Ni(110)上氯和氧共吸附表面的结构和性质

用XPS,UPS,AES和功函数测定等方法考察了氯和氧在Ni(110)上的共吸附。氯强烈阻碍了氧的接续吸附;相反,氯接续吸附的速度和吸附量却因氯能驱使预吸附的氧溶入体相而没有明显影响。角分辨XPS分析为这一共吸附模型提供了进一步的证据。共吸附表面上氯和氧的热脱附和两者单独在Ni(110)表面上热脱附过程相似,但两者的脱附温度都有明显的降低。对共吸附和热脱附的机理进行了详细的讨论。     

~(15)NO与Mo(100)-c(2×2)N表面相互作用的HREELS和TDS研究

利用高分辨电子能量损失谱（ Ｈ Ｒ Ｅ Ｅ Ｌ Ｓ） 和热脱附谱（ Ｔ Ｄ Ｓ）, 研究了１５ Ｎ Ｏ 在 Ｍｏ（１００）ｃ（２×２） Ｎ 表面上的吸附态及其随温度的变化． １２０ Ｋ 时, 在 Ｍ ｏ（１００）ｃ（２×２） Ｎ 表面低暴露量的１５ Ｎ Ｏ 发生解离和分子吸附, 解离生成的１５ Ｎ 在１ ２３０ Ｋ 与另一１５ Ｎ 原子或氮化钼中的１４ Ｎ 原子并合、脱附． 在升温时大部分分子吸附的１５ Ｎ Ｏ 发生解离和反应, 解离生成的１５ Ｎ 原子与另一１５ Ｎ 原子生成１５ Ｎ２ 而脱附, 或与表面残存的１５ Ｎ Ｏ 生成１５ Ｎ２ Ｏ 脱附． １５ Ｎ２ Ｏ 的脱附峰温与 Ｍｏ（１００）表面相比, 升高了约１５０ Ｋ, 可能与形成氮化钼后电子由金属钼向非金属氮转移有关． 电子能量损失谱（ Ｅ Ｌ Ｓ）表明, １５ Ｎ Ｏ 在 Ｍｏ（１００）ｃ（２×２） Ｎ 表面生成了一种新的１４ Ｎ１５ Ｎ Ｏ 物种． ３００ Ｋ 时, 低暴露量的１５ Ｎ Ｏ 在 Ｍ ｏ（１００）ｃ（２×２） Ｎ 表面解离吸附; 高暴露量时, 存在分子吸附的１５ Ｎ Ｏ．     

预吸附氧对NO在Pt(110)表面吸附和分解的影响

 利用程序升温反应谱、X射线光电子能谱和高分辨电子能量损失谱研究了NO在清洁和预吸附氧的Pt(110)表面的吸附和分解. 在清洁的Pt(110)表面,室温下低覆盖度时NO以桥式吸附为主,高覆盖度时NO以线式吸附为主. 加热过程中部分NO(主要是桥式吸附物种)分解,生成N2和N2O. 室温下O2在Pt(110)表面发生解离吸附. Pt(110)表面预吸附氧会抑制桥式吸附NO的生成,并导致其脱附温度降低40 K. 降低脱附温度有利于桥式吸附NO的分子脱附,从而抑制分解反应. 这些结果从表面化学的角度合理地解释了铂催化剂在富氧条件下对NO分解能力的降低.     

氧在C－Ni（100）表面反应动力学的研究──Ⅱ．动力学计算结果

根据Ｏ２＋Ｃ－Ｎｉ（１００）表面反应的推广ＬＥＰＳ势能面，并用ＱＣＴ方法研究了该体系的反应动力学行为．结果给出了分子化学吸附和解离原子化学吸附及ＣＯ脱附反应的分子动态特征，以及态－态过程的吸附几率．考察了各种能量形式对吸附、脱附几率的影响和各类吸附、脱附几率的变化规律．     

