CO_2在Fe(111)表面吸附的密度泛函理论研究

采用量子化学的密度泛函理论,研究二氧化碳在Fe(111)表面的可能吸附态(M1-M5),计算出稳定的吸附构型和吸附能.结果表明,当CO2的O与表面形成强O-Fe双吸附键(M2,M5)时,吸附能最大,为强化学吸附;形成较弱双吸附键C-Fe及配位键O-Fe(M3)时,吸附能次之;当CO2垂直底物表面吸附(M4)时,氧原子只能与Fe原子形成单键,吸附力很弱,为弱物理吸附;在M1吸附模式中,CO2分子的C原子吸附在Fe原子上,M1的吸附能也不太大,约为1.87 ev,属于弱化学吸附.Mullik-en电荷计算表明,当吸附分子CO2电荷愈负,与底物的吸附力愈强,与吸附能的计算结果相一致,同时由于电子转移形成CO2x-,导致金属失去电子而易被腐蚀.     

H2在Pt表面的吸附行为研究进展

在多相催化反应中,催化剂表面的吸附是一个重要关键的步骤。Pt作为一种常见的金属催化剂,具有良好的选择性、稳定性和活性,同时对H₂有良好的吸附行为,研究H₂在Pt表面的吸附行为对于多相催化和储氢材料的研究具有重要的价值。本文简要介绍了H₂在Pt表面的吸附态,吸附位置以及吸附的影响。通过对H₂在Pt表面吸附行为的相关研究进行阐述和分析,推测H₂是直接在Pt表面缺陷处发生物理吸附至化学吸附的转变解离活化的,H₂在Pt表面的吸附行为有待进一步研究。     

几种含氮化合物在MoS_2晶面的吸附研究

油品中的含氮化合物易使加氢脱硫催化剂中毒,对脱硫反应有很强的抑制作用,因此,研究含氮化合物在加氢脱硫催化剂上的吸附行为,对了解其对加氢脱硫反应的作用机理有重要意义。本文利用基于密度泛函理论(DFT)的Vienna ab-inito simulation package(VASP)程序包计算了碱性含氮化合物(喹啉、吡啶、苯胺)、非碱性含氮化合物(吲哚和咔唑)在硫化钼(MoS_2)晶体表面吸附形式和吸附能。研究结果表明:5种含氮化合物的平行吸附能大于倾斜和垂直吸附能,它们最可能以平行吸附的形式自发的吸附在MoS_2晶面上。碱性含氮化合物中喹啉的吸附能最大、吡啶其次、苯胺最小;非碱性含氮化合物咔唑的吸附能大于吲哚;咔唑的吸附能略大于喹啉。     

Fe2O3/SnO2和SnO2/Fe2O3双层薄膜的XPS分析

用X光光电子能谱(XPS),结合Ar~+刻蚀对Fe_2O_3/SnO_2及Fe_20_3/SnO_2双层薄膜进行分析.结果表明:Fe_2O_3/SnO_2膜表面,晶格氧的结合能为529.85eV,热处理前有大量吸附氧存在,在600℃退火后,大部分羟基、羰基形态的吸附氧解吸;SnO_2/Fe_2O_3膜表面,热处理前后都只有少量的吸附氧,经热处理后表面吸附氧却略有增加.双层薄膜中锡向氧化铁层的扩散较铁向氧化锡层的扩散强.扩散的结果,形成了一个数十纳米的过渡层,对元件的气敏性质产生一定的影响.     

Fe_2O_3基陶瓷的气湿敏特性

论述了由不同制备工艺获得的Ｆｅ２Ｏ３陶瓷及各种添加剂下表面羟基和吸附氧的形成和性质，分析了表面羟基和吸附氧的酸碱性对气湿特性的影响。     

茂金属聚乙烯催化剂结构与活性关系的分子模拟研究

利用分子模拟技术对一系列茂金属聚乙烯催化剂的结构进行了优化，计算了乙烯插入过程中不同中间态产物的能量，考察了中间态产物的构象能与茂金属聚乙烯催化剂活性之间的关系。发现两种中间态产物构象能的差与活性之间有着很好的对应关系。这一规律可帮助优化茂金属聚乙烯催化剂的结构，理性开发性能更加优良的茂金属聚乙烯催化剂。     

活性炭酚羟基和羧基对二苯并噻吩吸附作用的分子模拟研究

采用密度泛函理论计算酚羟基、羧基和二苯并噻吩的结构以及酚羟基和羧基吸附二苯并噻吩后的结构;用分子内原子理论计算酚羟基和羧基吸附二苯并噻吩后体系的电荷密度及其拉普拉斯值;用自然键轨道理论计算酚羟基与二苯并噻吩之间的电荷转移。结果表明:酚羟基与二苯并噻吩之间形成了O-H…π芳香氢键,其结合能为7.97 kJ·mol~(-1);成键路径为从酚羟基的H_(34)开始,指向二苯并噻吩的C_1=C_2;酚羟基与二苯并噻吩形成芳香氢键的原因是其反键轨道σ_(O33-H34)~*与二苯并噻吩的π体系π_(C1=C2)存在交互作用;约有5.29×10~(-22) C的电荷从二苯并噻吩的C_1=C_2转移至酚羟基的σ_(O33-H34)~*;羧基未与二苯并噻吩形成氢键。增加活性炭表面酚羟基含量,将有利于提高活性炭对DBT的吸附容量。     

