纳米TiO2的表面能态及光生电子-空穴对复合过程的研究

以液相法制备了水溶态纳米TiO2,并通过X射线衍射(XRD)、X射线光电子能谱(XPS)和傅里叶红外光谱仪(FTIR)对纳米TiO2的结构和组成作了细致分析.并对其紫外-可见光谱(UY-Vis spectrum)和荧光发光光谱(PL spectrum)进行了分析.结果发现纳米TiO2呈现较好的锐钛矿型,平均粒径为5 nm.水溶态纳米TiO2由于吸附而在表面形成了Ti-OH和Ti-H2O的表面态,其能级位于其价带以上约0.6和0.54eV;500℃热处理后样品的表面吸附水基本消失,但OH-仍然存在,同时在纳米TiO2晶格中出现了氧空位,其能级位于价带以上3.13 eV.对于水溶态纳米TiO2,表面复合是电子-空穴对的主要复合过程;热处理后的样品,由于表面态遭到破坏,粒子半径变大,直接复合成为电子-空穴对的主要复合过程,同时还伴随有通过氧空位的间接复合和通过Ti-OH的表面复合.     

粒径对表面包覆硬脂酸的TiO2超微粒光学性质的影响

制备了一系列表面包覆硬脂酸的TiO2超微粒,发现表面包覆硬脂酸的TiO2超微粒随着超微粒粒径减小,其表观光学带隙(Eg)降低,即吸收光谱带边红移加大.     

Fe3O4@SiO2@TiO2复合纳米结构的尺寸与磁性调控

采用共沉淀法和溶剂热法制备了不同尺寸的Fe3O4纳米粒子,通过Stöber法和溶胶-凝胶法在Fe3O4磁核上包覆SiO2和TiO2壳层获得不同尺寸的Fe3O4@SiO2@TiO2复合纳米结构．采用X射线衍射仪(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)和振动样品磁强计(VSM)等对其结构、形貌和磁性进行了研究．结果表明,大尺寸复合纳米粒子包覆均匀,分散性好,饱和磁化强度较大,有利于TiO2光催化剂的磁回收与再利用．     

Cu/N表面沉积共掺杂TiO_2光催化剂作用机理的理论研究

本文采用基于周期性密度泛函理论研究了Cu/N表面沉积共掺杂对锐钛矿相TiO2(001)面的修饰作用.计算了Cu在不同位置掺杂TiO2(101)面和(001)面的形成能,并在此基础上计算N不同位置掺杂TiO2(001)面及Cu/TiO2(001)面的形成能,通过形成能的比较获得了表面共掺杂的最优化结构.在此基础上计算了最稳定结构的能带结构及态密度,并与S单掺杂TiO2(001)面最稳定结构进行了对比.通过对结果的分析发现:Cu/N在(001)表面的沉积共掺杂有效降低了TiO2的禁带宽度,并在表面形成CuO2相,更利于提高其光催化活性.     

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。     

BaAl_(12)O_(19)∶Mn~(2+)荧光粉的表面包覆与发光性能

采用传统的高温固相反应法合成出BaAl12O19∶Mn2+荧光粉,利用乳胶法对荧光粉颗粒表面包覆MgF2。对包覆过程中的反应物浓度、反应过程进行研究,得到最佳包覆条件,确定荧光粉表面包覆的制备工艺。通过X射线衍射、透射电镜图、红外光谱等对表面包覆的荧光粉颗粒的结构性能进行分析,并在彩色等离子体平板显示器(PDP)上进行涂屏老化实验。结果表明在BaAl12O19∶Mn2+荧光粉颗粒表面成功地包覆上MgF2 层,包覆后的荧光粉的初始发光亮度下降 1. 6%,而老化 8h后,包覆的荧光粉亮度衰减明显优于不包覆的材料。     

Ti/Si比例对Tb3+掺杂TiO2-SiO2复合粉末的发光影响

用溶胶-凝胶法制备了Tb3+离子掺杂的TiO2-SiO2复合粉末并研究了Ti/Si比例对复合粉末光致发光的影响。采用X射线衍射(XRD)、Raman和光致发光谱(PL)对Tb3+离子掺杂的TiO2-SiO2复合粉末进行了一系列的表征。PL谱的结果表明Tb3+离子5D4-7F5跃迁对应的550nm绿光发射最强。随着Ti/Si比例的减小, Tb3+离子在可见光范围的发光逐渐增强, 这可能是由于Tb3+离子周围环境的非晶化加剧引起的。     

