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1.
纳米TiO2的光致发光性能与SERS效应的关系   总被引:2,自引:0,他引:2  
以采用溶胶-水热法制备的纯TiO2及Zn掺杂的TiO2纳米粒子作为SERS活性基底, 研究了其光致发光机制及其与表面增强拉曼散射(SERS)性能的关系. 结果表明, TiO2纳米粒子的表面缺陷和氧空位等表面性质在其光致发光和增强拉曼散射性能中发挥着重要的作用. 在表面缺陷和氧空位含量较低时, TiO2纳米粒子的光致发光光谱(PL)信号越强, 其SERS性能就越高; 当TiO2纳米粒子的表面缺陷和氧空位含量达到一定程度时, TiO2纳米粒子的PL信号越弱, 其SERS性能越高.  相似文献   

2.
通过光还原沉积法, 利用氧空位诱导作用, 在Ni掺杂的缺陷态TiO2纳米管阵列(TNT-Ni)上得到金属 Pd含量不同的Pd-TNT-Ni催化剂. 采用场发射扫描电子显微镜(SEM)、 X射线光电子能谱(XPS)、 紫外-可见 漫反射(UV-Vis DRS)、 表面光电压(SPV)、 光致发光光谱(PL)和电化学测试等表征手段, 探究了Pd与Ni掺杂的缺陷态TiO2纳米管阵列之间的强相互作用对其光吸收特性和载流子分离及传输效率的影响, 阐明了强相互 作用对材料光催化活性的调控机理, 提出了Pd增强Pd-TNT-Ni光催化性能的作用机理. 结果表明, 通过光还 原法制备的Pd纳米颗粒尺寸为10~20 nm的Pd120-TNT-Ni样品的光响应值为4.22 mA/cm2, 是未负载Pd样品光 响应值(1.14 mA/cm2)的3.7倍, 其具有最佳的平均产氢速率(5.16 mmol·g?1·h?1), 是TNT样品平均产氢速率 (0.45 mmol·g?1·h?1)的12倍, 表明Pd与缺陷态TiO2纳米管阵列之间的强相互作用驱动了载流子的分离及传输, 且Pd作为电子捕获势阱及反应活性位点, 显著提高了材料的光催化性能.  相似文献   

3.
利用太阳能在温和条件下实现CO2还原反应,不仅可以缓解过度消耗化石能源造成的能源危机,还可以改善诸如温室效应和海洋酸化等环境问题.光热协同催化可以有效降低催化反应温度,具有较大的应用前景.本文利用Ru与暴露TiO2{001}晶面的TiO2载体产生的金属-载体相互作用,经过高温氢气煅烧后,获得具有丰富表面氧空位的Ru/TiO2催化剂.活性测试结果表明,具有丰富表面氧空位的Ru/TiO2表现出优异的CO2甲烷化活性,反应过程中甲烷的TOF值在300°C时可以达到22 h-1,但该催化剂却表现出较差的稳定性,在反应10小时后,甲烷的TOF值逐渐降低到19 h-1.将紫外光引入到Ru/TiO2热催化甲烷化体系中,甲烷的TOF值增加到30 h-1,且兼具高稳定性.热催化反应过程中逐渐消失的表面氧空位和部分氧化的Ru是活性降低的主要原因.在光热协同反应中,光生电子的产生稳定了Ru表面的电子密度,同时也再生了催化剂上表面氧空位,这有效地提高了反应的活性和稳定性.程序升温原位红外和X射线光电子能谱实验结果表明,当催化剂表面具有丰富的表面氧空位时,CO2可以有效地在Ru纳米粒子上解离成CO中间体,随后吸附在Ru上的CO中间体解离成表面碳物种,并加氢产生甲烷.在热催化反应过程中,Ru纳米粒子逐渐被氧化成Ru Ox物种,且表面氧空位被CO中间物种覆盖,降低了催化反应的稳定性.当紫外光引入到上述反应中,催化剂的表面氧空位可有效提高光生载流子的分离能力.TiO2载体产生的光电子转移至Ru表面,稳定了金属Ru纳米粒子的价态.另外,载体产生的光生空穴加速了H2质子化,提高了催化剂对氢气的活化迁移能力,促进了CO中间体的加氢甲烷化反应,进而再生表面氧空位.因此在紫外光照下,兼顾提高了热催化CO2甲烷化的活性和稳定性.值得注意的是,当Ru负载于暴露少量TiO2{001}晶面的TiO2载体上时,产生了强金属-载体相互作用并抑制了H2在催化剂上的吸附活化,不利于产生表面氧空位.因此暴露少量TiO2{001}晶面的Ru/TiO2催化剂也不利于光生载流的产生和分离,这导致热催化或光热协同催化反应活性较低.  相似文献   

