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1.
采用实时双光子光电子能谱和时间分辨双光子光电子能谱技术分别研究了乙醇在该表面光催化解离的动力学和超快电子动态学过程. 通过测量与乙醇光催化解离相关的电子激发态随时间的演化,发现这个反应满足分型动力学. 乙醇在还原性TiO2(110)上的光催化解离比在氧化性表面快,这归结于缺陷的存在降低了反应能垒. 这样一个反应的加速过程很可能是与缺陷电子相关的. 通过干涉双脉冲相关的测量,得到了乙醇-TiO2界面电子激发态的超快动态学. 与甲醇的情况类似,这个电子激发态的寿命为24 fs. 激发态的出现为TiO2和它周围环境的电子转移提供了一个通道.  相似文献   

2.
通过高分辨的扫描隧道显微术研究并比较了金红石型TiO2(110)-(1×1)和锐钛矿型TiO2(001)-(1×4)两种表面的活性位点. 在金红石型TiO2(110)-(1×1)表面, 观察到氧空位缺陷是O2和CO2分子的活性吸附位点,而五配位的Ti原子是水分子和甲醇分子的光催化反应活性位点.在锐钛矿型TiO2(001)-(1×4)表面,观察到完全氧化的表面,Ti原子更可能是六配位的,H2O和O2分子均不易在这些Ti原子上吸附.经还原后表面出现富Ti的缺陷位点, 这些缺陷位点对H2O和O2分子表现出明显的活性. 锐钛矿型TiO2(001)-(1×4)表面的吸附和反应活性并不具有很高的活性,某种程度上其表现出的活性似乎低于金红石型TiO2(110)-(1×1)表面.  相似文献   

3.
用光电子能谱的方法研究了甲醇/TiO2(110)界面的电子结构.在激发波长为400 nm的双光子光电子能谱(2PPE)中,探测到了一个末态能量在费米能级以上5.5 eV的共振信号.之前的研究[Chem. Sci. 1, 575 (2010)]表明,这个共振信号与甲醇在5配位的钛离子(Ti5c)上的光催化解离相关.双光子光电子能谱同时携带初态和中间态的信息.为此设计了一个调谐激发光波长的2PPE实验以及一个单光子光电子能谱(1PPE)和2PPE对比的实验,结果一致表明这个共振信号来自于未占据的中间态,也就是激发态.能带色散关系测量表明这个激发态是局域的.时间分辨2PPE测得这个激发态的寿命是24 fs.  相似文献   

4.
基于C60受体和有机分子给体的太阳能电池是目前非常重要的一个研究热点, 利用同步辐射真空紫外光电子能谱(SRUPS) 技术研究了酞菁铁(FePc)与TiO2(110)及C60的界面电子结构, 以及FePc与C60分子混合薄膜的电子结构. SRUPS价带谱显示, FePc沉积在化学计量比与还原态两种不同的TiO2(110)表面时, FePc分子的HOMO能级均随FePc厚度的变化发生了移动, 而在化学计量比的TiO2(110)表面位移较大, 同时发生界面能带弯曲, 说明存在从有机层向衬底的电子转移. 在FePc/C60和C60/FePc界面形成过程中, FePc与C60分子的最高占据分子轨道(HOMO)位移大小基本相同. 由界面能级排列发现, 在FePc与C60的混合薄膜中, FePc分子的HOMO与C60分子的最高占据分子轨道能级差较大, 这有利于提高器件开路电压, 改善器件性能.  相似文献   

5.
利用同步辐射高分辨光电子能谱研究了金团簇在部分还原TiO2-(1×1)表面的生长和稳定性.价带谱实验结果观察到非常少量金团簇的沉积导致了Ti3+的3d峰完全消失,表明金团簇成核在TiO2-(1×1)表面的氧缺陷位.Au4f芯电子光电子能谱实验结果证明了TiO2-(1×1)表面氧缺陷位向金团簇转移电荷.还对比研究了化学剂量比和部分还原的TiO2-(1×1)表面上金团簇的热稳定性.当金团簇尺寸相近时部分还原的TiO2-(1×1)表面上金团簇要比化学剂量比的TiO2-(1×1)面上金团簇稳定;在相同的表面上尺寸大的金团簇要比尺寸小的金团簇稳定.  相似文献   