~(13)CH_3OH在Pd-La_2O_3/SiO_2催化剂上的程序升温脱附和分解及共吸附物类的相互作用

用质谱检测的程序升温脱附研究了~(13)CH_3OH在不同La_2O_3含量的Pd-La_2O_3/SiO_2催化剂上的脱附和分解。高温He处理的催化剂室温下对甲醇的吸附容量随La_2O_3含量增加而增加,但其脱附和分解产物之比几乎为常数。氢还原的催化剂室温下对甲醇吸附容量在Pd/La体相原子比为1:1时达最大值,但甲醇脱附和分解产物之比值随La_2O_3含量增加而增加,且产物中CO_2随La_2O_3含量增加而减少。CH_3OH和~(13)CH_3OH次序吸附后的TPD谱表明在催化剂上有对甲醇的分子吸附中心,可置换的解离吸附中心和不可置换的强解离吸附中心。CO和~(13)CH_3OH共吸附的TPD谱表明:在CO和~(13)CH_3OH共吸附物类之间有相互排斥的作用。这种作用有利于CO吸附态的重新分布和脱附,因此阻止了CO的岐化反应。     

乙酸在Rh(100)表面吸附和分散的HREELS和TDS研究

 用高分辨电子能量损失谱（HREELS）和热脱附谱（TDS）研究了乙酸在Rh（100）表面上的吸附和分解,提出了乙酸吸附和分解反应的模式．130K时,高暴露量的乙酸在Rh（100）表面上形成多层吸附的凝聚态乙酸．升温至290K时,部分乙酸以分子形式直接脱附,另一部分乙酸分子通过O—H键断裂形成乙酸根和氢吸附在表面上;在升温至400K的过程中,乙酸根在表面发生两个相互竞争的反应,即乙酸根分解成CO,CHx,O和H,以及乙酸根分解成CHx,H和CO2;升温至500K,只剩下CHx,O和CO吸附在表面上;600K后,表面吸附的CHx完全解离,同时表面吸附的碳原子和氧原子结合成CO脱附．     

用分子轨道理论研究NO气体在TiO2表面吸附

根据一氧化氮(NO)气体在二氧化钛(TiO)表面吸附和脱附的实验结果,揭示了气体脱附量的变化规律．利用MOPAC和GAUSSIAN分子轨道理论计算了在TiO2(110)表面上吸附NO分子的原子簇模型,电荷分布以及原子簇的能级,推断了NO在TiO(110)表面吸附的稳定性．     

用分子轨道理论研究NO气体在TiO2表面吸附

根据一氧化氮(NO)气体在二氧化钛(TiO₂)表面吸附和脱附的实验结果, 揭示了气体脱附量的变化规律. 利用MOPAC 和GAUSSIAN分子轨道理论计算了在TiO₂(110)表面上吸附NO分子的原子簇模型, 电荷分布以及原子簇的能级, 推断了NO在TiO₂(110)表面吸附的稳定性.     

NO2在Ag/Pt(110)双金属表面上的吸附和分解

利用俄歇电子能谱(AES)和程序升温脱附谱(TDS)研究了NO₂在Ag/Pt(110)双金属表面的吸附和分解.室温下NO₂ 在Ag/Pt(110)双金属表面发生解离吸附, 生成NO(ads)和O(ads)表面吸附物种. 在升温过程中NO(ads)物种发生脱附或者进一步分解. 500 K时NO₂在Ag/Pt(110)双金属表面发生解离吸附生成O(ads)表面吸附物种. Pt 向Ag传递电子, 从而削弱Pt－O键的强度, 降低O(ads)从Pt 表面的并合脱附温度. 发现能够形成具有稳定组成的Ag/Pt(110)合金结构, 其表现出与Pt(110)-(1×2)相似的解离吸附NO₂能力, 但与O(ads)的结合明显弱于Pt(110)-(1×2). 该AgPt(110)合金结构是可能的低温催化直接分解氮氧化物活性结构.     

^15NO与Mo（100）—c（2＊2）N表面相互作用的HREELS和TDS研究

利用高分辨子能量人谱和热脱附谱,研究了在Ｍｏ（１００）－ｃ（２＊２）Ｎ表面上的吸附态及其随温度的变化,１２０Ｋ时,在Ｍｏ（１００）－ｃ（２＊２）Ｎ表面低暴露的＾１５ＮＯ发生解度和分子吸附,解离生成的＾１５Ｎ在１２３０Ｋ与另一＾１５Ｎ原子或氮化钼中的＾１４Ｎ原子并合,脱附,在升温时大部分分子吸附的＾１５ＮＯ发生解离和反应,解离生成的＾１５Ｎ原子与另一＾１５Ｎ原子生成＾１５Ｎ２而脱附,与表面残存＾１５     

