermal gravimetric differential thermal analysis results indicated that the decomposition of pure ZnO and nanocomposite ZnO–Ag precursors occurred at 225 and 234 °C, respectively with formation of ZnO wurtzite crystals. The scanning electron microscopy and atomic force microscopy revealed that the surface structure (the porosity and grain size) of the ZnO–Ag thin film (the film thickness is about 379 nm) was changed compared to pure ZnO thin film. The result of transmission electron microscopy showed that Ag particles were about 5 nm and ZnO particles 58 nm with uniform silver nanoclusters. Optical absorption results indicated that optical absorption of ZnO–Ag thin films decreased with increase of annealing temperature. Nanocomposite ZnO–Ag thin films with [Ag] = 0.068 M and [Ag] = 0.110 M showed an intense absorption band, whose maximum signals appear at 430 nm which is not present in pure ZnO thin films. The result of X-ray photoelectron spectroscopy revealed that the binding energy of Ag 3d_5/2 for ZnO–Ag shifts remarkably to the lower binding energy compared to the pure metallic Ag due to the interaction between Ag and ZnO.     

室温球磨固相反应法制备纳米SnO_2的研究

室温固相反应合成法是近二十年来发展起来的一种全新的合成手段,由于该法具有工艺简单、便于操作控制、团聚少、不使用溶剂、高产率、污染少、节省能源、成本低等优点,利于实现工业生产,符合当今社会绿色化学发展的要求,因而受到人们的重视,目前,已有较多研究报道了利用该技术成功制备多种新材料和纳米材料[1-4].     

CPF/ZnO纳米复合催化材料的制备

通过原位聚合-热转化两步法,利用ZnO纳米微粒和糠醇(F)制备出了具有大共轭结构的高分子(CPF)和ZnO的纳米复合催化材料(CPF/ZnO);用TG-DTA、TEM、XRD、XPS、IR和UV-Vis等技术对其热稳定性、形貌、尺寸、结构及吸光特性等进行了表征,以亚甲基蓝(MB)溶液的催化降解研究了该材料在自然光条件下的催化性能。结果表明,由该方法可以得到平均尺寸约为 50 nm的CPF/ZnO纳米复合催化材料;其中的CPF为具有极性基团和大共轭结构的高分子;ZnO与CPF化学键合在一起;CPF的引入将ZnO的光谱响应拓展到了整个紫外-可见区,从而极大地改善了ZnO在自然光条件下的催化性能。如在460 ℃下处理40 min所得的纳米复合材料,在自然光条件下,10 min即可使MB溶液完全脱色,而在相同条件下,纯纳米ZnO仅能使MB的脱色率为10%左右;该催化材料重复使用3次仍可使MB溶液的脱色率保持在80%以上。     

Mechanism and degradation kinetics of zinc complex containing isophthalato and 2,2′-dipyridylamine ligands under different atmospheres

The design of mixed-ligand complexes are of increasing interest from fundamental as well as technological and curative aspects. Having that in mind, we studied zinc complex containing 2,2′-dipyridylamine (dipya) and dianion of isophthalic acid (ipht), [Zn(dipya)(ipht)]_n, as promising precursor for synthesis of nanostructured metal oxide. In that sense, the mechanism and degradation kinetics of [Zn(dipya)(ipht)]_n was analyzed under non-isothermal conditions in nitrogen and in air atmospheres. Peak deconvolution of the [Zn(dipya)(ipht)]_n decomposition profile, in the form of a derivative thermogram (DTG), in nitrogen atmosphere, revealed the presence of three decomposition steps, while in air five single steps were isolated. In both cases ZnO is formed as residue at 530 °C: pure (in air) or in amorphous matrix (nitrogen). In air we obtained well crystalized ZnO nanospheres (∼25 nm), by thermal treatment in temperature range 370–530 °C showing that this complex could be considered as good precursor for production of nanosized ZnO.     

Non-isothermal kinetic studies on thermal decomposition of energetic materials

Thermal stability and decomposition kinetics for two energetic materials, potassium nitroform (KNF) and 5-Nitro-2,4-dihydro-3H-1,2,4-triazol-3-one (NTO), were investigated to obtain information on their safety for handling, storage, and use. Differential scanning calorimetry (DSC) and simultaneous thermogravimetry-differential thermal analysis (TG-DTA) techniques have been used to study thermal behavior of these energetic compounds. The results of TG analysis revealed that the main thermal degradation for the KNF occurs during two temperature ranges of 270?C330 and 360?C430?°C. Meanwhile, NTO decomposes completely in temperature range of 250?C300 °C. TG-DTA analysis of KNF indicates that this energetic compound dehydrated (at about 108?°C) before its decomposition. However, NTO is thermally stable until its decomposition. The decomposition kinetic of energetic materials was studied by non-isothermal DSC under various heating rates. Kinetic parameters such as activation energy and frequency factor for thermal decomposition of energetic compounds were obtained via the methods proposed by ASTM E696 and Starink. Also, thermodynamic parameters correspond to the activation of thermal decomposition and critical ignition temperatures of the compounds were obtained.