Density functional theory study on the structural and electronic properties of low index rutile surfaces for TiO2/SnO2/TiO2 and SnO2/TiO2/SnO2 composite systems

The present study is concerned with the structural and electronic properties of the TiO2/SnO2/TiO2 and SnO2/TiO2/SnO2 composite systems. Periodic quantum mechanical method with density functional theory at the B3LYP level has been carried out. Relaxed surface energies, structural characteristics and electronic properties of the (110), (010), (101) and (00) low-index rutile surfaces for TiO2/SnO2/TiO2 and SnO2/TiO2/SnO2 models are studied. For comparison purposes, the bare rutile TiO2 and SnO2 structures are also analyzed and compared with previous theoretical and experimental data. The calculated surface energy for both rutile TiO2 and SnO2 surfaces follows the sequence (110) < (010) < (101) < (001) and the energy increases as (010) < (101) < (110) < (001) and (010) approximately = (110) < (101) < (001) for SnO2/TiO2/SnO2 and TiO2/SnO2/TiO2 composite systems, respectively. SnO2/TiO2/SnO2 presents larger values of surface energy than the individual SnO2 and TiO2 metal oxides and the TiO2/SnO2/TiO2 system renders surface energy values of the same order that the TiO2 and lower than the SnO2. An analysis of the electronic structure of the TiO2/SnO2/TiO2 and SnO2/TiO2/SnO2 systems shows that the main characteristics of the upper part of the valence bands for all the studied surfaces are dominated by the external layers, i.e., by the TiO2 and the SnO2, respectively, and the topology of the lower part of the conduction bands looks like the core layers. There is an energy stabilization of both valence band top and conduction band bottom for (110) and (010) surfaces of the SnO2/TiO2/SnO2 composite system in relation to their core TiO2, whereas an opposite trend is found for the same surfaces of the TiO2/SnO2/TiO2 composite system in relation to the bare SnO2. The present theoretical results may explain the growth of TiO2@SnO2 bimorph composite nanotape.     

不同基材上TiO2膜的表征和光催化活性评价

 采用溶胶-凝胶法在平行条件下制备了负载于钛、铝、不锈钢和玻璃等不同基材上的TiO2浸渍提拉膜,利用原子力显微镜、俄歇电子能谱、X射线衍射、漫反射紫外-可见光谱和苯甲酰胺光催化降解等手段对TiO2膜进行了表征和催化活性评价. 实验结果表明,基材的种类对TiO2膜的性能有较大影响,各膜样品虽均为锐钛矿晶型,但表面形貌显著不同. TiO2/Ti, TiO2/steel, TiO2/Al和TiO2/glass上TiO2的平均粒径分别是152, 205, 241和477 nm,且前两者的粒径分布较为集中. TiO2/Ti和TiO2/Al样品表面仅有Ti和O元素存在,而TiO2/steel和TiO2/glass表面则分别检测到有Fe和Na,Ca及Si等基材元素渗出. 各膜样品对苯甲酰胺光催化降解的活性次序是:TiO2/Ti＞TiO2/Al＞TiO2/glass＞TiO2/steel. 根据实验结果可以推测,在焙烧阶段各基材上前驱体膜烧结行为的不同以及基材元素的渗出是造成不同基材上的TiO2膜在表面形貌、化学组成、光吸收性能以及光催化活性方面存在明显差异的主要原因.     

活性碳载体对TiO2光催化降解Cl2CHCOOH性能的影响

研究了活性碳(AC)载体对TiO₂光催化降解Cl₂CHCOOH性能的影响.结果表明,加入AC载体能提高TiO₂的光催化反应速度,而且AC加入方法及含量有明显影响.本文探讨了TiO₂光催化性能提高的原因.     

Synthesis of Fe- or Ag-doped TiO2–MWCNT nanocomposite thin films and their visible-light-induced catalysis of dye degradation and antibacterial activity

Research on Chemical Intermediates - Thin films of TiO2, TiO2-multiwalled carbon nanotubes (TiO2–MWCNT), Fe-doped TiO2–MWCNT (Fe–TiO2–MWCNT), and Ag-doped TiO2–MWCNT...     

