核-壳介孔SiO_2微球的超微结构及拉曼光谱分析

采用溶胶-凝胶法制备了核-壳介孔SiO2微球,分别利用透射电镜和拉曼光谱对该微球的超微结构进行了观察及光谱分析。结果表明:制备的核-壳介孔SiO2微球是由外表面孔径为7nm、厚度30nm的有序介孔SiO2壳层,包裹着核直径为200nm的实心SiO2微球所组成,介孔壳层具有较大的比表面积,具有良好的光谱性质。     

氮掺杂TiO2/SiO2核壳型复合微球的制备及其可见光催化性能

 以单分散性良好的SiO2微球为模板,以钛酸四丁酯为钛源,利用化学吸附和原位水解方法制备了TiO2/SiO2核壳结构复合微球,并在氨气气氛下进行了氮掺杂. 以罗丹明B水溶液的光催化降解为模型反应,评价了所制试样在可见光照射下的光催化活性,并借助透射电镜、高分辨透射电镜、 X射线衍射、紫外-可见漫反射光谱、红外光谱和X射线光电子能谱等测试手段对其结构、形貌和光谱性质进行了表征. 结果表明,氮掺杂TiO2/SiO2为核壳结构, TiO2包覆层厚约10 nm. 由于SiO2核与TiO2壳间形成了 Ti-O-Si 键, TiO2的热稳定性增强. 掺杂的氮形成了 Ti-O-N 键. 600 ℃下氮化1 h得到的试样的可见光活性最佳. 由于结合了SiO2核优良的吸附性能及氮掺杂TiO2壳的可见光响应性能,该复合微球在整体上表现出比P25更优的光催化活性.     

银/二氧化硅核壳纳米颗粒的制备及其壳层厚度对其光学性质的影响

通过溶胶-凝胶法,制备了银/二氧化硅核壳材料(Ag@SiO2),对SiO2壳层厚度进行了有效调控,并系统研究了壳层厚度对银的等离子体共振峰(LSPR)以及对折射率灵敏度(RIS)的影响。研究结果表明,随SiO2壳层包覆厚度的增加,银纳米颗粒的LSPR吸收峰呈现先红移后蓝移的规律。对于粒径为50 nm的银纳米颗粒,当SiO2壳层达到65 nm时,LSPR最大吸收波长为465 nm。进一步增加SiO2壳层厚度,LSPR发生蓝移并且强度变弱,当SiO2壳层达到120 nm时,LSPR吸收峰已无法清晰辨认。研究了Ag@SiO2材料的RIS效应,发现随着SiO2厚度的增大RIS效应逐渐变小。     

反应介质pH值和前驱体用量对PSt/TiO_2复合微球结构形态及TiO_2空心微球形貌的影响

首先用聚乙烯亚胺(PEI)对粒径为360 nm的单分散无皂聚苯乙烯(PSt)乳胶粒进行修饰,得到表面荷正电的PSt种子乳液,然后将其滴加到溶有钛酸正丁酯(TBT)的乙醇与水的混合介质中,通过溶胶-凝胶(sol-gel)法制备出了核壳结构PSt/TiO2复合微球,系统研究了体系pH和TBT用量对复合微球结构形态的影响.研究表明,酸性条件不利于核壳结构PSt/TiO2复合微球的形成;当体系pH值为7.2时,可得到包覆完整、TiO2壳层厚度均一的PSt/TiO2复合微球,此后随着体系pH值的升高,包覆厚度逐渐提高;当pH值升高到11.0时,壳层厚度达到最大,但出现了包覆层不完整的复合微球.在固定聚合体系pH为8.5,EtOH/H2O质量比为100/6,表面修饰PSt种子乳液用量为0.5 g(固含量为4%)的条件下,随着TBT用量从0.01 g增加到0.16 g,复合微球壳层厚度从约0 nm逐渐增加到60 nm;当TBT用量增加到0.32 g时,壳层厚度迅速降至12nm,微球表面变得粗糙,并出现大量未包覆微粒;此后随着TBT用量的增加,包覆层厚度逐渐减少,未包覆微球逐渐增多.结果显示,当复合微球中TiO2包覆层达到一定厚度时,经煅烧后才能得到形貌完整的TiO2中空微球.     

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.     

