γ-Mo2N催化剂上H2及NO吸附性质的TPD-MS研究

采用TPD-MS方法研究了H2及NO在γ-Mo2N上的吸附状况．单独的H2-TPD结果表明,当H2在673K吸附时,在443K、573K及723K得到了三个H2脱附峰,表明γ-Mo2N上有三种不同能量的H2吸附位．NO－TPD结果表明,NO吸附后亦有三个脱附峰（383K、493K、543K）,对应着γ-Mo2N上三种不同能量的NO吸附位：低、中、高能吸附位．NO既可以以解离状态,又可以以一种NO三聚态（dimerordinitrosyl）的形式吸附在γ－Mo2N上,这些吸附物种在脱附过程中产生大量的N2及少量的N2O.对比NO吸附在不同处理条件的γ-Mo2N上的TPD结果可知,NO是吸附在γ-Mo2N上的MO的配位不饱和中心上,这些吸附中心既可通过还原催化剂,又可通过在773K抽空钝化态的γ－Mo2N而产生,H2和NO共吸附的结果表明,预吸附H2再吸附NO后,H2和NO的脱附量均大大减少,且只有两个脱附峰出现.NO只在363K及493K出现两个脱附峰,表明预吸附氢占据了NO的强吸附位,且NO很难取代它,从而使NO只能吸附在能量较低的吸附位上;而H2只在523K及723K出现两个脱附峰,且伴随着H2的脱出有N2和H2O的产生,表明在γ－Mo2N上NO可能与预吸附氢形成了一种复合相MoHx（NO）y,它在脱附时分解为H2、N2及H2O.     

V2O5在硅胶表面的分散及助剂K2SO4作用的研究

用原位XRD方法证明V_2O_5能在硅胶表面自发分散, 但所需温度较高. 水汽对V_2O_5的分散有一定的阻碍作用. K_2SO_4可显著加快V_2O_5在SiO_2表面的分散速度, 并能降低V_2O_5/SiO_2的表面酸性. 被中和的主要是强酸位. 这可能是K_2SO_4能够改善V_2O_5/SiO_2催化剂在选择氧化反应中选择性的重要原因之一.     

可逆与不可逆氢在甲烷化反应中的作用

用自行设计和建立的加压动态分析装置研究了甲烷化催化剂上氢的吸附和反应行为．结果表明，在反应条件下吸附的氢可区分为不可逆吸附氢和可逆吸附氢两类，不可逆吸附氢又可分为能被ＣＯ顶替出来的和不能被顶替的两种．起甲烷化反应的是可逆吸附氢，而能被ＣＯ顶替出来的不可逆氢对吸附ＣＯ起促进作用，不能被ＣＯ顶替出来的不可逆氢是甲烷化催化剂必不可少的组分（或称“促进剂”）．     

Synthesis of SnO_2 nanorods from aqueous solution:The effect of preparation conditions on the formed patterns

<正>SnO_2 nanorods were deposited on the Si substrates in an aqueous solution containing both SnCl_4 and CO(NH_2)_2.It is found that different self-assembled patterns of SnO_2 nanorods can be obtained by changing the deposition conditions such as the molar ratio of CO(NH_2)_2 to SnCl_4 and the pretreatment of the substrate.Scattered SnO_2 nanorods,for example,can be changed into flower-like patterns when the molar ratio of CO(NH_2)_2 to SnCl_4 is raised,and well-aligned nanorod arrays can be formed when the pretreatment of the substrate is changed.In addition,some interesting patterns,e.g.tree-like patterns,can also be observed.     

