TiO2纳米粒子膜的表面态性质及其光催化活性的研究

TiO₂纳米粒子膜催化剂光催化降解水中污染物,与粉末相比具有可重复使用、易回收等优点,近年来,在光化学领域受到人们的高度重视^[1～3].膜催化剂的表面性质与其光催化活性直接相关,研究这些性质能够为研制、开发高效催化剂提供理论依据.本文采用TiCl₄水解法,制备了酸性、碱性条件下TiO₂纳米粒子膜.利用原子力显微镜(AFM)、X-射线衍射谱(XRD)、红外光谱(IR)和场诱导表面光电压谱(EFISPS)测定其表面微结构.考察了它们对苯酚降解的光催化活性,讨论了膜催化剂的表面性质对光催化活性的影响.     

阳极氧化水解法制备TiO2纳米膜

TiO2在光电化学电池领域已成为比较重要的半导体材料，自从1972年，Fuishima和Honda首次把TiO2电极用于光电解水以来，人们已经使用多种方法，如化学气相沉积、TiO2粉的烧结、RF射频溅射、等离子体喷涂或用胶体TiO2涂膜等各种方法，来制备单晶（金红石），多晶（金红石、锐钛矿     

TiO2与ZnO复合纳米结构电极的光电化学研究

利用尿素加压共沉淀法以Ti(SO4)2与Zn(NO3)2为原料制备了TiO2-ZnO复合纳米粒子, 其纳米结构电极的光电化学研究结果表明, 反应物摩尔比为3∶1, 于530 ℃煅烧制备的复合纳米结构电极的光电转换效率最高. 对吸附染料RuL2(SCN)2∶2TBA的纳米结构TiO2和各种复合纳米粒子的纳米结构电极进行光电研究的结果表明, 染料对各纳米结构电极都起到了敏化作用, 其中也是由反应物摩尔比为3∶1, 于530 ℃煅烧制备的纳米结构电极的光电转换效率最高. 对聚3-甲基噻吩修饰的纳米结构TiO2和摩尔比为3∶1, 于530 ℃煅烧的复合纳米粒子构成的纳米结构电极进行光电性能研究, 结果表明, 聚3-甲基噻吩与半导体纳米粒子之间存在p-n结, 在一定条件下p-n结的存在有利于光生电子/空穴的分离, 从而提高了光电转化效率.     

间接电氧化法合成甘油醛

通过电化学合成前驱体和溶胶-凝胶法在Ti表面修饰一层纳米TiO2膜,在纳米Ti02膜上电沉积分散的Pt微粒制成钛基纳米TiO2-Pt(Ti/nano-TiO2-pt)修饰电极。采用循环伏安法、间接电氧化法研究了纳米Ti02-Pt修饰电极的电催化活性以及Mn^3 ／Mn^2 媒质氧化甘油为甘油醛的过程。结果表明,纳米Ti02-Pt修饰电极对Mn^2 的电氧化具有高催化活性,电流效率可达90％以上,非均相电解得到的Mn^3 可一步氧化甘油为甘油醛,收率为91％。     

STS study of TiO2 film and Pt-deposited TiO2 film in air

Direct investigation of the electronic structure of catalyst surfaces on the near-atomic scale in general has not been impossible in the past. However, with the advent of the scanning tunneling microscope (STM), the opportunity arises for incorporating the scanning tunneling spectroscopy (STS) for correlation in-situ surface electronic structure with topography on a sub-nanometer scale. In this paper, we report the STS results of thin film TiO2 and Pt-deposited TiO2 annealed at 450℃. It was found that the TiO2 semiconductor changes from n-type to p-type after Pt deposition.Fig. 1 shows the surface electronic property (Ⅰ-Ⅴ curve) of thin TiO2 film measured in air by STS. A steep descent of the anodic tunneling current at ca.- 1.0 Ⅴ and a rapid ascent of cathodic tunneling current at ca. +2.0V. The zero bias represents the Fermi level (Ef). Ef is situated at the Ecb side indicating that the thin TiO2 film possesses the same band gap as that of bulk TiO2 phase ( Egs =3.0 to 3.2 eV). For the sample of Pt-deposited TiO2 film, Pt/(Pt+Ti+O) atomic ratio≈0.2, which indicates that the surface of TiO2 film is partly covered by Pt particles, and there are two types of Ⅰ-Ⅴ curves to be detected. One of them (Fig.2a)is attributed to the electronic property of TiO2, which has same Egs as that shown in Fig. 1. However, the Ef is transferred to valence side (△≈1eV). This phenomenon hints that TiO2 is doped by an impurity which can introduce h+ into TiO2 lattice.Such a type of defects may be described by Ti1-xPtxO2(h )2x, here Pt+2 as a substitutional site of Ti+4. Fig.2b is the Ⅰ-Ⅴ curve of a Pt particle situated on a TiO2 particle contained Ti1-xPtxO2(h )2x.     

