具有高活性能量{001}晶面锐钛矿TiO2的进展研究

概述了近年来国内外众多有关高活性能量{001}晶面锐钛矿TiO2的研究进展。简述了其在光催化分解水制氢、降解有机物、染料敏化太阳能电池、光催化选择性及锂电池等方面的应用,以及展望了其今后的研究方向。     

[111]-/{101}晶面共暴露的锐钛矿型TiO2纳米晶的制备及可提高的光催化性能

本文以层状钛酸H1.07Ti1.73O4为前驱体，以不同含量的HF溶液为形貌控制剂，在温和的水热条件下(120~180 ℃)采用一锅法合成了共暴露[111]-/{101}晶面的方块状为主的锐钛矿型TiO2纳米晶；对制备的xHF-T180 (x = 0.5, 1.0, 1.5, 2.0, 2.5, 3.0 mL)锐钛矿型TiO2纳米晶的晶体结构、形貌、微观结构、比表面积、元素电子态、光学性能和电荷迁移行为进行了表征；并对其光催化降解MB性能进行了评价. 研究结果表明，与CM-TiO2和其他xHF-T180锐钛矿型TiO2纳米晶相比，2.5HF-T180显示了最高的k值(0.0165 min-1)，分别是Blank (0.0009 min-1)、CM-TiO2 (0.0083 min-1)、0.5HF-T180 (0.0126 min-1)、1.0HF-T180 (0.0113 min-1)、1.5HF-T180 (0.0142 min-1)、2.0HF-T180 (0.0130 min-1)和3.0HF-T180 (0.0123 min-1)样品的18.33、1.99、1.31、1.46、1.16、1.27和1.34倍. 2.5HF-T180显示了最高的光催化活性可以归因于其最小的颗粒尺寸、最大的比表面积、最弱的荧光光谱强度和最小的电阻的协同效应. 本研究为合成具有较高光催化性能的锐钛矿型TiO2纳米晶以处理有机染料废水提供了新思路.     

氮掺杂暴露（001）面二氧化钛的制备及其可见光催化性能研究

以尿素为氮源、HF为调控剂,采用水热法制备了以（001）活性面为主的氮掺杂型TiO2催化剂.SEM、TEM、XRD、Raman及UV-Vis测试结果表明,TiO2及N-TiO2产品均为暴露（001）面的纳米片状锐钛矿结构,TiO2在高温900℃煅烧仍能保持锐钛矿结构.F-不仅对（001）面的暴露起到很好的调控作用,而且抑制了TiO2在高温下向金红石相的转化.氮的掺杂窄化了TiO2的禁带宽度,使其边带红移,在可见光区域有很强的吸收峰.并且,随着氮掺杂量的增多,N-TiO2在可见光的吸收峰增强.以可见光降解染料罗丹明B溶液作为探针反应,研究了不同N/Ti配比的N-TiO2的可见光催化活性,氮掺杂TiO2的可见光催化活性比照纯TiO2有明显的改善.     

3D TEM study on hollow α-Fe_2O_3 nanostructures and nanorings

Controlled synthesis of hollow structures with non-spherical holes is significant in fabricating nanomaterials with well-defined geometries and specific catalytic and electrochemical properties. Here we report the synthesis of uniform hexagonal bipyramid hematite(α-Fe_2O_3) nanoparticles with hollow and faceted interior via directional etching process in solution. The delicate hollow structures were investigated by electron tomography and growth mechanism was revealed unambiguously. The three-dimensional visualization demonstrates the outside surfaces of hematite particles are enclosed by six {104} and twelve {113} planes, due to the stabilizing effect of the F-anions on the exposed surfaces. The concurrent etching process is a reverse process of crystal growth and leads to the dissolution occurring at the edges and tips of the hexagonal bipyramid particles, resulting in the perforated crystals with exposed {102} internal facets or overetched nanorings with hexagonal cross-sections.This nanoscale growth and etching process still strictly follows the bulk crystal growth mechanism, thus shedding light on the synthesis of other nanoparticle with controlled morphologies and porous structures.     

