Lipid bilayer membrane with atomic step structure: supported bilayer on a step-and-terrace TiO2(100) surface

The formation of a supported planar lipid bilayer (SPLB) and its morphology on step-and-terrace rutile TiO 2(100) surfaces were investigated by fluorescence microscopy and atomic force microscopy. The TiO 2(100) surfaces consisting of atomic steps and flat terraces were formed on a rutile TiO 2 single-crystal wafer by a wet treatment and annealing under a flow of oxygen. An intact vesicular layer formed on the TiO 2(100) surface when the surface was incubated in a sonicated vesicle suspension under the condition that a full-coverage SPLB forms on SiO 2, as reported in previous studies. However, a full-coverage, continuous, fluid SPLB was obtained on the step-and-terrace TiO 2(100) depending on the lipid concentration, incubation time, and vesicle size. The SPLB on the TiO 2(100) also has step-and-terrace morphology following the substrate structure precisely even though the SPLB is in the fluid phase and an approximately 1-nm-thick water layer exists between the SPLB and the substrate. This membrane distortion on the atomic scale affects the phase-separation structure of a binary bilayer of micrometer order. The interaction energy calculated including DLVO and non-DLVO factors shows that a lipid membrane on the TiO 2(100) gains 20 times more energy than on SiO 2. This specifically strong attraction on TiO 2 makes the fluid SPLB precisely follow the substrate structure of angstrom order.     

利用原位APXPS与STM研究H2在ZnO(10${\rm{\bar 1}}$0)表面的活化

Cu/ZnO/Al₂O₃是工业中最广泛使用的甲醇合成催化剂。然而该催化反应的活性位点和机理目前仍存争议。H₂作为反应物之一,研究其在ZnO表面的活化和解离对于弄清甲醇合成反应的催化机理具有重要的帮助。本工作利用近常压光电子能谱(APXPS)和扫描隧道显微镜(STM)原位研究了H₂在ZnO(10${\rm{\bar 1}}$0)表面上的活化和解离。APXPS结果表明：在0.3 mbar (1 mbar = 100 Pa)的H₂气氛中,室温下ZnO表面形成羟基(OH)吸附物种。STM实验发现通入H₂后ZnO表面发生了(1×1)到(2×1)的重构。上述结果和原子H在ZnO(10${\rm{\bar 1}}$0)表面的吸附结果一致。然而吸附H₂O可以导致同样的现象。因此,我们还开展了H₂O在ZnO(10${\rm{\bar 1}}$0)表面吸附的对比实验。结果表明：H₂气氛中ZnO表面发生0.3 eV的能带弯曲,而H₂O吸附实验中几乎观察不到能带弯曲发生。同时,热稳定性实验表明H₂气氛中ZnO表面的OH不同于H₂O解离吸附产生的OH,前者具有更高的脱附温度。因此,本工作的结果表明常温和常压下H₂在ZnO(10${\rm{\bar 1}}$0)表面发生解离吸附。这一结果和以往超高真空下未发现H₂在ZnO(10${\rm{\bar 1}}$0)表面上的解离不同,说明H₂的活化是一个压力依赖过程。     

ZrO_2酸碱性质的TPD表征Ⅰ.单组分吸附研究

以NH3、吡啶、Et3N、CO2和苯酚为探针，用TPD－MS方法对ZrO2催化剂的酸碱性质进行了表征．ZrO2上碱性探针（NH3、吡啶和Et3N）的脱附温度远低于在强酸性SiO2－Al2O3上；而酸性探针CO2的脱附温度远低于在强碱性MgO上的结果．为ZrO2的弱酸弱碱性质提供了证明．NH3吸附IR结果表明ZrO2表面配位不饱合Zr4＋为酸（Lewis酸）中心．NH3、吡啶和Et3N与这些酸中心作用的方式和能量分布相似．NH3和CO2的TPD谱图均存在三个脱附峰，且相应脱附峰的温度范围相近．表明ZrO2的酸中心和碱中心具有匹配相当的酸、碱强度，ZrO2为典型的酸－碱双功能催化剂，在苯酚的TPD过程中，ZrO2的特征表现为对苯酚的强吸附和对苯酚分解的高活性．文中结合IR结果，对与NH3和CO2的脱附相联系的表面吸附物种分别进行了讨论．     