4.
通过半导体催化剂利用太阳能分解水制氢被认为是解决人类面临的环境问题和能源危机的有效途径.在众多的半导体光催化剂中,TiO2由于其良好的光化学稳定性、无毒性、丰富的形貌以及低廉的价格,在光催化制氢领域备受关注.然而TiO2的内在缺陷,如较宽的带隙、较窄的光响应范围,光生电子空穴对的快速复合,极大限制了其太阳能制氢效率.构建异质结结构被认为是解决以上问题的一个有效方法,通过将TiO2与另一个半导体复合可以提升催化剂对太阳光的吸收范围,也可降低光生电子空穴对的复合速率.但构建一个成功的异质结结构不仅要满足上述的要求,还需要保留异质结催化剂体系中光生电子和空穴的氧化还原能力.研究表明,S型异质结是将两个具有合适能带结构的半导体进行耦合,由于费米能级的差异,两个半导体间将发生电子转移,从而引起能带弯曲并形成内建电场.光照条件下,具有较弱还原能力的光生电子在内建电场和能带弯曲的作用下与较弱氧化能力的光生空穴复合,实现异质结催化剂体系中各个半导体内部光生载流子有效分离的目标,同时保留了异质结催化剂体系中较强氧化能力和较强还原能力的光生电子和空穴,进而实现光催化活性的提高.本文采用水热合成方法,将具有更强还原能力和可见光响应特性的半导体(ZnIn2S4)原位生长在TiO2纳米纤维表面,构建了1D/2DTiO2/ZnIn2S4S型异质结光催化剂.最优比例的TiO2/ZnIn2S4复合材料表现出优越的光催化制氢活性(6.03mmol/h/g),分别是纯TiO2和纯ZnIn2S4制氢活性的3.7倍和2倍.TiO2/ZnIn2S4复合材料光催化活性的提高可以归因于紧密的异质结界面、光生载流子的有效分离、丰富的反应活性位点以及增强的光吸收能力.通过原位XPS和DFT计算研究了异质结内部光生电子的转移机制.结果表明,在光照条件下电子由TiO2向ZnIn2S4迁移,遵循了S型异质结内部电子的转移机制,实现了TiO2和ZnIn2S4内部光生载流子的有效分离,同时保留了具有较强还原能力的ZnIn2S4价带电子和较强氧化能力的TiO2导带空穴,从而显著提升光催化制氢效率.综上,本文制备的TiO2/ZnIn2S4S型异质结光催化剂很好地克服了TiO2在光催化制氢领域所面临的诸多障碍,为设计和制备高效异质结光催化剂提供了新的思路.  相似文献   

5.
水热法制备掺杂铁离子的TiO2纳米粒子及其光催化反应研究   总被引:29,自引:0,他引:29  
以TiCl4为前驱体,采用水热法制备了掺杂铁离子的TiO2纳米粒子,利用XRD对不同条件下制备的产物进行了表征,探讨了反应温度、胶体溶液pH值和反应时间对水热反应的影响.考察了所制备的Fe3+-TiO2纳米粒子光催化降解罗丹明B的催化性能,实验发现,制备的掺杂0.1%Fe3+-TiO2纳米粒子与纯TiO2相比,具有更好的催化活性.  相似文献   

