稀土金属Y掺杂锐钛矿TiO2(101)表面的改性

为了掌握Y原子掺杂在锐钛矿TiO₂(101)表面的稳定吸附位置和电子结构变化,提高其表面光催化活性,本文利用基于密度泛函理论的第一性原理计算研究了Y原子掺杂在完美的、带有亚表层氧空位和带有表层氧空位的锐钛矿TiO₂(101)表面的结构稳定性和电子性能。结构优化和电荷密度结果表明,Y原子可以稳定吸附在三种不同的表面上。在完美表面吸附时,Y原子最稳定的吸附位置是两个三配位O原子之间的空位;与完美表面类似,在带有亚表层氧空位表面吸附时,Y原子最稳定吸附位置是与氧空位邻近的两个三配位O原子之间的空位;而在带有表层氧空位表面吸附时,Y原子则停留于氧空位邻近的四配位Ti原子位置上最稳定。电荷密度计算结果也表明Y原子与这三种表面结合非常稳固。电子态密度计算结果表明,在带有表层氧空位的锐钛矿TiO₂(101)表面引入Y原子会在费米面附近的带隙中引入缺陷态,带隙从1.67 eV降至1.44 eV,这有可能引起电子的分级跃迁,提高表面光催化能力。本文的研究为利用单原子Y掺杂提高TiO₂(101)表面光催化能力提供了理论...     

Ge在Si(100)-2×1表面化学吸附的第一性原理研究

应用密度泛函理论,构造了具有非对称二聚体结构的Si(100)-2×1重构表面,在系统研究了其表面结构及特性的基础上,计算了Ge在不同吸附位置的表面吸附能,以及吸附前后的表面投影态密度.计算结果表明:Ge原子在基位(pedestal)吸附最稳定.另外,在吸附Ge原子之后,我们得到了一个具有完整对称性的特殊Si原子二聚体结构.此结构中相邻的两个二聚体链互相平行且分别与Si表面平行,每对二聚体Si原子呈对称分布.     

扶手椅型石墨烯纳米带吸附镍、铜原子链的电子结构

采用基于密度泛函理论的第一性原理方法,研究了扶手椅型石墨烯纳米带吸附3d过渡金属磁性Ni和非磁性Cu单原子链的结构、电子性质和磁性.吸附体系经过弛豫后,不同宽度纳米带吸附单原子链的稳定结构是不同的.Ni比Cu原子链在石墨烯纳米带表面的吸附更为稳定.原子链吸附在纳米带的边缘洞位(即5AG-1、6AG-1和7AG-1位置)时较为稳定,且稳定程度随着纳米带宽度的增加而增加.原子链和石墨烯纳米带的相互作用使得Ni单原子链吸附体系的磁矩为零.Cu原子链吸附5AG-1的复合体系具有磁性.Ni原子链的吸附体系呈现出带隙较小的半导体性质,而Cu原子链的吸附体系全都表现出金属性质.     

MOVPE生长m面GaN薄膜的表面吸附研究

采用基于密度泛函理论的Materials Studio中的CASTEP模块,对金属有机物气相外延MOVPE生长m面GaN薄膜的表面反应前体的吸附过程进行研究.针对吸附粒子GaCH3和NH3在m面GaN表面不同的初始吸附位,优化计算了GaCH3和NH3在表面的吸附能、与近邻原子的距离、态密度、电荷密度分布、电子布居.计算结果表明,GaCH3在表面Ga brg2位优化之后的位置最稳定,吸附能最低,GaCH3中的Ga原子与表面邻近的N原子、Ga原子分别形成Ga-N、Ga-Ga共价键.NH3在表面N brg2位最稳定,吸附能最低,NH3中的N原子与表面邻近的Ga原子形成N-Ga共价键.通过对比在最佳吸附位的MMG中的Ga原子和NH3中的N原子与表面原子的电荷分布情况和布居数,证明上述吸附粒子与表面确实存在共价作用,形成共价键.     

多孔硅基WO3气敏传感器的制备与性能研究

以钨酸钠和氯化钠为原料,采用水热法在硅基多孔硅上原位生长WO3纳米棒薄膜,制成p型多孔硅基-n型WO3复合结构气敏传感器.为了获得最大比表面积的复合形貌,详细研究了水热反应时间和温度对多孔硅基WO3复合结构显微组织表面形貌的影响.利用扫描电镜、粉末衍射等表征手段测试并分析了多孔硅基表面WO3纳米棒薄膜的形貌以及晶体结构,并测试了复合结构传感器在不同工作温度下的气敏响应特性,结果表明:该气敏传感器在室温下便对有毒气体NO2具有高灵敏度以及稳定的重复性.     