Reaction of silanes in supercritical CO2 with TiO2 and Al2O3

Infrared spectroscopy was used to investigate the reaction of silanes with TiO2 and Al2O3 using supercritical CO2 (Sc-CO2) as a solvent. It was found that contact of Sc-CO2 with TiO2 leads to partial removal of the water layer and to the formation of carbonate, bicarbonate, and carboxylate species on the surface. Although these carbonate species are weakly bound to the TiO2 surface and can be removed by a N2 purge, they poison the surface, resulting in a lower level of reaction of silanes with TiO2. Specifically, the amount of hexamethyldisilazane adsorbed on TiO2 is about 10% of the value obtained when the reaction is performed from the gas phase. This is not unique to TiO2, as the formation of carbonate species also occurs upon contact of Al2O3 with Sc-CO2 and this leads to a lower level of reaction with hexamethyldisilazane. This is in contrast to reactions of silanes on SiO2 where Sc-CO2 has several advantages over conventional gaseous or nonaqueous methods. As a result, caution needs to be applied when using Sc-CO2 as a solvent for silanization reactions on oxides other than SiO2.     

2-Nitrobenzaldehyde as a chemical actinometer for solution and ice photochemistry

2-Nitrobenzaldehyde (2NB) is a convenient, photochemically sensitive, and thermally robust actinometer. Although 2NB has been used in a number of solution and ice experiments in the laboratory, the quantum efficiencies and molar absorptivities of 2NB have not been critically evaluated, especially on ice. Using a series of laboratory and field measurements we have measured the light absorbance and photochemical properties of 2-nitrobenzaldehyde in solution (water and/or acetonitrile) and in/on water ice. Our results show that the molar absorptivities of 2NB are only weakly dependent upon temperature and that the quantum yield is independent of temperature in water; the quantum yield is also independent of wavelength, as shown by past reports. Furthermore, we find that the photochemistry of 2NB in/on water ice is the same as in liquid water. While most studies employing 2NB cite and use a quantum yield of 0.50, based on a review of the literature, and on our new experimental data, we recommend a quantum yield of 0.41 for 2NB photolysis for both solution and water ice.     

Supercritical carbon dioxide: an inert solvent for catalytic hydrogenation?

Various surface species originating from the reaction between CO2 and H2 over Al2O3-supported Pt, Pd, Rh, and Ru model catalysts were investigated by attenuated total reflection infrared (ATR-IR) spectroscopy under high-pressure conditions. Two different spectroscopic cells were used: a variable-volume view cell equipped with ATR-crystal and transmission IR windows (batch reactor) and a continuous-flow cell also equipped with a reflection element for ATR-IR spectroscopy. The study corroborated that CO formation from dense CO2 in the presence of hydrogen occurs over all Pt-group metals commonly used in heterogeneous catalytic hydrogenations in supercritical CO2 (scCO2). In the batch reactor cell, formation of CO was detected on all metals at 50 and 90 degrees C, with the highest rate on Pt. Additional surface species were observed on Pt/Al2O3 at 150 bar under static conditions. It seems that further reaction of CO with hydrogen is facilitated by the higher surface concentration at higher pressure. In the continuous-flow cell, CO coverage on Pt/Al2O3 was less prominent than that in the batch reactor cell. A transient experiment in the continuous-flow cell additionally revealed CO formation on Pt/Al2O3 at 120 bar after switching the feed from a H2-ethane to a H2-CO2 mixture. The in situ ATR-IR measurements indicate that CO formation in CO2-H2 mixtures is normally a minor side reaction during hydrogenation reactions on Pt-group metal catalysts, and dense ("supercritical") CO2 may be considered as a relatively "inert" solvent in many practical applications. However, blocking of specific sites on the metal surface by CO and consecutive products can affect structure sensitive hydrogenation reactions and may be at the origin of unexpected shifts in the product distribution.     