用AFM观测凝胶法下KClO4晶体的生长机理

用原子力显微镜(atomic force microscopy,AFM)对凝胶法生长的KClO4晶体的最重要面{001}面微观形貌进行了研究。结果表明,在不同的过饱和度下,KClO4晶体分别表现为二维成核生长、三维成核生长、层核生长以及多层堆垛生长等生长机理。从热力学角度解释了过饱和度对KClO4晶体生长机理的影响。对二维成核生长机理,揭示了KClO4晶体生长中二维核的形状和取向,及生长台阶的取向。研究结果还表明,杂质的存在将阻止台阶的向前推进,并导致聚并台阶及弯曲台阶的形成。     

非水相一步合成TiO2纳米晶及其光催化性能

利用正丁醇与TiCl4反应,在非水溶剂和无表面活性剂的条件下,通过改变反应物TiCl4与丁醇的摩尔比制备了纯锐钛矿TiO2纳米粒子和金红石TiO2纳米棒.利用X射线衍射分析、拉曼光谱分析、透射电镜和比表面积测定等测试分析手段对样品进行了表征,并以罗丹明B的脱色降解为模式反应,考察了样品的光催化性能.结果表明:所制备的纳米级TiO2比表面积大、晶粒尺寸小、结晶性完好,具有比商用P25更好的光催化活性.     

制备条件对纳米TiO_2粒子粒径与形貌的影响

研究钛酸丁酯水解沉淀法制备纳米 Ti O2 粒子的方法 ,考察水解反应介质组成、酸碱性、回流与共沸处理 ,添加聚合物等反应与处理条件对所制得 Ti O2 粒子粒径、形貌的影响 .发现钛酸丁酯在碱性或中性条件下 ,醇水之比较小的含少量聚乙二醇的介质中水解反应 ,低温短时间脱除有机溶剂并经低温短时煅烧所制得的纳米 Ti O2 粒子是由数个锐钛晶型晶粒构成的纳米 Ti O2 粒子 ,粒子粒径小 ,是近似单分散外表轮廓清晰的球形粒子     

Observation of Pt-{100}-p(2×2)-O reconstruction by an environmental TEM

The surface structure of noble metal nanoparticles usually plays a crucial role during the catalytic process in the fields of energy and environment. It has been studied extensively by surface analytic methods, such as scanning tunneling microscopy. However, it is still challenging to secure a direct observation of the structural evolution of surfaces of nanocatalysts in reaction(gas and heating) conditions at the atomic scale. Here we report an in-situ observation of atomic reconstruction on Pt {100} surfaces exposed to oxygen in an environmental transmission electron microscope(TEM). Our high-resolution TEM images revealed that Pt-{100}-p(2×2)-O reconstruction occurs during the reaction between oxygen atoms and{100} facets. A reconstruction model was proposed, and TEM images simulated according to this model with different defocus values match the experimental results well.     

Synthesis of well-defined functional crystals by high temperature gas-phase reactions

Over the past decades, there have been many synthesis methods on producing well-defined crystals, due to their enormous application potentials in industrial field. Among them, high temperature gas-phase reactions （HTGR） approach may be one of the most promising processes for fabrication of well-defined crystals with controllable structure, size, shape, and composition. This review is focused on the recent progresses in synthesizing well-defined crystalline TiO2 dominated with, respectively, {001 } facets and { 105 } facets, one-dimensional ZnO and SnO2 nanorods/nanowires, MoS2 nanosheets as well as GaP, InP, and GaAs nanowires via HTGR approach. Although these research works were currently carried out on experimental scale, it is worth to note that the industrial importance of this HTGR approach for design and fabri- cation of well-defined crystals in the future owing to its advantages of continuous and scalable production with controlled dimensions and low cost.     

Facet effect of copper(I) sulfide nanocrystals on photoelectrochemical properties

14-facets polyhedra chalcocite Cu2S nanocrystals were synthesized by a solvothermal method. It was found that the presence of trio-n-octylphosphine during the synthesis was essential for the exposure of unconventional {110} faces. Results from photoelectrochemical measurements indicated that the polyhedra bounded by {110} facets exhibited much higher activities than the Cu2S hexagonal plates with only {001} facets.     