Study on the optical properties of PPV／TiO2 nanocomposites

The optical properties of poly(Phenylenevinylene)(PPV)/TiO2 nanocomposites,prepared via the sol-gel process,were investigated by UV-VIS,FT-IR,FL spectroscopy and TEM.TEM images indicated that the surfaces of TiO2 nanoparticles became rough,and finally formed the connected network as the TiO2 content increased.FT-IR spectra showed the titanium butoxide hydrolyzed to from Ti organic compound,which can result in the connected network of TiO2 nanoarticles.The conjugation of PPV polymer chains can be interrupted by the TiO2 network structure,as evdenced in UV-VIS spectra.The investigation of the PL spectra revealed that the emitted light of the PPV/TiO2 nanocoposites blue shifted wihout fine structure,and the PL intensity enhanced,when the TiO2 net work fromed.These phenomena suggested that the optical properties of the PPV/TiO2 nanocomposites were dependent on the interfacial structure between PPV and TiO2 nanoparticles.2001 Elsevier Science B.V.All rights reserved.     

磁性光催化剂TiO2/Fe3O4的制备和表征

以Fe3O4为磁核,制备了易于分离的磁性光催化剂.采用X射线粉末衍射(XRD)、扫描电镜(SEM)、光电子能谱(XPS)、傅里叶红外光谱(FTIP)等手段表征催化剂的表面形貌、晶型组成、化学结构等.结果表明,TiO2包覆在Fe3O4表面,且包覆较为牢固.利用降解斯蒂酚酸考察其光催化性能,制得的催化剂具有较高的光催化活性和较好的可分离性.     

基于密度泛函理论的DBDS与DBS对铜绕组腐蚀性能对比研究

二苄基二硫醚(DBDS)与二苄基硫醚(DBS)是变压器内部主要腐蚀性硫化物,能腐蚀铜绕组,破坏变压器的安全运行.为从微观层面探究两者腐蚀性能的差异,基于密度泛函理论(DFT)对DBDS与DBS的腐蚀性能进行对比研究.计算了DBDS/Cu(110)吸附模型与DBS/Cu(110)吸附模型的功函变化,发现DBDS/Cu(110)的功函变化ΔΦ_1(-0.388 eV)绝对值要小于DBS/Cu(110)功函变化ΔΦ_2(-1.118 eV)绝对值,说明DBS更易吸附Cu(110)表面;DBDS在Cu(110)表面的吸附能E_(ads1)为8.571 eV,DBS在Cu(110)表面吸附能E_(ads2)为6.077 eV,表明两者都不能自发吸附,需要从外界吸热才能吸附,且DBS从外界获取能量更少,更容易吸附.同时比较了DBDS分子与DBS分子前线轨道分布以及HOMO轨道与LUMO轨道能量差,计算了DBDS分子与DBS分子的电负性,结果表明:DBDS电负性大小为3.132 eV,DBS电负性大小为3.100 eV,两者基本相等.而DBDS前线轨道能量差(2.610 eV)明显小于DBS前线轨道能量差(3.610 eV), DBDS优化前后的S-S键长分别为2.033?和3.057?,说明DBDS更容易与Cu发生反应.以上模拟结果说明,DBS更易吸附于Cu,而DBDS更易与Cu发生反应.     

Enhancement of the photocatalytic activity of TiO2 nanoparticles by surface-capping DBS groups

TiO₂ nanoparticles capped with sodium dodecylbenzenesulfonate (DBS) are synthesized by a sol-hydrothermal process using tetrabutyl titanate and DBS as raw materials. The effects of surface-capping DBS on the surface photovoltage spectroscopy (SPS), photoluminescence (PL) and photocatalytic performance of TiO₂ nanoparticles are principally investigated together with their relationships. The results show that the surface of TiO₂ nanoparticles can be well capped by DBS groups while the pH value and added DBS amount are controlled at 5.0 and 2% of TiO₂ mass weight, respectively, and the linkage between DBS groups and TiO₂ surfaces is mainly by means of quasi-sulphonate bond. The intensities of SPS and PL spectra of TiO₂ obviously decrease after DBS-capping, while the activity can greatly increase during the photocatalytic degradation of Rhodamine B (RhB) solution, which are mainly attributed to the electron-withdrawing character of the DBS groups. Moreover, the enhancement of photocatalytic activity of DBS-capped TiO₂ is also related to the increase in the capability for adsorbing RhB.     