Active Sites for Adsorption and Reaction of Molecules on Rutile TiO2(110) and Anatase TiO2(001) Surfaces (cited: 1)

The reactivity of specific sites on rutile TiO₂(110)-(1×1) surface and anatase TiO₂(001)-(1×4) surface has been comparably studied by means of high resolution scanning tunneling microscopy. At the rutile TiO₂(110)-(1×1) surface, we find the defects of oxygen vacancy provide distinct reactivity for O₂ and CO₂ adsorption, while the terminal fivefold-coordinated Ti sites dominate the photocatalytic reactivity for H₂O and CH₃OH dissociation. At the anatase TiO₂(001)-(1×4) surface, the sixfold-coordinated terminal Ti sites at the oxidized surface seem to be inert in both O₂ and H₂O reactions, but the Ti-rich defects which introduce the Ti³⁺ state into the reduced surface are found to provide high reactivity for the reactions of O₂ and H₂O. By comparing the reactions on both rutile and anatase surfaces under similar experimental conditions, we find the reactivity of anatase TiO₂(001) is actually lower than rutile TiO₂(110), which challenges the conventional knowledge that the anatase (001) is the most reactive TiO₂ surface. Our findings could provide atomic level insights into the mechanisms of TiO₂ based catalytic and photocatalytic chemical reactions.     

Kinetics and Dynamics of Photocatalyzed Dissociation of Ethanol on TiO2(110) (cited: 2)

The kinetics and dynamics of photocatalyzed dissociation of ethanol on TiO₂(110) sur-face have been studied using the time-dependent and time-resolved femtosecond two-photon photoemission spectroscopy respectively, in order to unravel the photochemical properties of ethanol on this prototypical metal oxide surface. By monitoring the time evolution of the photoinduced excited state which is associated with the photocatalyzed dissociation of ethanol on Ti_5c sites of TiO₂(110), the fractal-like kinetics of this surface photocatalytic reaction has been obtained. The measured photocatalytic dissociation rate on reduced TiO₂(110) is faster than that on the oxidized surface. This is attributed to the larger defect density on the reduced surface which lowers the reaction barrier of the photocatalytic reaction at least methodologically. Possible reasons associated with the defect electrons for the acceleration have been discussed. By performing the interferometric two-pulse corre-lation on ethanol/TiO₂(110) interface, the ultrafast electron dynamics of the excited state has been measured. The analyzed lifetime (24 fs) of the excited state is similar to that on methanol/TiO₂(110). The appearance of the excited state provides a channel to mediate the electron transfer between the TiO₂ substrate and its environment. Therefore studying its ultrafast electron dynamics may lead to the understanding of the microscopic mechanism of photocatalysis and photoelectrochemical energy conversion on TiO₂.     

Direct Observation of Ethanol Photocatalysis on Rutile TiO2(110) Surface

Photocatalytic dissociation of ethanol molecules on the rutile TiO₂(110) surface after UV irradiation has been investigated by scanning tunneling microscope at 80 K. Most of the ethanol molecules adsorb molecularly at Ti sites, similar to the case of methanol. After UV irradiation, two different protrusions of products were observed, one of them has been identified by the technique of tip manipulation, which was likely composed of an acetaldehyde in the middle and two bridge-bonded hydroxyls on both neighbored oxygen sites. Multi-time irradiation experiments have also been performed to further understand the relationship between the two protrusions and the process of ethanol photocatalytic dissociation. These results provide detailed insights into the photocatalysis of ethanol on rutile TiO₂(110), which would help us to understand how phtotocatalytic reactions of ethnaol proceed at the fundamental level.     

Thermal-, photo- and electron-induced reactivity of hydrogen species on rutile TiO2(110) surface: Role of oxygen vacancy

The formation and reactivity of various types of hydrogen species on rutile TiO₂(110), including surface hydroxyl group, surface hydride species and bulk hydrogen species sensitively depend on the oxygen vacancy concentration and structure.     