第一性原理计算锐钛矿（101）面的电子结构

采用基于密度泛函理论的平面波赝势方法计算了锐钛矿（101）表面的电子结构．首先对锐钛矿完整（101）表面模型进行结构优化,在此基础上计算了电子结构,得到了能带结构和态密度等数据．结果分析表明表面的电子结构与体相基本相同,在完整表面上没有出现表面态,驰豫后完整的锐钛矿（101）表面是稳定的,表面价带主要由O2p组成,导带主要由Ti3d组成,表面导带态密度变窄导致表面能隙比体相能隙略增大．通过表面原子局域态密度和Mulliken净电荷的分析,推测O2c、O3c、Ti5c可能是活性位置．     

反应物体积分数和pH值对水热合成二氧化钛微粒的影响

采用水热合成工艺,以钛酸丁酯(Ti(OC4H9)4)为前驱体,通过改变反应物的体积分数和体系的pH值,合成了不同晶型和形貌的二氧化钛(TiO2)微粒.同时,使用X射线衍射仪(XRD)和扫描电子显微镜(SEM)对此产物进行了表征.结果表明:反应物的体积分数和pH值对TiO2微粒的晶型、形貌和晶粒尺寸均有较大的影响.当Ti(OC4H9)4体积分数较大时,出现锐钛矿型晶体,但结晶不完善,微粒较大,且有团聚现象;Ti(OC4H9)4体积分数较小时,出现金红石型晶体,微粒相对较小,随着反应物体积分数的减小微粒的晶型由锐钛矿型转为金红石型,晶粒尺寸逐渐增大.在酸性溶液中,有利于形成金红石型微粒,而在碱性溶液中,有利于形成锐钛矿型微粒,随着体系的pH值增加,晶粒尺寸也逐渐增大.     

高比表面积TiO_2纳米颗粒的制备及光催化性能研究

以钛酸四丁酯为钛源,采用流变相法制备出了具有高比表面积的二氧化钛（TiO2）纳米颗粒.采用X射线衍射仪（XRD）,扫描电子显微镜（SEM）和比表面积及孔径分析仪（BET）对TiO2的晶型、形貌及比表面积进行了表征,结果显示产物为锐钛矿型,平均粒径约为8.4 nm,比表面积为423.7 m2/g.光催化实验表明,样品在可见光（λ〉420 nm）下反应180 min后,能将罗丹明B（RhB）降解95%左右.     

Surface study of the reconstructed anatase TiO_2(001) surface

The anatase TiO_2(001) surface has attracted extensive attention in surface science and for practical applications because of its excellent performance. However, the highly reactive(001) surface usually reconstructs to a(1 ×4)-(001) surface, which may potentially alter its properties. As a result, there are still controversial issues concerning the intrinsic performance of this surface. Recently, significant advances have been made in the surface science study of TiO_2(001), which have elucidated its intrinsic physical and chemical properties. In this review,we summarize our present understanding of the structure and properties of the reconstructed TiO_2(001) surface.First, we provide a brief background of the anatase TiO_2 surfaces, including its low-index surface structures and the synthesis of anatase TiO_2 nanocrystals with the(001) surface exposed. Next, we focus on the structure,formation mechanism, stability, and surface chemistry of the reconstructed TiO_2(001) surface. Finally, we finish this review by highlighting the current challenges of this subject and providing future research perspectives.     

High temperature oxidation behavior of aluminide on a Ni-based single crystal superalloy in different surface orientations

An investigation on oxidation behavior of coated Ni-based single crystal superalloy in different surface orientations has been carried out at1100 ℃. It has been found that the {100} surface shows a better oxidation resistance than the {110} one, which is attributed that the {110}surface had a slightly higher oxidation rate when compared to the {100} surface. The experimental results also indicated that the anisotropic oxidation behavior took place even with a very small difference in the oxidation rates that was found between the two surfaces. The differences of the topologically close packed phase amount and its penetration depth between the two surfaces, including the ratio of α-Al2O3 after 500 h oxidation, were responsible for the oxidation anisotropy.     