6.
采用溶胶-凝胶-浸渍法制备了La3+/S-TiO2纳米光催化剂,通过XRD、BET、XPS、UV-Vis等手段进行了表征.以甲基橙溶液为光催化降解反应的模型化合物,考察了光催化剂的活性,探讨了低量La3+掺杂对TiO2纳米粒子光催化活性的影响机制.实验结果表明:S改性TiO2后明显提高了TiO2纳米粒子的光催化活性,而La3+掺杂S-TiO2后,进一步提高了TiO2纳米粒子的光催化活性,La3+的最佳掺杂量(相对于TiO2的质量分数)为0.369%;La3+/S-TiO2(ω(La3+)=0.369%)为纳米光催化剂时,甲基橙的脱色率达到92.4%(光照120min);XRD和BET分析表明,低量La3+掺杂抑制了TiO2由锐钛矿向金红石的转变,阻碍了TiO2晶粒的生长,提高了TiO2的比表面积;XPS分析表明,S、La3+掺杂可以导致粉体的表面羟基含量增加,掺杂S以S6+形式置换TiO2晶格中的Ti4+;UV-Vis分析表明,光催化剂La3+/S-TiO2比纯TiO2具有较强的紫外光吸收性能.与纯TiO2相比,La3+掺杂TiO2纳米粒子光催化氧化活性的提高应归因于La3+掺杂增加了表面羟基含量,增大了比表面积,增强了样品表面的紫外光吸收能力.  相似文献   

7.
刘兵  宫辉力  刘锐  胡长文 《应用化学》2019,36(8):939-948
利用溶胶凝胶法制备了金纳米棒(GNR)与TiO2的核壳结构复合材料--GNR@TiO2,粒径为200 nm左右。 经水热晶化后的材料粒径为300 nm左右,GNR形貌和局域表面等离子共振(LSPR)峰保持稳定,其外边包裹着树枝状的锐钛矿相TiO2壳层。 采用X射线衍射(XRD)、高分辨透射电子显微镜(HRTEM)、X射线光电子能谱分析(XPS)、紫外可见吸收光谱、光催化制氢性能等技术手段测试表征了样品的结构及性能。 结果表明,晶化后的GNR@TiO2在可见光范围内制氢速率为31.0 μmol/(g·h),相较与晶化前7.3 μmol/(g·h)得到了明显提升。 最后结合实验结果和时域有限差分(FDTD)分析了催化产氢机理:LSPR促进了可见光吸收,锐钛矿TiO2对电场的增强促进了光生电子-空穴分离,同时晶化后的TiO2壳层疏松多介孔,增加了活性位点,有利于传质。  相似文献   

8.
采用溶胶-凝胶-原位碳热还原处理的方法,制备了一种含有氧空位(OV)的新型Zn掺杂β-Bi2O3纳米材料(OV-Zn∶Bi2O3),氧空位的浓度可以通过改变Zn2+的掺杂量进行调节。作为参照,只有氧空位没有Zn2+的新型β-Bi2O3(OV-β-Bi2O3)也通过类似的方法制得。通过紫外可见漫反射光谱、X射线光电子能谱、电子顺磁共振、光致发光光谱和光电化学测试,系统研究了氧空位和Zn2+掺杂对OV-Zn∶Bi2O3降解亚甲基蓝(MB)和2,4,6-三氯苯酚(2,4,6-TCP)可见光催化活性的综合影响。结果表明,氧空位的引入不仅可以使光吸收向长波方向拓展,而且可以促进光生载流子的分离。因此,与传统的β-Bi2O3相比,OV-β-Bi2O3对亚甲基蓝(MB)和2,4,6-三氯苯酚(2,4,6-TCP)的降解活性显著增强。对于OV-Zn∶Bi2O3催化剂,Zn2+掺杂可使光催化剂的价带边缘向下移动,增强了光激发空穴的氧化能力,并且适量的锌掺杂也能提高光生载流子的分离效率。因此,OV-Zn∶Bi2O3的可见光活性优于OV-β-Bi2O3,而且当Zn与Bi物质的量之比为0.3时,OV-Zn∶Bi2O3-0.3对MB和2,4,6-TCP的降解活性最高。  相似文献   

9.
层状双氢氧化物(LDH)的光生电子-空穴对易复合,虽然纳米薄片的结构促进了载流子分离,但其光催化效率仍然较低。我们利用LDH薄片结构的优势,将FeNi LDH和TiO2通过静电自组装复合,设计制备出新型高效的FeNi LDH/TiO2复合光催化材料,评价了其光催化分解水产氢性能。对其结构、光催化性能和光电化学等进行了详细表征。结果表明,FeNi LDH的高比表面积、复合物的异质结结构都有利于光生电荷的转移。光催化产氢结果表明,FeNi LDH/TiO2复合材料的产氢速率(22.6mmol·g-1·h-1)分别比纯TiO2(0.1 mmol·g-1·h-1)和FeNi LDH(0.05 mmol·g-1·h-1)提高了226和452倍,表明了异质结在提高LDH光催化效率方面的重要作用。  相似文献   