Formation of dense self-assembled monolayers of (n-decyl)trichlorosilanes on Ta/Ta2O5

Tantalum pentoxide (Ta2O5) is a promising material for the realization of biological interfaces because of its high dielectric constant, its high chemical stability, and its excellent passivating properties. Nevertheless, the deposition of highly organized silane SAMs to realize well-defined and tailored Ta2O5-based (bio)interfaces, has not been studied in great detail as of yet. In this work, we have investigated the formation of a highly ordered, dense monolayer of trichlorosilanes on Ta2O5 surfaces. Specifically, two different cleaning procedures for Ta2O5 were compared and (n-decyl)trichlorosilane (DTS) was used to study the effect of both cleaning methods on the silanization of Ta2O5. Both types of cleaning allowed the formation of complete and crystalline DTS monolayers on Ta2O5, in contrast with the incomplete, disordered silane layer assembled on uncleaned Ta2O5. The deposited self-assembled monolayers were studied by means of contact angle goniometry, Brewster angle FTIR, X-ray photoelectron spectroscopy, cyclic voltammetry, and ellipsometry. Infrared analysis exhibited a highly ordered DTS silane film on Ta2O5 and indicated a larger tilt angle of the alkyl chains on this substrate by comparison to DTS on SiO2. Furthermore, with use of ellipsometry and XPS, the silane film thickness on Ta2O5 was determined to be substantially smaller than that reported in the literature for DTS on SiO2, supporting the observations of an increased tilt angle (approximately 45 degrees ) on Ta2O5 than on SiO2 (approximately 10 degrees ). By means of cyclic voltammetry, the formation of a dense, essentially pinhole-free, silane film was observed on the cleaned samples. In conclusion, the fully characterized and optimized procedure for the silanization of Ta2O5 surfaces with trichlorosilanes will allow the formation of well-defined, reproducible, and controllable chemical interfaces on Ta2O5.     

Self-Assembled Bilayers on Indium-Tin Oxide (SAB-ITO) Electrodes: A Design for Chromophore-Catalyst Photoanodes

A novel approach for creating assemblies on metal oxide surfaces via the addition of a catalyst overlayer on a chomophore monolayer derivatized surface is described. It is based on the sequential self-assembly of a chromophore, [Ru(bpy)(4,4'-(PO(3)H(2)bpy)(2))](2+), and oxidation catalyst, [Ru(bpy)(P(2)Mebim(2)py)OH(2)](2+), pair, resulting in a spatially separated chromophore-catalyst assembly.     

Low-temperature reduction of NO(2) on oxidized Mo(110)

The reactions of nitrogen dioxide (NO(2)) were investigated on oxidized Mo(110) containing both chemisorbed oxygen and a thin film oxide. NO(2) reacts on both oxidized Mo(110) surfaces via a combination of reversible adsorption and reduction to NO, N(2), and trace amounts of N(2)O below 200 K. On the surface containing chemisorbed O, there is some complete dissociation of NO(2) to yield N(a) and O(a). N(2) forms at high temperatures through atom combination. On both surfaces, NO is the predominant product of NO(2) reduction. However, the chemisorbed layer which has a low oxidation state, and hence a greater capacity to accept oxygen, more effectively reduces NO(2). The selectivity for N(2) formation over N(2)O is greater for NO(2) as compared with NO on both surfaces studied. The selectivity changes are largely attributed to an increase in the concentration of Mo=O species and a change in the distribution of oxygen on the surface. Notably, more oxygen, in particular Mo=O moieties, is deposited by NO(2) reaction than by O(2) reaction, indicating that NO(2) is a stronger oxidant. The fact that there are several N-containing species on the surface at low temperatures may also affect the product distribution. On both surfaces, N(2)O(4), NO(2), and NO are identified by infrared spectroscopy upon adsorption at 100 K. All N(2)O(4) desorbs by 200 K, leaving only NO(2) and NO on the surface. Infrared spectroscopy of NO(2) on (18)O-labeled surfaces provides evidence for oxygen transfer or exchange between different types of sites even at low temperatures.     