取向硅钢薄带形变再结晶组织及织构演变

利用背散射电子衍射微织构分析技术及X射线衍射织构分析技术,结合对取向硅钢薄带再结晶各阶段退火板磁性能的分析,系统研究了其形变再结晶过程中的组织及织构演变。结果表明,薄带内原始高斯晶粒取向发生绕TD轴向{111}<112>的转变,同时晶粒取向还表现出绕RD轴的附加转动,这种附加转动及其导致的表层微弱立方形变组织可为再结晶立方织构的形成提供核心。退火各阶段样品磁性能的变化对应了{110}-{100}<001>有益织构及其他织构的强弱转变以及再结晶晶粒不均匀程度的变化,综合织构类型及晶粒尺寸的变化推断发生了二次及三次再结晶过程。升温过程再结晶织构演变主要体现了织构诱发机制,也即与基体存在绕<001>轴取向关系的晶粒长大优势结合高斯织构的抑制效应发挥作用;而在高温长时间保温后三次再结晶过程,{110}低表面能诱发异常长大发挥主要作用使得最终得到锋锐的高斯织构。     

用AFM研究杜仲抗真菌蛋白的晶体生长

随着后基因组时代的到来以及蛋白质组学研究的深入开展,研究蛋白质晶体生长成为生物化学和结构生物学领域一个广泛关注的课题.通过使用原子力显微镜(Atomic Force Microscope,简称AFM)对杜仲抗真菌蛋白(eucommia antifungal protein,简称EAFP)的晶体在有母液存在下原位实时动态地进行了晶面生长观察.研究结果表明:不同过饱和度对EAFP晶体生长形貌的影响较大,较高的过饱和度下生长很快,生长台阶密度高,较高的过饱和度下主要进行各向异性二维台阶的发生、发展,较低的过饱和度下主要采用螺旋位错的生长方式,当过饱和度极低时生长缓慢,且晶体表面有很多小孔存在,晶面生长很不完整;还对不同过饱和度下晶体生长速率进行了定量的测量,也反映了过饱和度对EAFP晶体生长的影响;同时对在AFM观察过程中由探针的扫描速度和方向对表面形貌的影响进行了讨论.     

第一性原理计算Zr/S共掺杂锐钛矿相TiO_2的电子结构

利用基于密度泛函理论的第一性原理平面波赝势方法对Zr/S共掺杂锐钛矿相TiO2的晶格参数、电荷布居、能带结构、电子分态密度和吸收光谱进行了计算.计算结果表明:Zr/S共掺杂导致锐钛矿相TiO2的晶格畸变使其体积变大,共掺杂时Zr和S的电荷布居数与单掺杂前的布居数略有不同;Zr/S共掺杂还导致锐钛矿相TiO2的禁带宽度变大0.1eV,达到2.30eV,但是由于Zr/S共掺杂在TiO2禁带之内引入了杂质能级,这些杂质能级可以作为电子跃迁的"台阶"而降低电子从价带跃迁到导带所需的激发光子能量,这有可能是实验上制备的Zr/S共掺杂TiO2具有较高光催化活性的内在原因.     

溶胶-凝胶法制备不同晶相组成TiO_2及其可见光催化活性

采用溶胶-凝胶法制备了不同晶型的TiO2纳米粒子,以X-射线衍射、扫描电镜、红外光谱和紫外-可见固体漫反射吸收光谱对其进行了表征及光吸收特性研究,以可见光下TiO2对罗丹明B的降解率评价其光催化活性.结果表明TiO2纳米粒子的晶相分别为锐钛矿纯相、锐钛矿/金红石混晶和金红石纯相,粒子的平均粒径为10 nm左右,许多纳米粒子聚集形成较大的颗粒,且表面含有活性羟基.制备的三种晶相组成的TiO2对罗丹明B均具有较高的可见光催化活性,活性均高于商品TiO2（P25）,且活性按锐钛矿纯相、混晶和金红石纯相的顺序依次降低,可见TiO2的可见光催化活性与其晶相组成密切相关.     

纳米TiO2光降解触媒丝的制备

以草酸氧钛酸为前驱物,采用"浸渍-提拉法"在玻璃纤维丝基体上生成纳米TiO2前驱物薄膜,经过热分解得到纳米TiO2光降解触媒丝.XRD分析表明触媒丝表面薄膜为锐钛矿型TiO2, SEM形貌分析表明有部分小颗粒TiO2团聚在薄膜表面,颗粒粒度≤100 nm.该纳米TiO2光降解触媒丝能够在1 h内使罗丹明B在紫外光作用下降解66.67%～72.22%.