10.
以电纺TiO2纳米纤维为基质, 柠檬酸为软模板, 采用一步水热法制备了具有三维立体网状结构的稀土Dy 3+掺杂YVO4/TiO2复合纤维. 通过X射线衍射、 扫描电子显微镜、 X射线光电子能谱、 N2吸附-脱附、 紫外-可见漫反射光谱及荧光光谱等手段对材料的组成、 表面形貌和性能进行表征, 以光分解水产氢实验考察其光催化活性. 结果表明, Dy 3+∶YVO4纳米枝与TiO2纳米纤维相互交联构筑的纳米纤维网具有大比表面积, 可提供更多活性位点, 改善了多相光催化反应的传递过程; 稀土Dy 3+掺杂的YVO4与TiO2复合形成异质结相互促进, 在拓宽光谱响应范围、 提高太阳光利用率的同时使光生电子-空穴对得到较好分离, 从而提高了样品的光催化活性. 模拟太阳光照射下, Dy 3+∶YVO4/TiO2复合纤维光催化产氢速率达到8.63 mmol· h -1·g -1, 是纯TiO2纳米纤维的10倍.  相似文献   

11.
Single-phase Co-doped TiO2(CoxTi1-xO2) nanoparticles(NPs) synthesized via a simple sol-hydrothermal method were used as surface-enhanced Raman scattering(SERS) substrates. Interestingly, it was found that SERS signals were enhanced greatly compared to those of pure TiO2 nanoparticles when an amount of Co2+ ions were doped into the TiO2 lattice. Detailed results clearly show that Co element as Co2+ was incorporated into the TiO2 lattice and the defects were created due to the substitution of Co2+ ions for the Ti4+ ions. The Co2+ doping increases the defect concentration of CoxTi1-xO2 NPs. An amount of defects is beneficial to the charge-transfer so as to increase the SERS activities. A possible mechanism of charge-transfer from CoxTi1-xO2 NPs to molecules was then briefly discussed.  相似文献   

12.
The threat and global concern of energy crises have significantly increased over the last two decades. Because solar light and water are abundant on earth, photocatalytic hydrogen evolution through water splitting has been considered as a promising route to produce green energy. Therefore, semiconductor photocatalysts play a key role in transforming sunlight and water to hydrogen energy. To date, various photocatalysts have been studied. Among them, TiO2 has been extensively investigated because of its non-toxicity, high chemical stability, controllable morphology, and high photocatalytic activity. In particular, 1D TiO2 nanofibers (NFs) have attracted increasing attention as effective photocatalysts because of their unique 1D electron transfer pathway, high adsorption capacity, and high photoinduced electron–hole pair transfer capability. However, TiO2 NFs are considered as an inefficient photocatalyst for the hydrogen evolution reaction (HER) because of their disadvantages such as a large band gap (~3.2 eV) and fast recombination of photoinduced electron–hole pairs. Therefore, the development of a high-performance TiO2 NF photocatalyst is required for efficient solar light conversion. In recent years, several strategies have been explored to improve the photocatalytic activity of TiO2 NFs, including coupling with narrow-bandgap semiconductors (such as ZnIn2S4). Recently, microwave (MW)-assisted synthesis has been considered as an important strategy for the preparation of photocatalyst semiconductors because of its low cost, environment-friendliness, simplicity, and high reaction rate. Herein, to overcome the above-mentioned limiting properties of TiO2 NFs, we report a 2D/1D ZnIn2S4/TiO2 S-scheme heterojunction synthesized through a microwave (MW)-assisted process. Herein, the 2D/1D ZnIn2S4/TiO2 S-scheme heterojunction was constructed rapidly by using in situ 2D ZnIn2S4nanosheets decorated on 1D TiO2 NFs. The loading of ZnIn2S4 nanoplates on the TiO2 NFs could be easily controlled by adjusting the molar ratios of ZnIn2S4 precursors to TiO2 NFs. The photocatalytic activity of the as-prepared samples for water splitting under simulated solar light irradiation was assessed. The experimental results showed that the photocatalytic performance of the ZnIn2S4/TiO2 composites was significantly improved, and the obtained ZnIn2S4/TiO2 composites showed increased optical absorption. Under optimal conditions, the highest HER rate of the ZT-0.5 (molar ratio of ZnIn2S4/TiO2= 0.5) sample was 8774 μmol·g-1·h-1, which is considerably higher than those of pure TiO2 NFs (3312 μmol·g-1·h-1) and ZnIn2S4nanoplates (3114 μmol·g-1·h-1) by factors of 2.7 and 2.8, respectively. Based on the experimental data and Mott-Schottky analysis, a possible mechanism for the formation of the S-scheme heterojunction between ZnIn2S4 and TiO2 was proposed to interpret the enhanced HER activity of the ZnIn2S4/TiO2heterojunctionphotocatalysts.   相似文献   