芥子气模拟剂2-氯乙基乙基硫醚的光催化降解

利用连续流动微反、原位红外和GC/MS等手段考察了芥子气模拟剂2-氯乙基乙基硫醚（2-CEES）在P25 TiO2上的光催化降解反应,证实CO2和H2O是这个反应的最终产物.详细的跟踪分析表明,除了CO2和H2O外,在反应的气相混合物中可检测到C2H4、CH3CHO、CH4、CO、HCl和H2S；少量小分子的羧酸、醚和砜；微量C2H5SC2H5、C2H5S2C2H5、C2H5SC2H4Cl和CH2ClCH2Cl等中间产物;在反应后的催化剂表面可检测到C2H5S2C2H5、C2H5SC2H4OH、C4H9S2C2H5和C2H5S2C2H4OH、等物.根据这些结果提出了2-CEES光催化降解的反应机理,推断2-CEES的光催化降解涉及脱氯、C－S键断裂、有机硫化物光聚合和裂解等复杂过程最终转化为CO2和H2O.认为各种硫物种在表面的积聚引起了催化剂的缓慢失活.     

Two-Dimensional Polymer Networks Locking on Inorganic Nanoparticles

Two-dimensional polymers (2DPs), single-layer networks of covalently linked monomers, show perspectives as membranes and in electronics. However, 2D polymerization of monomers in orthogonal directions limited the formation of 2DPs on nanoparticles (NPs) with high surface curvatures. Here we propose a high-curvature 2D polymerization to form a single-layer 2DP network as a non-contacting ligand on the surface of NPs for their stabilization and functionalization. The high-curvature 2D polymerization of amphiphilic Gemini monomers was conducted in situ on surfaces of NPs with various sizes, shapes, and materials, forming highly cross-linked 2DPs. Selective etching of core–shell NPs led to 2DPs as a non-contact ligand of yolk-shell structures with excellent shape retention and high NP-surface accessibility. In addition, by copolymerization, the 2DP ligands can covalently link to other functional molecules. This work promotes the development of 2DPs on NPs for their functional modification.     

Catalytic role of gold in gold-based catalysts: a density functional theory study on the CO oxidation on gold

Gold-based catalysts have been of intense interests in recent years, being regarded as a new generation of catalysts due to their unusually high catalytic performance. For example, CO oxidation on Au/TiO(2) has been found to occur at a temperature as low as 200 K. Despite extensive studies in the field, the microscopic mechanism of CO oxidation on Au-based catalysts remains controversial. Aiming to provide insight into the catalytic roles of Au, we have performed extensive density functional theory calculations for the elementary steps in CO oxidation on Au surfaces. O atom adsorption, CO adsorption, O(2) dissociation, and CO oxidation on a series of Au surfaces, including flat surfaces, defects and small clusters, have been investigated in detail. Many transition states involved are located, and the lowest energy pathways are determined. We find the following: (i) the most stable site for O atom on Au is the bridge site of step edge, not a kink site; (ii) O(2) dissociation on Au (O(2)-->2O(ad)) is hindered by high barriers with the lowest barrier being 0.93 eV on a step edge; (iii) CO can react with atomic O with a substantially lower barrier, 0.25 eV, on Au steps where CO can adsorb; (iv) CO can react with molecular O(2) on Au steps with a low barrier of 0.46 eV, which features an unsymmetrical four-center intermediate state (O-O-CO); and (v) O(2) can adsorb on the interface of Au/TiO(2) with a reasonable chemisorption energy. On the basis of our calculations, we suggest that (i) O(2) dissociation on Au surfaces including particles cannot occur at low temperatures; (ii) CO oxidation on Au/inactive-materials occurs on Au steps via a two-step mechanism: CO+O(2)-->CO(2)+O, and CO+O-->CO(2); and (iii) CO oxidation on Au/active-materials also follows the two-step mechanism with reactions occurring at the interface.     