6.
搭建了一套研究金属和金属氧化物表面的超快激发态电子动力学和光化学动力学的飞秒双光子光电子能谱仪. 该装置将半球形电子能量分析仪和成像技术相结合,同时测量光电子的能量和角度分布.通过Mach-Zehnder干涉仪测量时间分辨的双光子光电子能谱获得超快激发电子态的动力学信息. 这一功能在Cu(111)上得到了证实. 另外还发展了一个通过实时测量双光子光电子能谱来研究表面光化学的方法,并成功应用到CH3CH2OH/TiO2(110)体系. 研究表明,只有将两种方法结合起来才能正确地研究光诱导的表面激发共振的动力学.  相似文献   

7.
本文利用程序升温脱附技术(TPD)研究了乙醛吸附在锐钛矿型TiO2(001)-(1×4)表面的化学性质. 实验结果表明完整晶格位点对乙醛反应表现极为惰性,而表面上的还原型缺陷位点在热驱动下可有效地使乙醛分子通过碳-碳偶联反应生成2-丁酮和丁烯. 提出了乙醛在锐钛矿型TiO2(001)-(1×4)表面偶联反应主要是通过表面还原型缺陷位吸附成对的乙醛分子,因为表面已有的钛原子对还原型缺陷为乙醛分子提供了合适的吸附位点.  相似文献   

8.
李冬冬  王丽莉 《物理学报》2012,61(3):34212-034212
首次用二氧化钛(TiO2)纳米材料修饰的547孔微结构聚合物光纤(MPOF)二次预制棒作为阵列化微管式光催化反应器对亚甲基兰的光催化分解进行研究.将高光催化活性的P25型二氧化钛纳米粒子均匀分散在TiO2溶胶中,对547孔微结构聚合物光纤孔洞内壁进行铺膜,得到了负载光催化剂的阵列化微管材料.该TiO2MPOF有序复合的阵列化微管不仅对二氧化钛纳米粒子起到负载作用,还可以作为光波导介质(rolling-up薄膜波导,聚光、导光进入二氧化钛薄膜层)、污染物反应流体通道.以有机染料亚甲基兰为模拟污染物,研究了TiO2负载量、亚甲基兰的初始浓度及溶液pH值等因素对光降解效果的影响.该反应器547个孔道的内表面用于负载光催化剂,不仅增加了固-液接触面积,也提高了光的吸收效率,从而提高了光催化效率.迄今为止,这种兼具导光、聚光、传质、负载功能于一体的光催化反应器还未见报道.  相似文献   

9.
通过水解TiCl4制备了锐钛矿结构TiO2纳米粒子, 并用时间分辨荧光光谱研究了5(6)CFL(5(6)-Carboxyfluorescein, 简称5(6)CFL)染料敏化TiO2纳米粒子体系的光致电子转移动力学. 5(6)CFL染料敏化TiO2纳米粒子能形成电荷转移复合物, 这归因于染料分子的激发电子态波函数Ψ(D*)与电荷分离态波函数Ψ(D+ +e-)之间的耦合作用. 当激发5(6)CFL染料敏化TiO2纳米粒子体系时, 电子以两种不同方式注入TiO2纳米粒子导带: 第一, 通过5(6)CFL染料分子的激发态注入; 第二, 从电荷转移复合物(5(6)CFL/TiO2)直接注入. 时间分辨荧光光谱表明, 在水溶液中纯5(6)CFL染料的荧光以寿命为τ1=41 ps (74.4%) 和τ2=3.22 ns (25.6%) 的双e指数衰减, 而5(6)CFL染料敏化TiO2纳米粒子体系的荧光分别以时间常数为τ1=44 ps (90.4%), τ2=478 ps (8.6%) 和τ3=2.41 ns (1.0%) 的三e指数衰减. 本文的研究工作能够为染料敏化太阳能电池的光致电子转移机理提供有价值的参考.  相似文献   