温敏性异丙基丙烯酰胺-二氧化硅透明质酸核壳型杂化微凝胶的合成和体积相变行为

通过溶胶-凝胶法,利用硅烷偶联剂(KH550)对纳米SiO2颗粒进行原位改性,使其表面带正电。改性后的SiO2颗粒(MSiO2)通过静电作用吸附带负电的透明质酸(HA)形成核壳颗粒(HA-MSiO2)。进一步在壳层HA链上接枝聚合N-异丙基丙烯酰胺(NIPAM)制得核壳结构温敏性杂化微凝胶(PNIPAM-HA-MSiO2),并用AFM和SEM表征其在云母表面的成膜性能。结果表明:HA-MSiO2核壳颗粒平均粒径约为182 nm,壳层厚度15 nm,其粒径或壳层厚度可以通过改变MSiO2溶液或HA溶液的浓度来调节;温敏性PNIPAM-HA-MSiO2微凝胶的体积相变温度为32°C,与PNIPAM溶液的最低临界溶解温度(LCST)一致,在体积相变温度以下旋涂于云母表面的微凝胶呈现球形颗粒,体积相变温度以上旋涂膜可以转变为致密的膜。     

超临界干燥法制备TiO2气凝胶

以钛酸四丁酯为原料,采用溶胶-凝胶过程及及超临界干燥法制备了TiO2气凝胶,并通过XRD,BET和TEM等方法对所得样品进行了表征.结果表明,该法制备的TiO2气凝胶具有很高的比表面积(488 m2/g),平均粒径为4.6nm,具有锐钛矿型晶体结构.经400℃煅烧2 h所得的纳米粉体,其锐钛矿型晶体结构更为明显,平均粒径6.7 nm,比表面积158 m2/g.     

纳米晶粒TiO2多孔微球的合成与表征

 钛酸四丁酯经酸性水解得到TiO2溶胶，将溶胶与苯酚混合后加入到正庚烷分散介质中，再滴加甲醛水溶液，通过反相悬浮聚合和溶胶－凝胶过程制备了聚合物与TiO2的复合微球．对复合微球进行焙烧处理，使聚合物分解，从而得到由纳米TiO2晶粒组成的多孔微球．以示差扫描量热法、热重分析、X射线衍射、扫描电子显微镜和氮吸附等方法对TiO2多孔微球的物理性质进行了表征．结果表明，所得TiO2多孔微球主要由锐钛型TiO2纳米晶粒组成，晶粒尺寸为20～30nm；TiO2多孔微球的直径为200～500μm，比表面积为87．40m2／g，平均孔径为8．65nm，孔径的分布具有单分散特征．     

SiO2/LaF3:Eu3＋核壳结构发光粒子的制备与表征

采用简单的液相法合成了SiO2/LaF3:Eu3＋核壳结构发光粒子, 并对其结构及发光性能进行了表征. XRD分析表明包覆层LaF3:Eu3＋为立方晶相结构, 红外光谱表明SiO2颗粒表面有柠檬酸的修饰, 电镜照片表明合成了球形的核-壳结构的复合粒子, 包覆层厚度为10～20 nm, 光谱测试表明核-壳复合粒子与纯的LaF3:Eu3＋具有相同的发光性能, 均以589 nm附近的5D0—7F1磁偶极跃迁为最强发射峰, 说明Eu3＋在LaF3基质中占据的格位相同.     

改进型溶胶-凝胶法制备粒径可调高染料吸附量TiO2微球及其在染敏电池光散射层中的应用

利用改进型的溶胶-凝胶法,制得了由锐钛矿相纳米颗粒组成的TiO2多孔微纳小球。通过调节前驱物浓度,合成出粒径可控的尺寸分别为100,175,225,475 nm的TiO2微纳小球,并通过电泳沉积法将合成出的小球作为光散射层引入到染料敏化太阳电池(DSSC)中。由于这种微纳小球在具备良好的光散射性能的同时也具备较高的染料吸附量,因此相较于基于纳米颗粒的单层结构的DSSC拥有更高的光电转换效率。通过比较分析,粒径尺寸为475 nm的微球作为光散射层的DSSC光电转换效率可以达到6.3%,较之于基于纳米颗粒的DSSC提高了30%。     