Cr掺杂金红石相TiO2(110)单晶薄膜的制备、表征及光催化活性

采用脉冲激光沉积术(PLD)同质外延生长了表面原子级平整的6%(原子比)Cr 掺杂的金红石相TiO₂(110)单晶薄膜, 采用扫描隧道显微镜(STM)、扫描隧道谱(STS)、X 射线光电子能谱(XPS)和紫外光电子能谱(UPS)对其进行了表征. 结果表明: Cr 掺杂对TiO₂(110)-(1×1)表面的形貌没有明显影响, 但是提高了掺杂薄膜在负偏压的导电性; Cr与晶格O键合而呈现+3价态, 由此在TiO₂的价带顶上方~0.4 eV处引入杂质能级. 紫外-可见光吸收谱显示薄膜的光吸收能力被扩展到~650 nm, 处于可见光范围. 借助STM以单个甲醇分子的光解反应检测了薄膜的光催化活性. 仅观察到紫外光照射下甲醇分子的脱氢反应, 在可见光照射下(λ>430 nm)甲醇分子没有发生反应, 表明单独的Cr掺杂可能不足以提高TiO₂在可见光下的催化活性.     

Suppression of Photoinduced BBO Defects Generation on TiO2(110) by Water (cited: 1)

We have investigated creation of variable concentrations of defects on TiO₂(110)-(1×1) sur-face by 266 nm laser using temperature programmed desorption technique. Oxygen-vacancy defects can be easily induced by ultraviolet light, the defects concentration has a linear dependence on power density higher than 50 mW/cm² for 90 s irradiation. No observa-tion of O₂ molecule and Ti atom desorption suggests that UV induced defects creation on TiO₂(110)-(1×1) is an effective and gentle method. With pre-dosage of thin films of water,the rate of defects creation on TiO₂(110)-(1×1) is slower at least by two orders of magnitude than bare TiO₂(110)-(1×1) surface. Further investigations show that water can be moreeasily desorbed by UV light, and thus desorption of bridging oxygen is depressed.     

Photoelectron Spectroscopic Study of Methanol Adsorbed Rutile TiO2(110) Surface

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.     

Stepwise Photocatalytic Dissociation of Methanol and Water on TiO(2)(110)

We have investigated the photocatalysis of partially deuterated methanol (CD(3)OH) and H(2)O on TiO(2)(110) at 400 nm using a newly developed photocatalysis apparatus in combination with theoretical calculations. Photocatalyzed products, CD(2)O on Ti(5c) sites, and H and D atoms on bridge-bonded oxygen (BBO) sites from CD(3)OH have been clearly detected, while no evidence of H(2)O photocatalysis was found. The experimental results show that dissociation of CD(3)OH on TiO(2)(110) occurs in a stepwise manner in which the O-H dissociation proceeds first and is then followed by C-D dissociation. Theoretical calculations indicate that the high reverse barrier to C-D recombination and the facile desorption of CD(2)O make photocatalytic methanol dissociation on TiO(2)(110) proceed efficiently. Theoretical results also reveal that the reverse reactions, i.e, O-H recombination after H(2)O photocatalytic dissociation on TiO(2)(110), may occur easily, thus inhibiting efficient photocatalytic water splitting.     

Unique adsorption behaviors of NO and O2 at hydrogenated anatase TiO2(101)

The extra electron on the hydrogenated anatase TiO₂(101) is localized at the nearest Ti_5c only, and the chargetransfer promoted NO and O₂ adsorptions are also site-selective. These results are totally different from those at hydrogenated rutile TiO₂(110).     

Characterization of the Excited State on Methanol/TiO2(110) Interface (cited:2)

The electronic structure of methanol/TiO₂(110) interface has been studied by photoemission spectroscopy. The pronounced resonance which appears at 5.5 eV above the Fermi level in two-photon photoemission spectroscopy (2PPE) is associated with the photocatalyzed dissociation of methanol at vefold coordinated Ti sites (Ti_5c) on TiO₂(110) surface [Chemical Science 1, 575 (2010)]. To check whether this resonance signal arises from initial or intermediate states, photon energy dependent 2PPE and comparison between one-photon photoemission spectroscopy and 2PPE have been performed. Both results consistently suggest the resonance signal originates from the initially unoccupied intermediate states, i.e., excited states. Dispersion measurements suggest the excited state is localized. Time-resolved studies show the lifetime of the excited state is 24 fs. This work presents comprehensive characterization of the excited states on methanol/TiO₂(110) interface, and provides elaborate experimental data for the development of theoretical methods in reproducing the excited states on TiO₂ surfaces and interfaces.