H2O和O2在Al(111)表面吸附的密度泛函理论研究

采用第一原理密度泛函理论中的广义梯度近似计算方法对H2O和O2分子在Al(111)表面的吸附性质进行了结构、能量和电子分析,系统研究了这2种气体分子在Al(111)表面的吸附行为及其与Al(111)表面的相互作用机理。计算结果表明：H2O分子易在Al(111)表面的top位吸附且构型倾斜时最稳定,整个吸附过程为弱的化学吸附;吸附过程中表面铝原子的电子向H2O分子发生转移,H2O分子自身的构型仅受微扰作用。O2分子在Al(111)表面的吸附倾向于以分子键平行于表面,表面铝原子向O2分子的电荷转移是O2分子解离的驱动力,吸附过程中O2分子易发生解离,解离后的氧原子稳定吸附于fcc位,其次为hcp位,整个吸附过程为强的化学吸附。     

酰胺类驱避化合物与CO_2的缔合作用研究

为延续和完善此前蚊虫驱避化合物与引诱物之间的缔合作用。本文借助Gaussian、Ampac和Codessa软件研究了43个酰胺类蚊虫驱避化合物与蚊虫引诱物CO_2之间的双分子缔合作用及其对驱避活性产生的影响。结果表明驱避化合物与CO_2之间存在类似弱氢键的缔合作用,缔合能、缔合距离和缔合角度分别在(5~16.2)k J/mol、(2.8~3.0)?和(161~178)°之间;定量计算获得R~2为0.9032的最佳四参数定量构效关系模型,其中有2个参数来自双分子缔合体,说明双分子缔合作用会对驱避活性产生显著影响。     

掺锆SnO_2陶瓷的乙醇气敏特性研究

在研究SnO_2乙醇气体敏感陶瓷中,比较添加物,发现ZrO_2对乙醇气体有较高的灵敏度。进而从工艺上研究了添加ZrO_2时的最佳烧结温度和预烧温度。分析了烧结温度与测试初始电阻的关系。总结出不同条件下乙醇的分解物不同。提出ZrO_2的催化机理是活化表面羟基,释放占有的电子,释放表面的吸附位,从而提高氧离子的效率。     

Adsorption of phenol molecules by sodium dodecyl sulfate (SDS) surfactants deposited on solid surfaces: A computer simulation study

Adsorption studies of phenol molecules on a sodium dodecyl sulfate (SDS) micelle were investigated by molecular dynamics simulations. Simulations were carried out in bulk and on three distinct solid surfaces, silicon dioxide, titanium dioxide and graphite. It was observed that different surfactant micellar shapes were formed on the surfaces. For the silicon dioxide and titanium dioxide surfaces the surfactants were adsorbed by their headgroups whereas for the graphite surface they were adsorbed mainly by their tail groups. It was found that the amount of phenol adsorbed on the SDS micelle was altered by the surfactant shape deposited on the solid surface. However, the best phenol adsorption was obtained by the surfactant modified silicon dioxide surface. Moreover, in all cases, from structural investigations, it was determined that the phenol molecules were located inside the surfactant micelle with their hydroxyl groups close to the SDS headgroups.     

硅胶基催化涂层对Ag-SnO_2气敏性能的影响

采用不同的硅胶基催化涂层对广谱敏感型Ag-SnO2气敏元件进行了表面修饰,改善了Ag-SnO2气敏元件的气体灵敏度和气体选择性,提高了Ag-SnO2气敏元件对H2的选择性     

用于痕量胺类同系物检测的谐振式微悬臂梁传感器

采用化学修饰法,将酸性羧基基团嫁接于高比表面的积的SBA- 15介孔材料中,然后将该功能化介孔材料负载于集成谐振式微悬臂梁表面,制得一种高性能的挥发性胺类同系物传感器.胺类分子的吸附将导致质量型微悬臂梁传感器谐振频率的下降,传感器检测下限可达ppb量级.对一系列胺类同系物的检测结果表明,胺类分子在羧基功能化介孔表面的吸...     

PAAm􀀁g􀀁CB/Al2O3 凝胶杂合材料的制备及 负蒸气系数效应研究

利用自由基反应机理,以过氧化苯甲酰(BPO)为引发剂,在炭黑表面引入-CH2OH或-C(CH3)2OH;然后再以硝酸铈铵/CB-CH2OH或硝酸铈铵/CB-C(CH3)2OH 组成氧化还原引发体系,在CB表面接枝上聚丙烯酰胺(PAAm-g-CB);在PAAm-g-CB 存在下,进行AIP(异丙醇铝)的溶胶-凝胶化反应,制得了一种新颖的具有智能响应性的PAAm-g-CB/Al2O3凝胶杂合材料.研究了其气敏性能和湿敏性能.结果发现,该杂合材料在其良溶剂蒸气中电阻急剧下降,呈现负蒸气系数现象(NVC);而在不良溶剂蒸气中电阻几乎不发生变化.其响应性能与杂合体间氢键作用密切相关,并受接枝率大小的影响;结合IR、DTA、TGA等分析方法推断了杂合材料分子结构模型.     