微乳法制备纳米TiO2 /SiO2的结构及光催化研究

Nanosized TiO₂ and TiO₂/SiO₂ particles were prepared by hydrolysis of tetrabutyl titanate (TBOT) and tetraethyl orthosilicate (TEOS) in the TX-100 reverse microemulsion. These particles were characterized by TG-DSC, XRD, FTIR, TEM，N₂ adsorption-desorption. Their photocatalytic activity was tested by degradation of methyl orange. The result shows that TiO₂/SiO₂ nanoparticles are with a monodispersed spherical phase and a uniform size distribution，and TiO₂ particles are dispersed on the surface of SiO₂. The band for Ti-O-Si vibration in FTIR was observed, the Ti-O-Si bond increased the stability of anatase TiO₂, suppressed the phase transformation of titania from anatase to rutile. And due to the addition of SiO₂, the average size of titania decreased from 38 nm in pure TiO₂ to 5 nm in TiO₂/SiO₂. It was found, under UV light irradiation, TiO₂/SiO₂ particles showed higher activity than pure TiO₂, and TiO₂/SiO₂(1/1) particles showed the highest photocatalytic activity on the photocatalytic decomposition of methyl orange, which was influenced by crystal structure, particle size, crystallinity and Surface area Characteristics.     

负载型Pt-TiO2光催化剂的研究

TiO2粉末悬浮体系是一种研究比较早的光催化反应体系[1,2].由于它存在易凝聚和难回收等缺点,给实际应用带来了一定的困难.克服这一障碍的有效途径是制备负载型TiO2[3].所以,这些年来人们对负载型TiO2光催化体系颇有兴趣.从目前的文献报道来看,制备负载型TiO2的方法主要是溶胶法[4].采用溶胶法可在导体或非导体的基体上获得结合牢固、尺寸分布均匀的薄膜,但是膜的催化活性有待于提高.     

Preparation of metallodielectric composite particles with multishell structure

In this article, we demonstrated the synthesis of metallodielectric composite particles comprising a metal shell on a dielectric core and an outer coating of an insulating dielectric layer by depositing silver on silica supporting cores followed by coating of titania. A combination of surface reaction and surface seeding techniques is exploited for the formation of a complete silver shell on silica spheres. The additional outer coating of titania on silver shell particles is then performed by hydrolyzing tetra-n-butyl titanate in ethanol at room temperature. The morphologies of silver shells and titania coating are studied with electron microscopy, and their existences are confirmed with X-ray diffraction and energy-dispersive X-ray measurement.     

纳米结构TiO2/SiO2的逐层自组装

采用逐层自组装方法在二氧化硅球表面交替组装了十二烷基硫酸钠单分子膜和二氧化钛纳米粒子膜 ,该复合多层膜经高温煅烧后得到了核壳型纳米结构二氧化钛 /二氧化硅复合颗粒 .利用XRD ,SEM ,X射线能谱等对复合颗粒进行了表征 .结果表明 :二氧化钛在复合颗粒表面排列紧密、均匀 ,粒径在 5 0nm左右 ,为锐钛矿型结构 .复合颗粒中二氧化钛的含量随组装层数的增加而均匀增加     

TiO_2光催化/膜分离耦合过程降解偶氮染料废水

以钛酸丁酯为前驱体,采用酸性溶胶法在低温下(<100oC)制备了纳米级TiO2粉末,X射线衍射分析表明,样品为锐钛矿型,晶粒尺寸为3.6nm.以250W紫外灯为光源,在自制悬浮式光催化膜反应器中进行降解活性艳红X-3B有机染料废水实验,采用尼龙6(N6)和混合纤维素(CN-CA)两类微滤膜对TiO2颗粒进行截留分离.综合考察了影响光催化和膜分离效率的因素.结果表明,反应起始pH值和催化剂用量对光催化膜反应器运行性能影响很大,该耦合体系的最佳pH值为4,染料和催化剂最佳浓度比为2:1,0.45和0.22μm的CN-CA膜对TiO2颗粒截留率可达96.5%以上.     