直流反应磁控溅射制备的Mo掺杂TiO2薄膜的光电特性

通过直流反应磁控溅射制备了不同Mo掺杂量的Mo-TiO2薄膜.用原子力显微镜(AFM)、X射线衍射(XRD)仪、X射线光电子能谱(XPS)仪、紫外-可见(UV-Vis)分光光度计详细研究了Mo掺杂量对薄膜表面形貌、晶体结构、元素价态及吸收带边的影响.用瞬态光电流和循环伏安法考察了不同Mo含量ITO/Mo-TiO2电极的光电特性.结果表明:在TiO2薄膜中掺入的Mo以Mo6+和Mo5+两种价态存在;随着Mo掺杂量的增加,Mo-TiO2薄膜的晶粒尺寸逐渐减小,晶格畸变增大,吸收阈值显著红移;薄膜的禁带宽度先减小后增大,在Mo掺杂量为2.7%(n(Mo)/n(Ti))时禁带宽度最小;Mo掺杂量为0.9%的样品在氙灯下的光生电流最大,且随着所加阳极偏压的提高光生电流并未呈现出饱和的趋势.此后随着掺杂量的提高,薄膜的光生电流开始下降,当Mo掺杂量达到3.6%时,薄膜的光电流小于未掺杂的样品;说明适当浓度的Mo掺杂能够提高Mo-TiO2薄膜光电性能,光生电流最大可达未掺杂的2.4倍.     

电沉积二氧化钛纳米微粒膜的光电化学性能和表面形貌研究

采用光电流谱、透射光谱和扫描微探针显微镜技术对电沉积法制备的二氧化钛纳米微粒膜的光电化学性能和表面形貌进行了研究.结果表明,不同制备条件下的二氧化钛纳米微粒膜具有与紧密的半导体电极不同的光电化学性质,并探讨了其光电化学性能与表面形貌的关系.     

Self-assembly and photoelectric properties of cerium complexes with 3,4,9,10-perylenetetracarboxylic acid on nanocrystalline TiO_2 films

Self-assembled (SA) films (PMP, M = Ce3+ or Ce4+) of 3,4,9,10-perylenetetracarboxylic acid (PTA) on nanocrystalline TiO2 films with Ce3+ or Ce4+ as a bridge were fabricated and characterized with UV-Vis, IR, and XPS synchrotron radiation photoelectron spectroscopy (SRPES) which gave the HOMO energy levels for the SA films. It was shown that thin-layer sandwich-type solar cells based on these SA films possess good properties for photoelectric conversion. While PTA-loaded TiO2 electrode (P) generated 26.9% of incident monochromatic photon-to-electron conversion efficiency (IPCE), PMP-sensitized Ti02 electrodes yielded 55.8% and 39.1% for Ce4+ and Ce3+ respectively. PMP films can be considered as a kind of complexes whose HOMO energy levels were proved to be higher than that of film P, which is one of the major reasons for the increase in IPCE from film P to film PMP.     

Au改性纳米TiO2材料对NPE-10光催化降解的活性

以钛酸四丁酯和氯金酸为原料，通过溶胶凝胶法制备了Au掺杂的纳米TiO2光催化剂粉体，并用 XRD， BET，XPS和固体紫外可见吸收光谱等技术对其晶相结构，比表面积，表面组成及紫外可见光响应范围进行了表征，对其光催化降解非离子表面活性剂壬基酚聚氧乙烯醚（NPE-10）的活性进行了考察. 结果表明，掺杂的Au在纳米TiO2粉体材料中可能以两种形态存在，即以Au3+离子形式替代Ti4+进入TiO2晶格和以Au原子态形式暴露于粉体表面.前者使TiO2在480～650 nm出现了更强的光吸收，并大大地增强了粉体表面对氧物种的吸附；后者中处于表面原子态的Au又会成为光生电子的受体，有效地避免了光生电子空穴对的复合. 通过对掺杂量及处理温度的优化，在nAu3+/nTi4+=0.005， 500 ℃煅烧的条件下可以制得具有较高的光催化活性的Au/TiO2粉体. 对NPE-10的光催化氧化试验显示，日光照射4小时后降解效率可以达到91.8%；而用未改性的纳米TiO2，在同样条件下，NPE-10的光催化降解效率仅能达到50.2%，商品Degussa P-25也只能达到66%.     