TiO_2-Supported Binary Metal Oxide Catalysts for Low-temperature Selective Catalytic Reduction of NO_x with NH_3

Binary metal oxide（MnOx-A/TiO2）catalysts were prepared by adding the second metal to manganese oxides supported on titanium dioxide（TiO2）,where,A indicates Fe2O3,WO3,MoO3,and Cr2O3.Their catalytic activity,N2 selectivity,and SO2 poisonous tolerance were investigated.The catalytic performance at low temperatures decreased in the following order：Mn-W/TiO2〉Mn-Fe/TiO2〉Mn-Cr/TiO2〉Mn-Mo/TiO2,whereas the N2 selectivity decreased in the order：Mn-Fe/TiO2〉Mn-W/TiO2〉Mn-Mo/TiO2〉Mn-Cr/TiO2.In the presence of 0.01%SO2 and 6%H2O,the NOx conversions in the presence of Mn-W/TiO2,Mn-Fe/TiO2,or Mn-Mo/TiO2 maintain 98.5%,95.8%and 94.2%, respectively,after 8 h at 120°C at GHSV 12600 h？ 1 .As effective promoters,WO3 and Fe2O3 can increase N2 selectivity and the resistance to SO2 of MnOx/TiO2 significantly.The Fourier transform infrared（FTIR）spectra of NH3 over WO3 show the presence of Lewis acid sites.The results suggest that WO3 is the best promoter of MnOx/TiO2,and Mn-W/TiO2 is one of the most active catalysts for the low temperature selective catalytic reduction of NO with NH3.     

掺磷二氧化钛的制备及其光催化性能研究

以TiCl4为原料,在低温下分别制备了纯二氧化钛和掺磷二氧化钛水溶胶,通过XRD、TEM、FT-IR、UV-vis等进行了表征。结果表明,两类样品中的TiO2颗粒均呈锐钛矿型晶相结构,粒径小于10nm,但是掺磷二氧化钛比纯二氧化钛的结晶度更高,颗粒分散更均匀,且禁带宽度和吸光度也有一定的增大,同时掺磷二氧化钛中的磷有效地溶入二氧化钛晶格中。通过对亚甲基兰的光催化降解表明,掺磷二氧化钛水溶胶的光催化性能比纯二氧化钛水溶胶大约提高了2倍。     

Single-walled carbon nanotube-facilitated dispersion of particulate TiO2 on ZrO2 ceramic membrane filters

We report that SWCNTs substantially improve the uniformity and coverage of TiO2 coatings on porous ZrO2 ceramic membrane filters. The ZrO2 filters were dip coated with 100 nm anatase TiO2, TiO2/SWCNT composites, a TiO2+SWCNT mixture, and a TiO2/MWCNT composite at pH 3, 5, and 8. Whereas the TiO2+SWCNT mixture and the TiO2/MWCNT composite promote better coverage and less clumping than TiO2 alone, the TiO2/SWCNT composite forms a complete uniform coating without cracking at pH 5 ( approximately 100% coverage). A combination of chemical and electrostatic effects between TiO2 and SWCNTs forming the composite as well as between the composite and the ZrO2 surface explains these observations.     

二氧化钛纳米粒子-氧化石墨烯/聚酰亚胺混合基质膜的原位聚合及气体渗透性能

以钛酸四丁酯为前驱体,采用浸渍-沉淀法制备二氧化钛纳米粒子-氧化石墨烯(TiO_2-GO)复合物,再将TiO_2-GO复合物与4,4'-(六氟异亚丙基)邻苯二甲酸酐和4,4'-二氨基二苯醚通过原位聚合构建TiO_2-GO/TiO_2-GO/PI(聚酰亚胺)混合基质膜,用于CO_2的渗透脱除.采用傅里叶变换红外光谱(FTIR)、拉曼光谱(Raman)、透射电子显微镜(TEM)、扫描电子显微镜(SEM)、热失重(TG)和Zeta电位等表征了TiO_2-GO复合物和TiO_2-GO/PI混合基质膜的形貌与结构;探讨了TiO_2掺杂量对TiO_2-GO复合物及TiO_2-GO/PI混合基质膜的结构和气体渗透性能的影响.结果表明,TiO_2-GO复合物中TiO_2纳米粒子较均匀地沉积在GO片层上,TiO_2纳米粒子在形成的同时破坏了GO的结构,使其无序度增加.TiO_2的掺杂对TiO_2-GO/PI混合基质膜的形貌与结构影响较小,但提升了TiO_2-GO/PI混合基质膜的CO_2和N2渗透性能.但过量的掺杂使TiO_2粒子在GO片层上团聚,从而导致TiO_2-GO复合物在混合基质膜中的分散性变差,CO_2渗透性及CO_2/N2渗透选择性降低.当TiO_2掺杂质量分数为30%时,TiO_2-GO/PI混合基质膜的CO_2渗透性为360 Barrer[1 Barrer=10~(-10)cm~3(STP)·cm/(cm~2·s·cm Hg)=7.5×10~(-14)cm~3(STP)·cm/(cm~2·s·Pa)],CO_2/N_2的渗透选择性可达31.     