微乳法合成纳米SiO2/TiO2及其光催化性能

采用聚乙二醇辛基苯基醚(Triton X-100)/正己醇/环己烷/氨水微乳体系合成了纳米TiO2和SiO2/TiO2复合物,用X射线衍射、红外光谱和透射电镜对其结构进行了表征,并以甲基橙降解评价了其光催化性能,讨论了SiO2/TiO2摩尔比、晶相组成及粒径与光催化活性的关系.结果表明,SiO2/TiO2催化剂中形成了新的Ti-O-Si键和无定形SiO2;在纳米TiO2中复合SiO2能有效抑制锐钛矿向金红石的转变,增加锐钛矿的稳定性,并阻止TiO2晶粒的聚集生长.催化剂的光催化活性随金红石含量的增加而降低,加入适量SiO2能明显提高TiO2的光催化活性,其中摩尔比为1/7的SiO2/TiO2光催化活性最高.     

Fabrication of sub-micrometer-sized jingle bell-shaped hollow spheres from multilayered core-shell particles

Jingle bell-shaped hollow spheres were fabricated starting from multilayered particles composed of a silica core, a polystyrene inner shell, and a titania outer shell. Composite particles of silica core-polystyrene shell, synthesized by coating a 339-nm-sized silica core with a polystyrene shell of thickness 238 nm in emulsion polymerization, were used as core particles for a succeeding titania-coating. A sol-gel method was employed to form the titania outer shell with a thickness of 37 nm. The inner polystyrene shell in the multilayered particles was removed by immersing them in tetrahydrofuran. These successive procedures could produce jingle bell-shaped hollow spheres that contained a silica core in the titania shell.     

Preparation of nearly monodisperse multiply coated submicrospheres with a high refractive index

Nearly monodisperse SiO2/TiO2/SiO2 multiply coated submicrospheres with nearly monodisperse silica submicrospheres as cores, thick titania layers, and thin silica skin were prepared to increase the refractive index of complex submicrospheres while keeping their near monodispersity and perfect surface properties. Nearly monodisperse colloidal silica submicrospheres as cores with a diameter of 200 nm were synthesized by a seeding technique on the basis of the hydrolysis of tetraethyl orthosilicate (TEOS) in an aqueous ethanol solution with ammonia as catalyst. On the basis of the hydrolysis of tetrabutyl orthotitanate, a procedure combining continuous feeding with multistep coating was determined to prepare titania coatings about 40 nm thick and increase the refractive index of the complex submicrospheres. The hydrolysis of TEOS was still used to get the outmost silica coating about 10 nm thick on titania coated silica submicrospheres to eliminate random aggregation caused by the TiO2 surface properties of the TiO2/SiO2 complex submicrospheres during the final fabrication of photonic crystals.     

Preparation and characterization of silver/TiO2 composite hollow spheres

Silver-coated poly(methyl acrylic acid) (PSA) core-shell colloid particles were prepared by an in situ chemical reduction method. Crystalline silver/titania composite hollow spheres were obtained by coating the as-prepared PSA/silver particles with an amorphous titania layer and subsequently calcining in Ar atmosphere. SEM and TEM investigation indicated that the size of the as-prepared PSA/silver and PSA/silver/TiO(2) core-shell particles and silver/titania composite hollow particles was fairly uniform and the wall thickness of the hollow spheres was in the range of 40-80 nm. UV-vis absorption spectra were recorded to investigate their optical properties.     

Fabrication of hydroxyl group modified monodispersed hybrid silica particles and the h-SiO(2)/TiO(2) core/shell microspheres as high performance photocatalyst for dye degradation

The monodisperse hybrid silica particles (h-SiO(2)) were firstly prepared by a modified sol-gel process and the surface was modified in situ with double bonds, then abundant carboxyl moieties were introduced onto the surface of the silica core via thiol-ene click reaction. Afterward, the h-SiO(2)/TiO(2) core/shell microspheres were prepared by hydrolysis of titanium tetrabutoxide (TBOT) via sol-gel process in mixed ethanol/acetonitrile solvent, in which the activity of TBOT could be easily controlled. The carboxyl groups on the surface of silica particles promote the formation of a dense and smooth titania layer under well control, and the layer thickness of titania could be tuned from 12 to 100nm. The well-defined h-SiO(2)/TiO(2) core/shell structures have been confirmed by electron microscopy and X-ray photoelectron spectroscopy studies. After calcination at 500°C for 2h, the amorphous TiO(2) layer turned into anatase titania. These anatase titania-coated silica particles showed good photocatalytic performance in degradation of methyl orange aqueous solution under UV light.