Density functional theory study of adsorption geometries and electronic structures of azo-dye-based molecules on anatase TiO2 surface for dye-sensitized solar cell applications

Structural and electronic properties of eight isolated azo dyes (ArNNAr′, where Ar and Ar′ denote the aryl groups containing benzene and naphthalene skeletons, respectively) were investigated by density functional theory (DFT) based on the B3LYP/6-31G(d,p) and TD-B3LYP/6-311G(d,p) methods The effect of methanol solvent on the structural and electronic properties of the azo dyes was elucidated by employing a polarizable continuum model (PCM). Then, the azo dyes adsorbed onto the anatase TiO₂ (101) slab surface through a carboxyl group. The geometries and electronic structures of the adsorption complexes were determined using periodic DFT based on the PWC/DNP method. The calculated adsorption energies indicate that the adsorbed dyes preferentially take configuration of the bidentate bridging rather than chelating or monodentate ester-type geometries. Furthermore, the azo compounds having two carboxyl groups are coordinated to the TiO₂ surface more preferentially through the carboxyl group connecting to the benzene skeleton than through that connecting to the naphthalene skeleton. The dihedral angles (Φ_B-N) between the benzene- and naphthalene-skeleton moieties are smaller than 10° for the adsorbed azo compounds containing one carboxyl group. In contrast, Φ_B-N > 30° are obtained for the adsorbed azo compounds containing two carboxyl groups. The almost planar conformations of the former appear to strengthen both π-electrons conjugation and electronic coupling between low-lying unoccupied molecular orbitals of the azo dyes and the conduction band of TiO₂. On the other hand, such coupling is very weak for the latter, leading to a shift of the Fermi level of TiO₂ in the lower-energy direction. The obtained results are useful to the design and synthesize novel azo-dye-based molecules that give rise to higher photovoltaic performances of the dye-sensitized solar cells.     

Laser polishing and 2PP structuring of inside microfluidic channels in fused silica

This study presents the development of post-processing steps for microfluidics fabricated with selective laser etching (SLE) in fused silica. In a first step, the SLE surface—even inner walls of microfluidic channels—can be smoothed by laser polishing. In addition, two-photon polymerization (2PP) can be used to manufacture polymer microstructures and microcomponents inside the microfluidic channels. The reduction in the surface roughness by laser polishing is a remelting process. While heating the glass surface above softening temperature, laser radiation relocates material thanks to the surface tension. With laser polishing, the RMS roughness of SLE surfaces can be reduced from 12 µm down to 3 nm for spatial wavelength λ < 400 µm. Thanks to the laser polishing, fluidic processes as well as particles in microchannels can be observed with microscopy. A manufactured microfluidic demonstrates that SLE and laser polishing can be combined successfully. By developing two-photon polymerization (2PP) processing in microchannels we aim to enable new applications with sophisticated 3D structures inside the microchannel. With 2PP, lenses with a diameter of 50 µm are processed with a form accuracy rms of 70 nm. In addition, this study demonstrates that 3D structures can be fabricated inside the microchannels manufactured with SLE. Thanks to the combination of SLE, laser polishing and 2PP, research is pioneering new applications for microfluidics made of fused silica.     

NOx adsorption onto dehydroxylated or hydroxylated tin dioxide surface. Application to SnO2-based sensors

SnO₂-based sensors present strong interactions with NO_x-containing atmospheres. For this reason, it is fundamental to identify the nature of the adsorbed species resulting from the interaction of NO and NO₂ with the tin oxide surface. This aspect has been studied in literature by Temperature Programmed Desorption (TPD). To state more precisely structures of adsorbed species, we link TPD with Diffuse Reflectance Fourier Transform Spectroscopy (DRIFTS). Concerning NO₂ adsorption, DRIFTS experiments indicate the formation of monodentate nitrato species at room temperature. By increasing the temperature, a conversion of adsorbed species is observed. The nature of surface groups is discussed. In the presence of hydroxyl groups (two different OH groups are evidenced), the formation of hydrogeno nitrates is detected.     

Influence of oxygen backgrounds on hydrogen sensing with SnO2 nanomaterials

The influence of different oxygen backgrounds on the sensing of hydrogen with SnO₂ nanomaterials was investigated and a model was proposed. It is based on two hydrogen reaction mechanisms at the surface of tin oxide that can take place simultaneously; the weight of each mechanism depends on the concentration of oxygen in the ambient atmosphere. In the absence of oxygen the adsorbed hydrogen builds surface donors (rooted hydroxyl groups). In the presence of oxygen the reaction between hydrogen and pre-adsorbed oxygen ions dominates. Due to the fact that this behavior is present for very different nanomaterials, the model probably describes a SnO₂ specific feature.