13.
卤素离子对TiO2薄膜光致亲水性的影响   总被引:1,自引:0,他引:1  
将卤化钾盐KX(X=I、Br、Cl、F)分别引入至TiO2溶胶中, 利用提拉法在载玻片上制得含有卤素离子的TiO2-X薄膜样片, 通过测试样片紫外光照下水滴接触角的变化, 考察了不同浓度的KI以及不同卤素离子对TiO2薄膜光致亲水性能的影响, 并通过测试光照后的亲水薄膜样片暗处放置不同时间后接触角的变化, 比较了含TiO2-I和TiO2-F薄膜样片亲水性能的持久性. 结果表明, 适量的KI有助于提高TiO2薄膜的光致亲水性, 当TiO2溶胶中KI浓度为1.0×10-5 mol•L-1时, 其所制得TiO2薄膜的光致亲水性最好, 继续增大KI浓度时, 薄膜的光致亲水性逐步下降, 当KI浓度达1.0×10-2 mol•L-1时, 其光致亲水性较纯TiO2薄膜差;同时, 适量的KBr、KCl加入也有助于提高TiO2薄膜的光致亲水性, 且随KI>KBr>KCl的顺序逐渐减弱, 但KF的加入降低了薄膜的光致亲水性;另外, 卤素离子的加入还有助于提高TiO2薄膜亲水性能的持久性, 且KF>KI. 分析认为, 卤素离子对TiO2薄膜光致亲水性的影响与其给电子或捕获光致电子作用有关, 并提出了其作用模型, 而卤素离子与亲水基团(羟基)的氢键作用是使KX-TiO2薄膜能够延长亲水性时间的原因.  相似文献   

14.
Zn-doped and La/Zn co-doped TiO2 nanoparticles were prepared by sol–gel method and utilized as the photocatalysts for the isomerization of norbornadiene to quadricyclane that has significant potential for solar energy storage and high-energy fuel synthesis. For Zn-doped samples, Zn ions do not enter the TiO2 lattice, but distribute on the particle surface in the form of ZnO crystallites. These crystallites inhibit the agglomeration, growth and anatase-to-rutile phase transformation of TiO2. The prepared particles contain considerable amount of surface-bound OHs, especially for 1%Zn/TiO2. A red shift in the optical absorption is observed due to the electron transfer between TiO2 and ZnO. In the photocatalytic isomerization reaction, Zn-doped TiO2 exhibits higher activity than homogenous sensitizer like Ethyl Michler's Keton, and 1%Zn/TiO2 produces the highest yield of quadricyclane. To further enhance the activity, 1%Zn/TiO2 was co-doped with La. La2O3 crystallites also distribute on the surface of TiO2, similar to the case of ZnO. The particle size is reduced to <7 nm but the surface-bound OHs are decreased to some degree. There is a significant blue shift in the optical absorption with a sharply increased absorbance in the UV region due to the quantum-size effect. 5%La–1%Zn/TiO2 and 3%La–1%Zn/TiO2 exhibit higher activity compared with 1%Zn/TiO2, but higher or lower content of La is detrimental to the reaction. It is concluded that doping Zn can significantly increase the surface-bound OHs, whereas doping La reduces the particle to quantum-size at the expense of surface-bound OHs. A good compromise between the two factors eventually provides a high activity. The isomerization reaction over semiconductors is proposed to proceed through an exciplex (charge-transfer) intermediate.  相似文献   