Si(100)表面吸附Sr的建模与第一性原理计算

为了研究Sr在Si(100)表面的稳定吸附结构和吸附特性,采用基于密度泛函理论的第一性原理平面波赝势法,通过改变Sr在Si(100)表面的覆盖度和吸附位置,计算了Si(100)表面吸附Sr的吸附能、电子态密度、电子布居、电荷密度和差分电荷密度.计算结果表明,三种吸附位置中,空位的吸附能最低,Sr与Si(100)表面的作用力最大,结构最稳定;覆盖度越低,吸附能越小,Sr与Si(100)表面的作用力越大,吸附结构越稳定.Sr、Si原子间的作用力主要由Sr的3d轨道电子和Si的3s、3p轨道电子杂化耦合作用(d-sp3杂化)贡献,包括共价键和离子键.共价键和离子键的强度均随覆盖度增大而减弱,这可能是由于Sr与Sr之间的排斥力减弱了Sr与Si之间的作用力,并且这种排斥力随覆盖度增大而增大.     

MOVPE生长GaN薄膜的表面吸附和扩散研究

利用量子化学计算方法,对MOVPE生长GaN薄膜的表面反应进行研究.特别针对反应前体GaCH3(简称MMG)在理想、H覆盖和NH2覆盖GaN(0001)面的吸附和扩散进行计算分析.通过建立3×3 超晶胞模型,优化计算了MMG在三种不同覆盖表面的稳定吸附位、吸附能和电子布居,搜寻了MMG在稳定吸附位之间的扩散能垒.计算结果表明:对于三种表面,MMG的稳定吸附位均为T4位和H3位,H3位比T4位略微稳定.MMG在NH2覆盖表面吸附能最大,在H覆盖表面吸附能最小,在理想表面吸附能居中.MMG中的Ga与不同的表面原子形成的化学键的键强的大小顺序为:Ga-N>Ga-Ga>Ga-H.相比于理想表面和H覆盖表面,MMG在NH2覆盖表面的扩散能垒最大,因此表面过量的NH2会抑制MMG的扩散.     

AlN的MOCVD生长中表面吸附的量子化学研究

利用量子化学的密度泛函理论(DFT),对AlN的MOCVD生长中表面反应前体MMAl、DMAlNH2分别在理想、NH2覆盖AlN (0001)-Al面的吸附进行研究.通过分析表面吸附位、吸附能、分波态密度图等,确定可能的稳定吸附结构和吸附倾向.研究发现:在理想和NH2覆盖的AlN(0001)-Al面,MMAl吸附在T4位和H3位,吸附概率相近,MMAl与表面形成3个Al-Al8键(理想AlN表面)或3个Al-N8键(NH2覆盖的AlN表面).在理想AlN表面,DMAlNH2吸附在Top-Top位,与表面形成N-Al8键和Al-Al8键;在NH2覆盖的AlN表面,DMAlNH2吸附在Top位,与表面形成Al-N8键.对比两种粒子在理想和NH2覆盖表面的吸附能,发现在理想表面DMAlNH2的吸附能大于MMAl,即DMAlNH2优先吸附;在NH2覆盖表面,MMAl的吸附能明显大于DMAlNH2,即MMAl优先吸附.     

GaN的MOVPE生长中台阶表面吸附的 量子化学计算

利用量子化学的密度泛函理论,计算GaN的MOVPE生长中主要的表面反应前体NH3、GaCH3(简写为MMG)在GaN(0001)面台阶处的吸附特性,并与理想平台表面对比.结果表明,在台阶吸附时,NH3有分子吸附和分解吸附两种结构,MMG只有两种分子吸附结构.NH3分子吸附时,吸附能在台阶处大于在平台表面;NH3分解吸附时,吸附能在平台表面大于在台阶处.说明NH3在台阶处容易发生分子吸附,而在平台表面容易发生分解吸附.MMG在台阶处的吸附能均大于在平台表面,说明它们在台阶处吸附比理想表面更容易.     

Ca修饰石墨烯储氢性能的第一性原理研究

使用基于密度泛函理论的DMol3程序包,研究了纯石墨烯和5种不同结构Ca修饰石墨烯的几何结构、电子结构和储氢性能.结果表明:Ca原子不同位置吸附对石墨烯结构影响微弱;随Ca原子周围氢分子吸附数目增加,费米能级处电子态密度值增大,氢分子平均吸附能减小;单Ca修饰石墨烯能稳定吸附6个氢分子,吸附能为0.635eV,储氢密度为2.77wt;;双Ca修饰石墨烯结构Ⅲ和Ⅳ的氢平均吸附能最高,分别达到0.789 eV和0.733 eV,其储氢密度为4.95wt;.     