ZrO2酸碱性质的TPD表征 I. 单组分吸附研究

以NH_3、吡啶、Et_3N、CO_2和苯酚为探针，用TPD-MS方法对ZrO_2催化剂的酸碱性质进行了表征．ZrO_2上碱性探针（NH_3、吡啶和Et_3N）的脱附温度远低于在强酸性SiO_2－Al_2O_3上；而酸性探针CO_2的脱附温度远低于在强碱性MgO上的结果．为ZrO_2的弱酸弱碱性质提供了证明．NH_3吸附IR结果表明ZrO_2表面配位不饱合Zr~(4＋)为酸（Lewis酸）中心．NH_3、吡啶和Et_3N与这些酸中心作用的方式和能量分布相似．NH_3和CO_2的TPD谱图均存在三个脱附峰，且相应脱附峰的温度范围相近．表明ZrO_2的酸中心和碱中心具有匹配相当的酸、碱强度，ZrO_2为典型的酸－碱双功能催化剂，在苯酚的TPD过程中，ZrO_2的特征表现为对苯酚的强吸附和对苯酚分解的高活性．文中结合IR结果，对与NH_3和CO_2的脱附相联系的表面吸附物种分别进行了讨论.     

Nature identification and morphology characterization of cation-exchange membrane fouling during conventional electrodialysis

The aim of this work was to study the effect of a concentrate solution pH value and of the composition in calcium, carbonate, and protein of a diluate solution to be treated by conventional electrodialysis on the fouling of cation-exchange membranes (CEM). It appeared that after demineralization of solutions containing CaCl(2) and CaCl(2)+Na(2)CO(3) using a concentrate solution maintained at a pH of 12, mineral fouling appeared on both sides of the CEM. The nature of the deposits was identified as calcium hydroxide and/or carbonate on both surfaces. The mineral fouling presented an aggregation-like crystal following a carnation-like pattern of aggregates of small rhombohedral crystals with CaCl(2) added alone, while CaCl(2)+Na(2)CO(3) yielded a smoother spherical crystal. Protein fouling was detected only on the CEM surface in contact with the diluate after demineralization of a solution containing CaCl(2)+Na(2)CO(3) using a concentrate pH value of 2.     

Fabrication and characterization of core/shell structured TiO2/polyaniline nanocomposite

A novel core/shell structured TiO(2)/polyaniline nanocomposite was fabricated by grafting aniline on aminobenzoate monolayer that is chemically adsorbed on the TiO(2) nanocrystal surface. The formation and nanostructure of the nanocomposite were investigated by FT-IR and UV-Vis spectra, TEM, FE-SEM, and TG-DTA analysis. Adsorption of aminobenzoate on the TiO(2) surface is an effective method to obtain the uniform nanocomposite. The thickness of polyaniline layer coating on the TiO(2) nanocrystal surface can be controlled in a range of 2-5 nm by this method. A photoelectrochemical study was carried out on the TiO(2)/polyaniline nanocomposite, and found that polyaniline in the nanocomposite acted as a visible-light sensitizer in a photoelectrochemical reaction. The sensitization effect increased with increasing binding strength between polyaniline and TiO(2). A dye-sensitized solar cell with a short circuit current density of 0.19 mA/cm(2) and an open circuit voltage of 0.35 V was fabricated by using the TiO(2)/polyaniline nanocomposite film as a sensitized electrode.     

纳米晶镍-钼合金电沉积层的结构与性能

研究了Ｃｒ２Ｏ３、ＭｏＯ３、ＳＯ２－４和ＣｕＳＯ４在ＳｎＯ２表面的单层分散及其对ＳｎＯ２超细粉热稳定性的影响．结果表明,几种化合物在ＳｎＯ２上均能单层分散且分散阈值都接近按密置单层模型估算的分散容量极限值;表面单层覆盖能十分有效地抑制ＳｎＯ２的高温烧结,单层覆盖率与经５００℃焙烧后样品中ＳｎＯ２的粒径和比表面有很好的对应关系,表现出很强的阈值效应;单层覆盖率达到一定程度,ＳｎＯ２高温烧结便可基本得到抑制．     