铈离子清除超氧物自由基的机理

以光辐照核黄素作为超氧物自由基（Ｏ－２）源，研究了Ｃｅ３＋、Ｃｅ４＋对硝基四氮唑蓝（ＮＢＴ）还原、羟胺氧化的抑制作用和铈离子存在时Ｈ２Ｏ２含量、核黄素光分解、溶解氧消耗的变化以及铈离子价态的变化。从而得知，铈离子可清除Ｏ－２，其机理为：Ｃｅ３＋供给Ｏ－２电子氧化为Ｃｅ４＋，Ｏ－２还原为Ｈ２Ｏ２；Ｃｅ４＋从Ｏ－２获得电子还原为Ｃｅ３＋，Ｏ－２氧化为Ｏ２。所以微量的铈离子可清除大量的Ｏ－２。     

Hydrogen bonded arrays: the power of multiple hydrogen bonds

Hydrogen bond interactions in small covalent model compounds (i.e., deprotonated polyhydroxy alcohols) were measured by negative ion photoelectron spectroscopy. The experimentally determined vertical and adiabatic electron detachment energies for (HOCH(2)CH(2))(2)CHO(-)(2a), (HOCH(2)CH(2))(3)CO(-) (3a), and (HOCH(2)CH(2)CH(OH)CH(2))(3)CO(-) (4a)reveal that hydrogen-bonded networks can provide enormous stabilizations and that a single charge center not only can be stabilized by up to three hydrogen bonds but also can increase the interaction energy between noncharged OH groups by 5.8 kcal mol(-1) or more per hydrogen bond. This can lead to pK(a) values that are very different from those in water and can provide some of the impetus for catalytic processes.     

La2O3对Ni/γ-Al2O3甲烷化催化剂的助催化作用

我国将稀土作为助剂引入镍基甲烷化催化剂,大大提高了催化剂的活性和热稳定性,并已投入工业应用［1－3］．稀土对不同镍催化剂反应性能及其作用机理的研究已有一些报导［3－7］．谢有畅等观察到镍负载在经单层La2O3改性的γ－Al2O3表面,其晶粒要比没有La2O3时小得多．Rotgerink等认为添加La后反应速率的增加不只是由于几何效应,而是La对甲烷化本身有促进作用,单位镍表面的活性是随La含量不同而改变的,活性增加的同时表观活化能也增加［5］．作为助剂的La2O3在氢还原和反应过程中的变化及其作用的研究和讨论较少,目前一般认为添…     

Reversible fluorescent probe for highly selective and sensitive detection of mercapto biomolecules

A coumarin-derived complex, Hg(2)L(2), was reported as a highly sensitive and selective probe for the detection of mercapto biomolecules in aqueous solution. The addition of Cys to a 99% aqueous solution of Hg(2)L(2) resulted in rapid and remarkable fluorescence OFF-ON (emission at 525 nm) due to the ligand-exchange reaction of Cys with L coordinated to Hg(2+). The increased fluorescence can be completely quenched by Hg(2+) and recovered again by the subsequent addition of Cys. Such a fluorescence OFF-ON circle can be repeated at least 10 times by the alterative addition of Cys and Hg(2+) to the solution of Hg(2)L(2), indicating that it can be used as a convertible and reversible probe for the detection of Cys. The interconversion of Hg(2)L(2) and L via the decomplexation/complexation by the modulation of Cys/Hg(2+) was definitely verified from their crystal structures. Other competitive amino acids without a thiol group cannot induce any fluorescence changes, implying that Hg(2)L(2) can selectively determine mercapto biomolecules. Using confocal fluorescence imaging, L/Hg(2)L(2) as a pair of reversible probes can be further applied to track and monitor the self-detoxification process of Hg(2+) ions in SYS5 cells.     

Enhanced solid-state metathesis routes to carbon nanotubes

Ignition of three solids creates multiwalled carbon nanotubes in seconds. A solid-state metathesis (exchange) reaction between hexachloroethane (C2Cl6) and lithium acetylide (Li2C2) with 5% cobalt dichloride (CoCl2) added as an initiator produces up to 7% carbon nanotubes, as observed via transmission electron microscopy. Using the concept that sulfur can promote nanotube growth, the reaction yield can be increased to 15% by switching to CoS as the initiator. The more readily available, inexpensive calcium carbide (CaC2) can be substituted for lithium acetylide while maintaining comparable yields. Switching initiators to FeS can be used to further enhance the yield. A systematic study of the C2Cl6/CaC2 reaction system indicates that a yield up to 25% can be realized by using 6% FeS as the initiator. Reaction temperatures for the C(2)Cl6/CaC2 system of up to 3550 degrees C are calculated using thermodynamic data assuming quantitative yield and adiabatic conditions.     