Study of steady state and time resolved photoluminescence of thiol capped CdS nanocrystalline powders dispersed in N,N-dimethylformamide

The microwave (MW) assisted synthesis of thiol capped cadmium sulfide (CdS) nanocrystallites/quantum dots (QDs) was performed through the reaction of cadmium acetate with thiourea in N,N-dimethylformamide (DMF) by keeping the MW irradiation time fixed (40 s) in the presence of a thiol containing capping agent. Three capping agents, namely, benzyl mercaptan (BM), 1-butanethiol (BT) and 2-mercaptoethanol (ME) were used. The concentration of the precursors was varied to check the change in the average size of the thiol capped CdS nanocrystals formed. The nanocrystallites were characterized by usual procedure. The UV-vis absorption spectra and the photoluminescence (PL) spectra of the CdS nanocrystalline powders dispersed in DMF were studied. It was observed that with increase in concentration of the capping agent (BM), there is a shift in the nature of emission (PL) from trap associated PL to the band edge luminescence in the case of BM capped CdS nanocrystalline powders dispersed in DMF possibly due to better surface passivation. The relative PL quantum yield of the thiol capped CdS nanocrystalline powders dispersed in DMF was calculated under various experimental conditions. Time-correlated single-photon counting experiments were performed to study the time-resolved photoluminescence of the CdS nanocrystalline powders dispersed in DMF. The observed emission decay profiles have been simulated using the multiexponential model. The emission decay profiles for thiol capped CdS nanocrystalline powders dispersed in DMF depend on the nature of the capping agents (thiols) used to passivate the CdS nanocrystallites. The time resolved PL studies show that the average values of PL lifetime are related to the size and size distribution of the prepared thiol capped CdS nanocrystallites.     

Surface modification of ZnO nanocrystals

Nano-crystalline ZnO particles were synthesized using alcoholic solutions of zinc acetate dihydrate through a colloidal process. Five types of capping agents: 3-aminopropyl trimethoxysilane (Am), tetraethyl orthosilicate (TEOS), mercaptosuccinic acid (Ms), 3-mercaptopropyl trimethoxysilane (Mp) and polyvinylpyrrolidone (Pv) were added at the first ZnO precipitation time (first PPT) to limit the particle growth. The first three capping agents effectively capped the ZnO nanoparticles and limited the growth of the particles, while the last two capping agents caused agglomeration or larger clusters in the solutions. Particles synthesized were in the size range of 10-30 nm after capping, and grew to 60 and 100 nm in 3 and 6 weeks, respectively, during storage at ambient conditions. Refluxing time was found to only affect the first PPT time. Washing by ethanol and slow drying were very important in converting Zn(OH)₂ into ZnO. XRD analyses revealed single phase ZnO Wurtzite crystal structure. Photoluminescence (PL) spectra showed high-intensity in UV emission and very low intensity in the visible emission, which indicates a good surface morphology of the ZnO nanoparticles with little surface defects. Optical absorption spectra showed a blue shift by the capped ZnO due to the quantum confinement effect by the single crystal size of 5-6 nm as analysed by TEM. Capping effectiveness of each agent is discussed through possible capping mechanism and chemical reaction of each capping agent. This synthesis process is a low cost, high purity, easy to control method using only bio-compatible materials.     

水热法制备表面修饰的钛酸锶纳米微粉

以工业原料和常用试剂ＴｉＣｌ４、Ｓｒ（）ＮＯ３）２和ＫＯＨ为基础原料,通过添加表面活性剂十二烷基苯磺酸（ＤＢＳ）,并采用制备出表面包裹有ＤＢＳ的钛酸锶纳米微粉姘应用红外光谱,Ｘ射线衍射谱,透射电子显微镜,热分析等一系列手段对其微结构进行了表征。结果表明：样品为表面包裹ＤＢＳ的钛酸锶纳同粉,其形态较为规则,粒度分布较窄,单分散性较好,粒子的平均粒径为１２０ｍｍ,包裹膜的平均厚度为６ｎｍ左右,根据Ｘ光     

Optoelectronic characteristics of close-packed HgTe nanoparticles in the infrared range

Absorption, photoluminescence (PL), photoresponse, and I-V measurements were made for a close-packed HgTe nanoparticle film without organic capping materials to investigate its optoelectronic characteristics in the infrared (IR) range. In the absorption and PL spectra taken for the close-packed nanoparticle film, the wavelength of exciton peak was red-shifted, compared with 1-thioglycerol capped HgTe nanoparticles dispersed in solution. For the HgTe nanoparticle film, dark current was below several pA level, current was increased by about three orders of magnitude at a biased voltage of 3 V under the illumination, and photoresponse was very rapid compared with 1-thioglycerol capped HgTe nanoparticles. These optoelectronic characteristics illustrate that HgTe nanoparticles are one of promising materials for the photodetector in the IR range. Finally, the origin for the increase of photocurrent with increasing temperature observed in this study will be discussed.     