二氧化钛载Ir催化剂对氨氧化的电催化性能

用同一方法制备了Ir含量相同而载体TiO2-晶体结构不同的TiO2-载Ir（Ir/TiO2）催化剂,研究了TiO2-晶体结构对Ir/TiO2催化剂对氨氧化的电催化性能的影响,发现具有金红石结构的TiO2-载Ir（Ir/TiO2-R）催化剂对氨氧化的电催化性能远好于具有锐钛矿型结构的TiO2-载Ir（Ir/TiO2-A）催化剂。 物理化学和电化学的表征揭示了Ir/TiO2-R催化剂对氨氧化的电催化性能好的可能原因归结于Ir纳米粒子在TiO2-R上的均匀分布。     

Comparison of electrode structures and photovoltaic properties of porphyrin-sensitized solar cells with TiO2 and Nb, Ge, Zr-added TiO2 composite electrodes

Electrode structures and photovoltaic properties of porphyrin-sensitized solar cells with TiO2 and Nb-, Ge-, and Zr-added TiO2 composite electrodes were examined to disclose the effects of partial substitution of Ti atom by the other metals in the composite electrodes. The TiO2 and Nb-, Ge-, and Zr-added TiO2 composite electrodes were prepared by sol-gel process using laurylamine hydrochloride as a template for the formation of micellar precursors yielding well-defined mesoporous nanocrystalline structures, as in the cases of the formation of silica and titania tubules and nanoparticles by the templating mechanism. The TiO2 and Nb-, Ge-, and Zr-added TiO2 composite electrodes were characterized by transmission electron microscopy, BET surface area analysis, X-ray diffraction analysis, Raman spectroscopy, and impedance measurements. The TiO2 anatase nanocrystalline structure is retained after doping a small amount (5 mol %) of Nb, Ge, or Zr into the TiO2 structure, suggesting the homogeneous distribution of the doped metals with replacing Ti atom by the doped metal. The power conversion efficiency of the porphyrin-sensitized solar cells increases in the order Zr-added TiO2 (0.8%) < Nb-added TiO2 (1.2%) < TiO2 (2.0%) < Ge-added TiO2 cells (2.4%) under the same conditions. The improvement of cell performance of the Ge-added TiO2 cell results from the negative shift of the conduction band of the Ge-added TiO2 electrode. The Ge-added TiO2 cell exhibited a maximum power conversion efficiency of 3.5% when the porphyrin was adsorbed onto the surface of the Ge-added TiO2 electrode with a thickness of 4 microm in MeOH for 1 h.     

钛白粉载体对选择性催化还原脱硝催化剂性能的影响

钛白粉(TiO2)是钒钛类选择性催化还原(SCR)脱硝催化剂的载体,TiO2的晶型、比表面积、粒度、孔结构以及SO42-和P2O5含量直接影响所制备的SCR催化剂的性能。一般而言,TiO2的比表面积越大,以其制备的SCR催化剂的比表面积也越大,活性也较高;但对于纳米级TiO2,由于颗粒粒径太小,容易发生烧结,而且形成钒钛化合物,导致催化剂比表面积较载体明显下降,因而活性降低。锐钛型TiO2由于比表面积大和不易被硫化,较金红石型TiO2适合做载体。多孔结构的TiO2使得钒物种在载体表面处于高度分散状态,从而提高催化剂的活性。TiO2中本身含有的少量SO42-和P2O5有助于提高催化剂的性能。     

纳米TiO2的制备及对三甲胺气体的敏感性能

用硬脂酸凝胶法制备纳米TiO₂材料,并用XRD、TEM、IR对纳米晶的晶型、晶粒大小及形貌进行表征；用XPS分析不同晶型的纳米TiO₂表面吸附氧的情况，发现锐钛矿型纳米TiO₂比金红石型纳米TiO₂有较多的表面吸附氧. 检测了不同晶型纳米TiO₂对三甲胺（TMA）气体的敏感性能.结果表明锐钛矿型纳米TiO₂对TMA有较高的灵敏度. 对敏感性能的机理进行了讨论.     