10.
采用Adler法合成了5-(4-氨基苯基)-10,15,20-三苯基卟啉铜配合物(CuAPTPP),通过甲苯二异氰酸酯(TDI)的桥联作用对TiO2微球进行表面修饰,使TDI分子中的两个活性TDI基团分别与TiO2表面的羟基和CuAPTPP的氨基反应,将CuAPTPP敏化剂分子以化学键合的方式固定在TiO2表面,形成光催化微球CuAPTPP-TDI-TiO2.通过FT-IR、XRD、SEM、EA、UV-Vis和DRS等测试手段对CuAPTPP-TDI-TiO2进行结构表征.讨论了桥联分子TDI修饰量对光催化微球性能的影响,确定了TDI与TiO2的最佳摩尔比.以亚甲基蓝(MB)为降解对象,考察了CuAPTPP-TDI-TiO2微球的可见光催化性能.结果表明,桥联分子TDI在CuAPTPP与TiO2微球表面形成了牢固的化学键,复合微球在150 W氙灯辐照下降解10 mg/LMB溶液,120 min降解率可达98.7%,其降解率过程服从一级动力学规律,测得降解速率常数为5.1×10-2 min-1,半衰期为11.3 min.催化微球在回收4次的条件下,对MB的降解率仍保持在90%以上.  相似文献   

11.
We have investigated the photoinduced decomposition of formaldehyde (CH2O) on a rutile TiO2(100)-(1×1) surface at 355 nm using temperature-programmed desorption. Products, formate (HCOO-), methyl radical (CH3·), ethylene (C2H4), and methanol (CH3OH) have been detected. The initial step in the decomposition of CH2O on the rutile TiO2(100)-(1×1) surface is the formation of a dioxymethylene intermediate in which the carbonyl O atom of CH2O is bound to a Ti atom at the five-fold-coordinated Ti4+ (Ti5c) site and its carbonyl C atom bound to a nearby bridge-bonded oxygen (Ob) atom, respectively. During 355 nm irradiation, the dioxymethylene intermediate can transfer an H atom to the Ob atom, thus forming HCOO- directly, which is considered as the main reaction channel. In addition, the dioxymethylene intermediate can also transfer methylene to the Ob row and break the C-O bond, thus leaving the original carbonyl O atom at the Ti5c site. After the transfer of methylene, several pathways to products are available. Thus, we have found that Ob atoms are intimately involved in the photoinduced decomposition of CH2O on the rutile TiO2(100)-(1×1) surface.  相似文献   

12.
L.E. Firment 《Surface science》1982,116(2):205-216
Temperature dependent faceting of rutile TiO2 surfaces cut to the (001) plane has been reported [Tait and Kasowski, Phys. Rev. B20 (1979) 5178]. By comparing LEED data to beam positions calculated for various sets of facet planes, the facet planes have been identified. The first ordered structure observed on annealing ion bombarded surfaces is composed of {011} facets with the facet planes in a (2 × 1) reconstruction. The high temperature structure produced on annealing above 1300K is best described as {114} facets; however, there are deviations of the observed LEED pattern from that calculated for {114} facets, possibly because of the presence of related planes. LEED data have now been obtained on the behavior of (110), (100), (011), (114), and (001) surfaces in UHV. The observed stability of TiO2 surfaces can be related to the Ti ion coordination numbers in the surface plane as derived from stoichiometric terminations of the rutile lattice.  相似文献   

13.
利用程序升温脱附谱研究了用266 nm激光在表面制备不同氧空位浓度的方法.实验表明利用266 nm激光能够很容易产生表面氧空位.同样90 s光照,在光子数密度大于6.7×1016 photons/cm2s的时候,表面氧空位浓度和和光子数密度成线性关系.在光照过程中,没有观测到氧气和钛原子的脱附,表明利用266 nm激光在TiO2(110)-(1×1)制备氧空位是一种有效而且温和的方式.而在表面提前吸附水利用激光产生氧空位的速率比干净的表面慢了两个数量级.进一步研究表面,预先吸附了水后,在光照过程中水更容易脱附,导致桥氧原子的脱附被抑制,降低了氧空位产生的速率  相似文献   