CdS及其包裹型纳米颗粒PVA基复合膜的特性研究

以聚乙烯醇 (PVA)、六偏磷酸钠为分散剂 ,采用溶胶法合成了 Cd S纳米胶体颗粒 ,制备出 Cd S及其包裹型纳米颗粒 PVA基复合膜。通过光子相干光谱粒度仪 (PCS)、紫外 -可见吸收光谱 (UV- VIS)、荧光光谱 (PL)对样品进行了初步表征。结果表明 ,Cd S纳米颗粒 PVA基复合膜的紫外 -可见吸收光谱有明显的蓝移现象 ,所发荧光主要由表面态发射引起 ;包裹型 PVA基复合膜所发荧光主要由带边发射引起     

Influences of capping molecules on optical properties of nanocrystalline ZnS:Cu

ZnS:Cu nanocrystals capped with different capping molecules have been successfully synthesized by a simple aqueous method. The prepared nanocrystals were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and energy dispersive analysis by X-rays (EDAX). The surface characterization of the nanocrystals was done by FTIR spectroscopy. The effect of capping agents on absorption and photoluminescence (PL) spectra of the ZnS:Cu nanocrystals was studied. A blue shift of the absorption peaks was observed and attributed to a quantum confinement effect, which increases the band gap energy. The photoluminescence spectra of the capped ZnS:Cu nanocrystals showed a broad peak in the range of 460–480 nm. The intensity of the PL spectra strongly depended on the capping agents.     

Synthesis and characterization of Cu doped ZnS nanoparticles using TOPO and SHMP as capping agents

Undoped and Cu²⁺ doped (0.2-0.8%) ZnS nanoparticles have been synthesized through chemical precipitation method. Tri-n-octylphosphine oxide (TOPO) and sodium hexametaphosphate (SHMP) were used as capping agents. The synthesized nanoparticles have been analyzed using X-ray diffraction (XRD), transmission electron microscope (TEM), Fourier transform infrared spectrometer (FT-IR), UV-vis spectrometer, photoluminescence (PL) and thermo gravimetric-differential scanning calorimetry (TG-DTA) analysis. The size of the particles is found to be 4-6 nm range. Photoluminescence spectra were recorded for ZnS:Cu²⁺ under the excitation wavelength of 320 nm. The prepared Cu²⁺-doped sample shows efficient PL emission in 470-525 nm region. The capped ZnS:Cu emission intensity is enhanced than the uncapped particles. The doping ions were identified by electron spin resonance (ESR) spectrometer. The phase changes were observed in different temperatures.     

Synthesis and optical characterization of PVP and SHMP-encapsulated Mn-doped ZnS nanocrystals

Zinc sulfide semiconductor nanocrystals doped Mn²⁺ have been synthesized via a solution-based method utilizing optimum dopant concentration (4%) and employing polyvinyl pyrrolidone (PVP) and sodium hexametapolyphosphate (SHMP) as capping agents. UV-vis absorbance spectra for all of the synthesized nanocrystals show an exitonic peak at around 310 nm. The particle size and morphology were characterized by scanning electron microscopy (SEM), FT-IR, X-ray diffraction (XRD), transmission electron microscopy (TEM) and photoluminescence spectrum (PL). Diffraction data confirmed that the crystallite size is around 3-5 nm. Room temperature photoluminescence (PL) spectrum for the bare ZnS sample shows a strong band at ∼445 nm. The uncapped and capped(SHMP, PVP) ZnS:Mn²⁺ samples show a strong and broad band in the ∼580-585 nm range.     

纳米颗粒DBS/TiO_2的拉曼光谱

采用水热法制得表面包覆有十二烷基苯磺酸的二氧化钛纳米粒子 ,并应用拉曼光谱对其进行了检测。结果表明 :样品为表面包覆有十二烷基苯磺酸的二氧化钛纳米粒子的集合体。其拉曼峰与未包裹的二氧化钛拉曼峰相比 ,出现了蓝移现象 ,从纳米粒子的表面结构及包裹层的压力出发对此现象进行了定性解释和讨论