共沉淀法掺杂SiO_2对V_2O_5-WO_3/TiO_2催化剂SCR性能的影响

通过共沉淀法将SiO_2组分掺入到V2O5-WO3/SiO_2-TiO_2催化剂TiO_2载体中,并通过多种物理化学手段,考察了不同SiO_2掺杂量对催化剂结构、表面性质与SCR性能的影响.结果表明,SiO_2掺入到TiO_2中,Si与Ti形成Si—O—Ti键,使催化剂比表面积增加.Si—O—Ti键的生成以及Si Ox物种上的-OH基团使催化剂表面Br?nsted酸增加,但新增的Br?nsted酸对SCR反应不利,并且SiO_2的掺杂也使得V~(5+)含量降低,Si—O—V键合作用使分散的VOx物种更难还原.Si组分以共沉淀法掺入到V_2O_5-WO_3/TiO_2催化剂会造成脱硝活性的显著下降.     

碳纳米管内P—Ylide反应的理论研究

碳纳米管空腔不仅可以改变填充到其内部分子的性质,而且对其内部的SN2取代反应有促进或抑制作用,因而被视为一种新型的“固体溶剂”．本文通过密度泛函理论研究了CH2O和PH3CH2在气相、苯溶液和碳纳米管空腔内的[2＋2]加成反应．结果表明,与气相相比,碳纳米管空腔对于[2＋2]环加成反应影响不大,这是因为所研究的[2＋2]环加成反应中,反应物并不是轴对称的,不同于SN2取代反应的一维线性排列,所以具有较大轴向极化率的碳纳米管对[2＋2]环加成反应影响较小．     

2-[(8-Hydroxyquinolinyl)methylene]hydrazinecarboxamide: expanding the coordination sphere of 8-hydroxyquinoline for coordination of rare-earth metal(III) ions

The semicarbazone of 8-hydroxyquinoline-2-carbaldehyde can be easily synthesized and is an effective tetradentate ligand for the coordination of rare-earth(III) ions. Investigations with yttrium(III) and lanthanum(III) in solution and in the solid state show, that the small yttrium ion can form 2 : 2 (1 : 1 stoichiometry) and 2 : 1 ligand to metal complexes (X-ray structures: [LY(NO3)(DMF)2]2Cl2 x 2DMF and [LL'Y] x 3MeOH x Et2O). With the larger lanthanum(III) ion only a well defined 1 : 1 complex (X-ray structure: [LLa(NO3)(MeOH)2]2(NO3)2) can be observed but probably 2 : 1 complexes are also formed. The X-ray structure analyses of [(L-H)MCl3] x MeOH (M = Er, Ho) and Na[(micro-NO3){LEu(NO3)2}2] x 2DMF show different coordination modes of the ligand. It can coordinate in its deprotonated but also in the protonated form.     

超微粒La-Co氧化物催化剂对柴油机尾气碳黑催化燃烧性能的研究

用有机酸络合法制备了Co3O4，NiCo2O4和LaCo2O43种催化剂。通过程序升温氧化反应(TPO)技术对这3种催化剂进行模拟柴油碳黑催化燃烧反应的活性评价。研究发现以Co3O4为活性成分的催化剂能显著降低碳黑燃烧的温度。以Ni和La部分取代Co3O4后形成的复合氧化物NiCo2O4和混合氧化物LaCo2O4能改进Co3O4的氧化活性。但是NiCo2O4不能改进碳黑在松散接触时的燃烧活性；而混合氧化物LaCo2O4由于形成了超微粒含缺陷的LaCoO3钙钛矿型结构，它具有良好的低温氧化活性和表面原子移动性，因而能显著改进碳黑在松散接触时的燃烧活性。     