Characterization of organic adsorbates on model glass surfaces

Model silicate glasses in planar thin film structures are prepared using sol/gel techniques. A typical structure consists of 3.0–12.0 nm of glass on vapor deposited Ag. In this study, a pure silica and a 50/50 binary alumina-silica films are examined. Poly(methyl methacrylate) (PMMA) is adsorbed from chlorobenzene solution onto the surfaces. Infrared reflection (IR) spectroscopy, ellipsometry and quartz oscillator microgravimetry (QOM) are applied to characterize the PMMA/silicate glass interfaces formed. The QOM and IR data show that PMMA adsorption on the pure silica surface is irreversible with respect to removal by pure solvent rinse while on the binary glass surface and on a pure alumina surface, solvent rinses remove the initially adsorbed polymer. These results are interpreted in terms of Bronsted acid-base interactions involving the basic properties of the PMMA C=O group, the acidic nature of the silica and the more basic nature of the alumina containing surfaces. Further evidence for this interpretation is given by the IR spectral data which show broadening of the C=O stretching mode to lower frequencies for the irreversible adsorbed polymer on silica as compared with simulated spectra of non-surface bonding PMMA thin films. This spectral perturbation is interpreted as evidence for a hydrogen bonding interaction between OH groups on the silica surface and the C=O groups. The overall conclusion is that the surface of a 50/50 binary alumina-silica composition is dominated by the basic nature of alumina.     

三维Ag2O/WO3复合催化剂的制备及光催化性能研究

WO3是一种带隙约为2.7 eV的过渡金属半导体,可见光就能激发其光催化活性,这极大地提高了太阳光的利用率,但纯WO3纳米材料催化活性偏低,针对这一难题,本文选取了三维网格结构的WO3纳米材料为载体,利用化学搅拌法制备了不同摩尔比的Ag2O/WO3复合光催化剂.选择亚甲基蓝为研究对象,测定了不同摩尔比的Ag2O/WO3复合催化剂的光催化性能.实验表明,当Ag2O和WO3的摩尔配比为1∶2时,该复合催化剂的光催性能最好.过量的Ag2O纳米颗粒会增加Ag2O/WO3内部电子空穴的复合几率,反而导致光催化剂反应活性的降低.     

Photochemistry of azobenzene in sol-gel systems

The photophysical and photochemical behavior of azobenzene incorporated into sol-gel systems was studied. Sols doped with azobenzene were prepared by the hydrolysis of tetramethoxysilane. The absorption spectra of azobenzene in sols with and without HCl as a catalyst showed photochromism; UV irradiation changes trans-azobenzene to cis-azobenzene, which returns to trans-azobenzene by successive visible light irradiation. The results indicate that azobenzene is not protonated in the sol prepared by the present conditions. The absorption spectra showed that the azobenzene-doped xerogel prepared without HCl is mostly adsorbed on silica surfaces by the hydrogen bonding between the azo groups and silanol and/or water molecules. The adsorption did not affect photochromic behavior and photo-reversible changes were observed in the xerogels. UV photolysis of the azobenzene-doped xerogel prepared with HCl so produced protonated benzo[c]cinnoline that photochromic behavior was deteriorated. Surface modified xerogels were prepared from the mixture of tetraethoxysilane and methyltriethoxysilane in order to make clear the effect of the surface silanol groups. It was shown that the formation of the protonated benzo[c]cinnoline is suppressed by the introduction of Si-CH₃. These present results confirm that the acidic sites of Si-OH₂⁺ of xerogels play an important role in the photochemical reaction of azobenezene in silica xerogels.     

Understanding and Controlling the Morphology of ZnO Crystallites under Hydrothermal Conditions

The morphological features of ZnO crystallites influenced by solution basicity under hydrothermal conditions have been studied from the standpoint of the incorporation of the growth units. A crystal chemistry approach is developed to understand and thus to control a desirable morphology of the crystallites. The effects of the additive OH⁻ on the crystal morphology of ZnO crystallites are qualitatively but satisfactorily explained by a mechanism considering two aspects: (1) solution structures and the structural forms of growth units under a certain growth condition, i.e. the interactions between the solvent molecules and the growth units; and (2) the influence of the solvent molecules or additives on growth interfaces, particularly on two polar faces of ZnO crystallites in terms of the inhibition or promotion of the incorporation of various growth units depending on the solution basicity. Since the incorporation rates of the growth units are different on positive and negative polar faces, the relative growth rates of these faces are different and thus lead to the habit modifications. The approach clearly demonstrates that the hindrance of crystal growth is a consequence of surface adsorption processes.     