蛋氨酸改性TiO2空心纳米盒高效可见光催化RhB分解和NO氧化

由高能面 TiO2纳米片 (TiO2-NSs) 组装成的 TiO2空心纳米盒 (TiO2-HNBs)显示出比单独 TiO2-NSs 更强的光催化性能, 但是 TiO2-HNBs 依然属于紫外光催化剂, 无法充分利用太阳能. 因此, 开发具有可见光响应的由高能面 TiO2-NSs 组装而成的 TiO2-HNBs 具有重要意义. 本文将立方体 TiOF2与含有 N 和 S 元素的生物分子蛋氨酸混合, 通过一步焙烧制备了具有可见光响应活性的 N 和 S 元素共掺杂的 TiO2-HNBs(掺杂催化剂标记为 TMx, 未掺杂催化剂标记为 Tx, x 代表焙烧温度).由立方体 TiOF2到锐钛矿相 TiO2空心纳米盒的转变是一个自模板转化过程. 氟离子的存在降低了 TiO2高能面(001)面的表面能, 从而使得高能面 TiO2纳米片的形成变得可能. 因此, 热处理立方体 TiOF2可得到由高能面 TiO2纳米片组装的 TiO2空心纳米盒.本文系统研究了焙烧温度 (300-500 ℃) 对所制 TiO2-HNBs 结构与光催化性能的影响. 结果发现, 在 350 ℃下焙烧, TiOF2完全转化成锐钛矿相 TiO2-HNBs. 但是焙烧蛋氨酸与 TiOF2的混合物, 需 400 ℃才能完全实现 TiOF2到锐钛矿相TiO2-HNBs 的转变. 这说明蛋氨酸的加入阻碍了 TiOF2向锐钛矿相 TiO2-HNBs 的转变. XPS 结果显示, 经过 400 ℃焙烧的蛋氨酸改性样品 (TM400), N 和 S 元素成功掺入了 TiO2-HNBs 晶格, 使其产生可见光催化活性.相对于 400 ℃焙烧 TiOF2所得样品 T400, 蛋氨酸改性的 TM400 催化剂可见光降解罗丹明 B 染料 (RhB) 和 NO 氧化的性能分别提升了 1.55 倍和 2.0 倍, 这与其更强的可见光吸收性能和光生载流子分离效率有关. 400 ℃焙烧的蛋氨酸改性的 TM400 可见光催化活性稳定, 连续 5 次可见光催化 RhB 降解后, 其活性没有明显改变, 显示了潜在的应用前景.     

TiO2纳米微粒对PPV发光性能的影响

采用溶胶凝胶法制备了一系列PPV/TiO₂纳米复合膜,探讨了TiO₂纳米微粒对PPV发光性能的影响.研究发现,这些复合膜的发光性质依赖于TiO₂/PPV的质量比,.在TiO₂/PPV的质量比为1/9时,复合膜中的TiO₂微粒对PPV的荧光具有猝灭作用;当TiO₂/PPV的质量比为1/1时,复合膜中的TiO₂对PPV的荧光具有增强作用.通过FT-IR,UV-Vis,FL光谱和TEM探讨了复合膜微结构与其发光性质的关系.     

Comparison between the effects of TiO2 synthesized by photoassisted and conventional sol-gel methods on the photochromism of WO3 colloids

WO3 colloids can exhibit a blue color under UV-light irradiation due to the absorption of electrons trapped at the energy levels within the forbidden gap and this coloration performance can be improved by TiO2 nanoparticles. In this work, it is found that TiO2 prepared by the photoassisted method (TiO2-P) exhibits stronger enhancement effects than that prepared by the conventional sol-gel method (TiO2-C). Several possible mechanisms have been proposed to account for this phenomenon. The migration of charge carriers toward different directions is promoted since the flat-band potential of TiO2-P colloids is more negative than that of TiO2-C and the contact between WO3 and TiO2 particles is improved in the WO3/TiO2-P system; there are more efficient TiO2 and hole scavengers (i.e., Ti3+ and/or TiO2-O2*- species) in the system containing TiO2-P; the bandgap of TiO2-P becomes narrowed, and so on. In addition, the potential applications of this process are also discussed briefly.     

树叶为模版制备网状TiO2和Fex/TiO2及光催化活性研究

以梧桐树叶为模板制备了具有网状结构的TiO2和Fex/TiO2光催化材料.通过扫描电镜(SEM)、X-射线衍射(XRD)、X-射线光电子能谱(XPS)、荧光发射光谱(PL)、紫外-可见吸收光谱(UV-Vis)等对这两类光催化材料的结构和物理性能进行了表征.结果表明,以树叶为模板制得的Fe0.005/TiO2呈网状结构.在600～800℃范围内,随煅烧温度的升高,网状TiO2和Fe0.005/TiO2中锐钛型TiO2的含量减少,Fe3+的掺杂能促进锐钛型向金红石型的转变.与Degussa P25相比,网状TiO2和Fex/TiO2的荧光光谱强度明显减弱,光生电子-空穴对的复合情况得到改善;吸收光谱范围明显红移,禁带宽度有不同程度的缩小.孔雀石绿的光催化降解实验表明,网状TiO2和Fex/TiO2具有比Degussa P25更强的催化活性.光催化活性的稳定性研究表明,网状Fe0.005/TiO2具有良好的稳定性,能多次重复使用.     