N doping of TiO2(110): photoemission and density-functional studies

The electronic properties of N-doped rutile TiO2(110) have been investigated using synchrotron-based photoemission and density-functional calculations. The doping via N2+ ion bombardment leads to the implantation of N atoms (approximately 5% saturation concentration) that coexist with O vacancies. Ti 2p core level spectra show the formation of Ti3+ and a second partially reduced Ti species with oxidation states between +4 and +3. The valence region of the TiO(2-x)N(y)(110) systems exhibits a broad peak for Ti3+ near the Fermi level and N-induced features above the O 2p valence band that shift the edge up by approximately 0.5 eV. The magnitude of this shift is consistent with the "redshift" observed in the ultraviolet spectrum of N-doped TiO2. The experimental and theoretical results show the existence of attractive interactions between the dopant and O vacancies. First, the presence of N embedded in the surface layer reduces the formation energy of O vacancies. Second, the existence of O vacancies stabilizes the N impurities with respect to N2(g) formation. When oxygen vacancies and N impurities are together there is an electron transfer from the higher energy 3d band of Ti3+ to the lower energy 2p band of the N(2-) impurities.     

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.     

Large oriented arrays and continuous films of TiO(2)-based nanotubes

We report for the first time a one-step, templateless method to directly prepare large arrays of oriented TiO2-based nanotubes and continuous films. These titania nanostructures can also be easily prepared as conformal coatings on a substrate. The nanostructured films were formed on a Ti substrate seeded with TiO2 nanoparticles. SEM and TEM results suggested that a folding mechanism of sheetlike structures was involved in the formation of the nanotubes. The oriented arrays of TiO2 nanotubes, continuous films, and coatings are expected to have potentials for applications in catalysis, filtration, sensing, photovoltaic cells, and high surface area electrodes.     

The role of photoinduced defects in TiO2 and its effects on hydrogen evolution from aqueous methanol solution

The hydrogen evolution from aqueous methanol solutions was found to follow two stages of zero order kinetics during photoreactions using TiO 2 as the photocatalyst. Maximal hydrogen evolution was found at the 10% (v/v) methanol solution. X-ray photoelectron spectroscopy (XPS) shows that Ti(1566) defects are formed on the surface of TiO 2 and X-ray powder diffraction (XRD) indicates that Ti(1566) defects are also formed in the bulk after photoreaction. Formation of defects is also shown by broadening of Bragg peaks and blue shifts and peak broadening in Raman spectroscopy. The defect disorder results in the increase of hydrogen evolution. UV-vis diffuse reflection spectra confirm that new absorptions in the visible light region are related to the defect content. At high methanol concentration, XPS implies that the active sites of the surface are blocked by hydroxyl groups, which results in the decrease of hydrogen evolution. TEM images showed that the photoreaction occurred on the surface of the photocatalyst as the surface of the TiO 2 became rough after the photoreaction.     

铂、钌共修饰的氧化钛电极对甲醇的电催化氧化

燃料电池;铂、钌共修饰的氧化钛电极对甲醇的电催化氧化     

紫外光照下纳米TiO2电极的电化学行为

通过电沉积方法制备了纳米TiO2薄膜电极，应用循环伏安和交流阻抗技术研究了TiO2电极在253.7 nm的紫外光照射下的电化学行为.结果表明, TiO2薄膜电极的循环伏安图在＋0.15 V处出现新的氧化峰,交流阻抗谱的半圆明显减小，电极的开路电位在有光和无光的情况下呈现规律变化.实验证实在紫外光照射下电极表面有新物种Ti3＋生成，但光生Ti3＋不稳定.     