14.
Methanol/TiO2(110) is a model system in the surface science study of photocatalysis where methanol is taken as a hole capture. However, the highest occupied molecular orbital of adsorbed methanol lies below the valence band maximum of TiO2, preventing the hole transfer. To study the level alignment of this system, electronic structure of methanol covered TiO2(110) surface has been measured by ultraviolet photoelectron spectroscopy and the molecular orbitals of adsorbed methanol have been clearly identified. The results indicate the weak interaction between methanol and TiO2 substrate. The static electronic structure also suggests the mismatch of the energy levels. These static experiments have been performed without band gap excitation which is the prerequisite of a photocatalytic process. Future study of the transient electronic structure using time-resolved UPS has also been discussed.  相似文献   

15.
Ultrafast interfacial electron transfer from the donor orbital of organic chromophores into empty electronic acceptor states of a semiconductor and of a metal was investigated by two-photon photoemission spectroscopy (2PPE). Experimental tools and procedures have been developed for carrying out wet-chemistry preparation of the molecule/solid interface. The organic chromophore perylene was investigated with several different bridge/anchor groups on TiO2(110). One perylene compound was investigated for comparison on Ag(110). Angle and polarization dependent 2PPE measurements revealed the orientation of the perylene chromophore on the surface as controlled by the adsorption geometry of the respective anchor group on TiO2. UPS measurements gave the position of the HOMO level of the chromophore with respect to the Fermi level of the solid. The donor level of each molecule was found high enough to fulfill the “wide band limit” of heterogeneous electron transfer dynamics. Time constants for heterogeneous electron transfer were extracted from 2PPE transients. A difference by a factor of four was found, 13 fs against 47 fs, when a conjugated bond was exchanged for a saturated bond in the otherwise identical bridge group. The two different contributions to the 2PPE transients arising firstly from the excited state of the chromophore and secondly from the injected electrons were separated by measuring the latter contribution separately in the case of instantaneous interfacial electron transfer realized with catechol as adsorbate. The time scales measured for the electron transfer step and for the subsequent electron escape process from the surface into the bulk of TiO2 showed both good agreement with recent theoretical predictions of other groups for these systems. PACS 42.65.Ky; 79.60.BM; 78.47.+p; 73.20.-r; 79.60.Jv; 79.60.-i  相似文献   

16.
Titanium oxides are used in a wide variety of technological applications where surface properties play a role. TiO2 surfaces, especially the (110) face of rutile, have become prototypical model systems in the surface science of metal oxides. Reduced TiO2 single crystals are easy to work with experimentally, and their surfaces have been characterized with virtually all surface-science techniques. Recently, TiO2 has also been used to refine computational ab initio approaches and to calculate properties of adsorption systems. Scanning tunneling microscopy (STM) studies have shown that the surface structure of TiO2(110) is more complex than originally anticipated. The reduction state of the sample, i.e. the number and type of bulk defects, as well as the surface treatment (annealing in vacuum vs. annealing in oxygen), can give rise to different structures, such as two different (1×2) reconstructions, a ‘rosette’ overlayer, and crystallographic shear planes. Single point defects can be identified with STM and influence the surface chemistry in a variety of ways; the adsorption of water is discussed as one example. The growth of a large number of different metal overlayers has been studied on TiO2(110). Some of these studies have been instrumental in furthering the understanding of the ‘strong metal support interaction’ between group-VIII metals and TiO2, as well as low-temperature oxidation reactions on TiO2-supported nanoscopic gold clusters. The growth morphology, interfacial oxidation/reduction reaction, thermal stability, and geometric structure of ultra-thin metal overlayers follow general trends where the most critical parameter is the reactivity of the overlayer metal towards oxygen. It has been shown recently that the technologically more relevant TiO2 anatase phase can also be made accessible to surface investigations. Received: 4 March 2002 / Accepted: 20 October 2002 / Published online: 5 February 2003 RID="*" ID="*"Corresponding author. Fax: +1-504/862-8279, E-mail: diebold@tulane.edu  相似文献   

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