TiO2纳米棒载Pd催化剂的制备及其对甲酸的电催化氧化

利用水热合成和无机溶胶法,分别制备了具有棒状(TiO2-R)和无规则结构(TiO2-I)的锐钛矿相TiO2,并以之为载体制备得到Pd/TiO2电催化剂.循环伏安测试显示,与无规则TiO2相比,具有棒状结构的TiO2载Pd催化剂对甲酸氧化的电催化性能提高了70%;计时电流测试显示,运行3000 s后,甲酸在棒状TiO2载Pd催化剂上的氧化电流是无规则TiO2载Pd催化剂的16倍.其原因可能与TiO2纳米棒拥有更好的电子传导性且表面拥有较多的活性含氧基团有关,从而能够有效提高催化剂对甲酸氧化的电催化活性和抗毒化性能.     

CdS/TiO2复合纳米粒子的光学性质

在Brij35/正己醇/环己烷/水构成的反相微乳体系中，分别合成了CdS、TiO2纳米粒子和TiO2包覆CdS（CdS/TiO2）的复合纳米粒子.测定了它们的紫外-可见吸收和荧光光谱.结果表明， CdS/TiO2复合纳米粒子在可见光区的吸收比相应的两组分的吸收之和更强.纳米CdS和纳米TiO2均有较强的荧光.而且在相同浓度时纳米TiO2的荧光比纳米CdS的荧光更强.但在CdS/TiO2复合纳米粒子中，TiO2的荧光被淬灭，而CdS的荧光稍有降低.     

N掺杂TiO_2光催化剂的微结构与吸光特性研究

以紫外可见漫反射光谱(UV-VIS-DRS)和X射线光电子能谱(XPS)分析和研究了四种方法制备的N掺杂TiO2光催化剂的结构,即水解法(N/TiO2-H)、氨热还原法(N/TiO2-A)、机械化学法(N/TiO2-M)和尿素热处理法(N/TiO2-T)等.结果表明,N/TiO2-H和N/TiO2-T两种催化剂在490 nm处有吸收带边,可见光激发途径是掺杂的N以填隙方式形成的杂质能级吸收电子发生的跃迁引起的;而N/TiO2-A和N/TiO2-M两种催化剂在整个可见光区域内具有可见光吸收,其对可见光的激发途径是掺杂N和氧空缺共同作用的结果.理论计算的N杂质能级位于价带上0.75 eV,与实验观察到的吸收带边结果十分吻合.XPS结果表明,几种催化剂的N1 s结合能位置都在399 eV附近,显示为填隙掺杂的N原子.填隙掺杂的N/TiO2,其Ti原子的2p结合能与未掺杂的TiO2相比增加了+0.3-+0.6 eV,而O1s电子的结合能增加了+0.2-+0.5eV,这是因为填隙的N原子夺取Ti和O的电子,Ti和O原子周围的电子密度降低了.电子能谱和吸光特性的研究都表明,掺杂的机理是在TiO2晶格内形成N原子的填隙.     

Evaluation of titanium dioxide as a pharmaceutical excipient for preformulation of a photo-labile drug: effect of physicochemical properties on the photostability of solid-state nisoldipine

To characterize the photocatalytic activity of TiO2 via solid-state reaction, the relationship between the physicochemical properties and photocatalytic activity of TiO2 was investigated and estimated from the results of photodegradation of nisoldipine. The photodegradation of nisoldipine was significantly enhanced by addition of TiO2. Two degradation products, nitroso-phenylpyridine derivative and nitro-phenylpyridine derivative, were formed. The degree of photocatalytic activity of TiO2 was quite different between the various types of TiO2 investigated, even when the crystalline phase was the same. As a result of the investigations into the relationship between the photocatalytic activity and physicochemical properties of TiO2, it was found that for the rutile form the photocatalytic activity has good correlation with specific surface area of TiO2, but poor correlation with water loss on drying of TiO2. However, for the anatase form, the photocatalytic activity has good correlation with water loss on drying of TiO2, but poor correlation with specific surface area. Moreover, it was found that the crystallinity of TiO2 has a moderate correlation with the photocatalytic activity of both crystal forms of TiO2. These results suggest that a degree of photocatalytic activity of TiO2 depends on the various physicochemical properties of each type of TiO2 investigated.