15.
通过溶胶-水热法合成纯的和不同量Ni离子掺杂的TiO2纳米粒子, 将其作为表面增强拉曼散射(SERS)活性基底, 研究了金属Ni掺杂对于纳米TiO2 SERS性能的改进. 结果表明, 适量的Ni掺杂能够在纳米TiO2的能隙中靠近导带底的位置形成丰富的掺杂能级, 促进TiO2-to-molecule的电荷转移过程, 进而提高纳米TiO2基底对吸附分子的SERS增强能力, 显著改进纳米TiO2的SERS性能.  相似文献   

16.
Nanosized pure TiO2 particles with high crystallinity and large surface area were prepared by hydrolysis of tetrabutyl titanate in water/Triton X-100/isooctane reverse micelle solutions as reaction media followed by hydrothermal treatment to improve crystallinity. The prepared TiO2 nanoparticles were characterized by XRD, BET, TGA, FT-IR and TEM. The size of ultrafine particles was controlled by changing the water content of the reverse micelle solution. The TiO2 particles showed monodispersity, large surface area and high degrees of crystallinity and thermostability. The photocatalytic activity of the TiO2 particles was evaluated by decomposition of toluene in the gas phase. The activity of the TiO2 nanoparticles was higher than that of commercially available anatase fine particles, such as ST-01, which is one of the most active photocatalysts for degradation of organic compounds in the gas phase.  相似文献   

17.
A facile approach was developed to prepare highly dispersed TiO2 nanoparticles with selected phase. The crystallization phase of the nanoparticles can be easily tuned from anatase to rutile by the dosage of hydrochloric acid in the reaction system. The crystallite size of the as-prepared anatase TiO2 nanoparticles was ca. 3.2 nm with high dispersion. A transparent TiO2 colloid was obtained by dispersing the as-prepared anatase TiO2 nanoparticles in deionized water without any organic additives added. The concentration of TiO2-H2O colloid can be as high as 1600 g/L. The optical transmittance of TiO2-H2O colloid with a low concentration was nearly 100% in the visible region. Furthermore, anatase TiO2 nanoparticles(TiO2-NPs) showed superior photocatalytic performance compared to rutile TiO2-NPs.  相似文献   

18.
TiO2 nanoparticles(TiO2 NPs) worked as an efficient heterogeneous catalyst in a one-pot,three-component,and solvent free Mannich reaction;producing variousβ-aminocarbonyls in good yields,and with good stereoselectivities.The catalyst was easily separated from the reaction mixture and was recycled four times with no significant loss of its catalytic activity.  相似文献   

19.
The performance of dye-sensitized solar cells(DSSCs) consisting of anatase TiO_2 nanoparticles that were synthesized via a hydrothermal method was studied.The synthesized TiO_2 nanoparticles were characterized by X-ray diffraction(XRD),nitrogen sorption analysis,scanning electron microscopy(SEM),high resolution transmission electron microscopy(HRTEM),and UV-vis spectroscopy.Then the J-Vcurve,electrochemical impedance spectroscopy(EIS),and open-circuit voltage decay(OCVD) measurement were applied to evaluate the photovoltaic performance of DSSCs.Compared with the commercial TiO_2nanoparticles(P25),the synthesized-TiO_2 nanoparticles showed better performance.By adding diethylene glycol(DEG) before the hydrothermal process,the synthesized TiO_2 nanoparticles(hereafter referred to as TiO_2-DEG particles) shows narrower size distribution,larger specific surface area,higher crystallinity,and less surface defects than TiO_2(DEG free) particles.The analysis of photovoltaic properties of DSSCs based on TiO_2-DEG particles showed that the recombination of electron-hole pairs was decreased and the trapping of carries in grain boundaries restrained.It was believed that the photoelectrode fabricated with the as-prepared TiO_2 nanoparticles improved the loading amount of dye sensitizers(N719).and enhanced the photocurrent of the DSSCs.As a result,the TiO_2-DEG particle based cells achieved a photo-to-electricity conversion efficiency(η) of 7.90%,which is higher than 7.53%for the cell based on TiO2(DEG free) and 6.59%for the one fabricated with P25.  相似文献   

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