甲醇在铂修饰的氧化钛电极上电催化氧化行为的研究

运用电化学方法评价了电化学阴极还原-阳极氧化两步法制得的以钛为基体的铂修饰的钛氧化物(Pt-TiO_x/Ti)电极对甲醇电催化氧化的性能,结果表明,制得的修饰电极对甲醇氧化呈现了很高的电催化活性和好的稳定性.通过X光电子能谱(XPS)、扫描隧道显微镜(STM)和现场傅立叶变换红外(FTIR)反射光谱等技术,发现修饰电极对甲醇氧化具有高的电催化性能,可归属于纳米级Pt粒子在TiO_x中的高度分散及由于Pt和TiO_x的相互作用,使电极表面对甲醇氧化中间产物CO的吸附量大大降低.     

Photophysical and photocatalytic properties of SrTiO3 doped with Cr cations on different sites

Usually, SrTiO3 monodoped with Cr cations at the Ti4+ site hardly shows visible light photocatalytic activity. Revealing the origin of this issue is important for us to find an alternative approach to make SrTiO3 active under visible light irradiation. In this paper, two Cr-doped SrTiO3-(Sr0.95Cr0.05)TiO3 and Sr(Ti0.95Cr0.05)O3-were synthesized by a conventional solid-state reaction method, and their photophysical and photocatalytic properties were studied comparatively. It was found that both (Sr0.95Cr0.05)TiO3 and Sr(Ti0.95Cr0.05)O3 showed considerable absorption to visible light. However, their photocatalytic activities for H2 evolution from aqueous methanol solution under visible light irradiation were significantly different: the H2 evolution rate over (Sr0.95Cr0.05)TiO3 (approximately 21 micromol/h) was more than 100 times that over Sr(Ti0.95Cr0.05)O3 (approximately 0.2 micromol/h). X-ray photoelectron spectroscopy analysis results revealed that the Cr cations doped at the Sr2+ site were all trivalent state (Cr3+), while those doped at the Ti4+ site were mixed valent states (Cr3+ and Cr6+). The different photocatalytic activities of H2 evolution are supposed to closely relate to the different valent states of Cr doped at different sites (Sr2+ or Ti4+) in SrTiO3. Possible electronic structures of (Sr0.95Cr0.05)TiO3 and Sr(Ti0.95Cr0.05)O3 were proposed in relation to their photophysical and photocatalytic properties.     

TiO2膜光催化剂的改进及表征

提出用粉末-溶胶法制备TiO2薄膜型光催化剂,介绍了粉溶法的制备工艺及改变pH值对催化活性的影响.研究结果表明, 利用粉溶法或添加浓HNO3后制备的TiO2薄膜光催化剂表现出了较高的光催化活性.结合结构表征详细分析了其中的原因.认为粉溶法制备的催化剂表面更粗糙,比表面积增大,膜厚度减小,这些都可能是其催化活性提高的原因.而加酸后膜催化活性提高主要是因为酸性条件下表面几乎没有Ti3+表面态,利于光生电子与光生空穴的分离.     

溶胶法制备的二氧化硅与二氧化钛复合薄膜的性能

在室温下, 采用溶胶法在玻璃基板上制备了厚度约为100 nm的均匀、透明的纳米SiO2-TiO2复合薄膜.研究了不同温度处理后薄膜的超亲水性、光催化能力等光致活性.通过XPS对薄膜表面及近表面元素的化学态的研究发现, Ti在表面及近表面不仅以Ti4＋形式存在, 也存在少量Ti3＋.紫外光照射后, 部分Ti4＋ 转变成了Ti3＋. XRD研究表明, 该薄膜中的TiO2主要以锐钛矿形式存在, 而且其晶粒大小为14～20 nm.用AFM研究了SiO2-TiO2薄膜的表面形貌及不同的温度处理对TiO2颗粒大小的影响.     

Synthesis and Spectral Properties of Novel Water-soluble Near-infrared Fluorescent Indocyanines

Two fluorescent pentamethine and a squarylium indocyanines containing at least one p-carboxybenzyl group on N atoms in the heterocyclic rings were synthesized. They had good water solubility and photostability. Their maximum absorption and maximum emission were 600-700 nm in water. When it was anchored onto nanostructured TiO2 electrode, compared with in water, the squaraine showed double absorption peaks (one blue shifted and another red shifted) and absorption intensity of the red shift peak increased with the increase of the time of irradiation. The intensity of the blue one decreased simultaneously. We proposed that the presence of two electronic charge forms of squaraine anchored on the TiO2 film might be the reason.