不同晶相WO3的热分解法制备及其光催化性能

以钨酸铵为钨源,硝酸为沉淀剂,首先通过沉淀法制备前驱体H2 WO4,随后采用热分解H2 WO4法合成六方及单斜晶相WO3催化剂.利用X射线衍射(XRD)、拉曼光谱、差热-热重(TG-DTA)、扫描电子显微镜(SEM)、X射线光电子能谱(XPS)及紫外-可见漫反射光谱(UV-Vis DRS)对H2 WO4向WO3转变过程中结构、形貌、组成及光学性质的变化进行研究.结果表明,热处理后前驱体发生如下相变过程:H2 WO4→六方相WO3→六方/单斜相WO3→单斜相WO3.此外,以罗丹明B为模拟污染物,考察不同晶相WO3的光催化活性,结果表明,六方相WO3具有更高的光催化性能,单斜相WO3的活性较低.     

Auger electron spectroscopic studies of the water vapour adsorption on the (100) surface of austenitic chromium-nickel steel

The water vapour adsorption on the (100) surface of chromium-nickel steel was studied by Auger electron spectroscopy (AES) in the temperature range of 300 K to 700 K at water vapour pressures of 13.3 μPa to 133 mPa. The water vapour adsorption goes on more slowly than the oxygen adsorption under the same conditions. The measured kinetic isotherms may be described by logarithmic time laws as they are typical of the adsorption on inhomogeneous surfaces. With rising temperature of the samples the rate of adsorption as well as the quantity of fragments of the water molecule adsorbed during saturation state increases, i.e. the adsorption is activated. By means of the measured adsorption isotherms it may be concluded that a dissociative adsorption takes place.     

Planned Multilayer Assemblies by Adsorption

Adsorption at liquid solid interfaces is employed to construct organized multilayer structures on polar solid substrates. We have recently demonstrated that oriented compact monolayers of good quality can be obtained under suitable conditions either by physisorption or by chemisorption, using either pure compounds as adsorbates or mixtures of several components, and even using mixtures of both physisorbed and chemisorbed species.¹ Monolayer formation by adsorption offers certain important advantages as compared with the Lanmuir-Blodgett method; adsorption is a spontaneous process leading to thermodynamically equilibrated film structures, there is no mechanical manipulation of the films, water is not indispensable for monolayer formation, monolayer composition and structure are usually dependent on the chemical nature and microscopic organization of the solid surface, covalent binding to the substrate and intralayer polymerization may take place simultaneously with the monolayer formation process, there are no restrictions regarding the macroscopic shape and size of the substrate. However, the adsorption method has been so far shown to be suitable only for formation of single mono-layers,¹ which limited severely its usefulness in the construction of multilayer assemblies.     

Interaction of vinyl trichlorosilane and water with E-glass surfaces

The objective of this work was to elucidate the nature of water vapor adsorption on E-glass fibers drawn under dry conditions and E-glass fibers drawn in a vinyl trichlorosilane (VTS) atmosphere. VTS was chosen as representative of trifunctional organosiliconchloride coupling agents. The long-range goal of this work is to provide guidance in the design of glass fiber and coupling agent compositions to reduce the influence of atmospheric water on the stability of glass reinforced plastics. The adsorption of VTS vapor on E-glass fibers was found to be time-dependent and to fit the Langmuir model. Water vapor was shown to have a lower affinity for E-glass surfaces drawn in dry air than for E-glass fibers drawn in a dry air/VTS atmosphere. The BET surface areas were found to vary with sequential adsorptions of water vapor. The adsorption of water vapor on E-glass surfaces was found to vary with the square root of time.     

Surface preparation of AlN substrates

The Al‐polar surfaces of AlN wafers cut from physical vapor transport grown crystals were lapped and polished. Polishing procedures were developed to produce surfaces for epitaxial growth. The surface scratches and subsurface damage caused by mechanical polishing were removed by a final chemical mechanical polishing (CMP) process, which yielded a perfect surface ready for epitaxial growth. After CMP the average root mean square surface roughness on a 5 µm × 5 µm area was 0.1 nm. Characterization of the polished surfaces by electron back scatter diffraction and cathodoluminescence showed no subsurface damage. The difference of orientation dependent material removal rate during CMP went up with the increase of the misorientation from (0001) surface. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)