不同导电基底对TiO2薄膜光致亲水性的影响

分别在导电铝合金片(Al)和具有阳极氧化铝层的非导电铝片(AAO/Al), 以及铟锡氧化物导电玻璃(ITO/glass)和普通非导电玻璃(glass)表面通过提拉法制备出TiO2/Al和TiO2/AAO/Al, 以及TiO2/ITO/glass和TiO2/glass两组TiO2薄膜样品, 通过测试紫外光照下水滴接触角的变化考察TiO2薄膜的光致亲水性. 结果表明, 相对于TiO2/Al2O3/Al, 基底导电的TiO2/Al表现出较好的光致亲水性能; 而相对于TiO2/glass, 基底导电的TiO2/ITO/glass表现出较差的光致亲水性能. 分析认为, Al和ITO两导电基底和TiO2薄膜间的不同电子转移方向影响TiO2薄膜的光致亲水性能, Al片提供电子给TiO2有助于提高以光生电子为主要初级活性物种的光致亲水性, 而ITO接受TiO2的光生电子, 导致光致亲水性的下降.     

水蒸气处理对Ni_2P/SiO_2催化剂催化氯苯加氢脱氯反应的促进作用

在303,514和543K下用0.8%H2O-99.2%H2对Ni2P/SiO2催化剂进行了水蒸气处理,利用N2吸附-脱附、X射线衍射、电感耦合等离子体发射光谱、H2程序升温脱附及原位漫反射红外光谱等技术对水蒸气处理前后Ni2P/SiO2催化剂的结构进行了表征,并在常压固定床反应器上评价了其催化氯苯加氢脱氯活性.结果表明,经水蒸气处理后,Ni2P/SiO2催化剂的物相及元素组成、Ni2P晶粒大小、比表面积及孔结构没有明显改变.与未处理和303K处理的Ni2P/SiO2催化剂不同,513和543K处理的催化剂表面暴露的Ni中心数量减少,表面P–OH基团数量增多.在513K,氯苯空速3.75ml/(g·h)及H2和氯苯的摩尔比为9.0的反应条件下,经不同温度水蒸气处理的Ni2P/SiO2催化剂上氯苯初始转化率高于93.8%,约是未预处理催化剂的17倍.这可能与金属Ni中心和表面P–OH基团的协同作用有关.     

酸性溶液中NaH2PO2在铂电极上氧化的原位红外光谱研究

用SNIFTIRS和循环伏安法研究酸性溶液中次亚磷酸钠在多晶铂电极上的电氧化机理.分析了0.5mol/LH2SO4+0.1mol/LNaH2PO2溶液中原位红外反射谱图与电极电位的关系,发现在发生反应的电位下Pt电极上的吸附物种有氢原子和H2PO2,最终的氧化产物是H3PO4而不是H2PO3-,据此提出了酸性介质中次亚磷酸根离子在Pt上氧化的新机理.     

Density functional theoretical calculations for a Co2/gamma-Al2O3 model catalyst: structures of the gamma-Al2O3 bulk and surface and attachment sites for Co2+ ions

First-principle density functional theory (DFT) calculations on the electronic state and structure of a [Co2+]2/gamma-Al2O3 model catalyst have been performed in relation to catalysis for unique NO-CO reactions on a Co2+ ensemble/gamma-Al2O3 catalyst. The DFT calculations reveal that a bulk structure of gamma-Al2O3 is energetically most favorable when aluminum vacancies are evenly dispersed at octahedral sites, and that the (110) plane is exposed as a top-most layer by its neutrality. Two Co2+ ions on the (110) surface are supported adjacently to each other in a tetrahedral symmetry. The calculations also demonstrate that the vacant d orbitals of the two Co2+ ions are directed toward each other, which brings about an adsorbate-adsorbate interaction between two molecules which adsorb on each of the Co2+ ions. This may be an origin of the unique aspect of Co2+ ensemble/gamma-Al2O3 catalysis.