负载型光催化材料CeO2-TiO2/SiO2的表面结构与光响应性能

采用表面改性法制备了负载型光催化材料CeO2-TiO2/SiO2,并用X射线衍射,比表面积测定,红外光谱,程序升温还原和紫外可见漫反射光谱技术对固体材料的结构和光响应性能进行了表征.结果表明,CeO2与TiO2在材料表面存在相互修饰作用,CeO2能拓展TiO2的光响应范围,使TiO2吸光区域由紫外拓宽至可见光区,从而提高材料的光能利用率;Ti4 可以进入CeO2晶格,形成Ce-O-Ti键合,使得Ti4 平均配位数增加,同时提高了CeO2体相晶格氧的活性;TiO2有助于提高CeO2在载体表面的分散程度,减小CeO2的微晶尺寸,提高固体材料的能隙值和氧化还原能力.     

Room-temperature hydrogen uptake by TiO(2) nanotubes

TiO(2) nanotubes can reproducibly store up to approximately 2 wt % H(2) at room temperature and 6 MPa. However, only about 75% of this stored hydrogen can be released when the hydrogen pressure is lowered to ambient conditions, suggesting that both physisorption and chemisorption are responsible for the hydrogen uptake. FTIR spectroscopy, temperature-programmed desorption (TPD), and pressure-composition (P-C) isotherms suggest that 75% of the H(2) is physisorbed and can be reversibly released upon pressure reduction. Approximately 13% is weakly chemisorbed and can be released at 70 degrees C as H(2), and approximately 12% is bonded to oxide ions and released only at temperatures above 120 degrees C as H(2)O.     

CO2-Folded Single-Chain Nanoparticles as Recyclable,Improved Carboxylase Mimics

Emulating the function of natural carboxylases to convert CO₂ under atmospheric condition is a great challenge. Herein we report a class of CO₂-folded single-chain nanoparticles (SCNPs) that can function as recyclable, function-intensified carboxylase mimics. Lewis pair polymers containing bulky Lewis acidic and basic groups as the precursor, can bind CO₂ to drive an intramolecular folding into SCNPs, in which CO₂ as the folded nodes can form gas-bridged bonds. Such bridging linkages highly activate CO₂, which endows the SCNPs with extraordinary catalytic ability that can not only catalyze CO₂-insertion of C(sp³)-H for imitating the natural enzyme's function, it can also act on non-natural carboxylation pathways for C(sp² and sp)-H substrates. The nanocatalysts are of highly catalytic efficiency and recyclability, and can work at room temperature and near ambient CO₂ condition, inspiring a new approach to sustainable C₁ utilization.     

UV irradiation controlled cold vapor generation using SnCl2 as reductant for mercury speciation.

A simple and ultrasensitive method, which was based on cold vapor generation (CVG) coupled to atomic fluorescence spectrometry (AFS), was proposed for speciation analysis of inorganic mercury (Hg2+) and methylmercury (MeHg) in water samples. In the presence of UV irradiation, all the mercury (MeHg+Hg2+) in a sample solution can be reduced to Hg0 by SnCl2; without UV irradiation, only Hg2+ species can be determined. So the concentration of MeHg can be obtained from the difference of the total mercury and Hg2+ concentration; thus, speciation analysis of Hg2+ and MeHg was simply achieved without chromatographic separation. Under the optimized experimental conditions, the limits of detection were 0.01 ng mL-1 for both Hg2+ and MeHg. The sensitivity and limit of detection were not dependent on the mercury species, and a simple Hg2+ aqueous standard series can be used for the determination of both Hg2+ and MeHg.     

光照下自然水体生物膜产生H2O2及其对十二烷基苯磺酸钠降解的影响

通过模拟实验研究了不同活性的自然水体生物膜在光照条件下生成过氧化氢(H₂O₂)的反应. 并研究了光照对自然水体生物膜体系中十二烷基苯磺酸钠(SDBS)降解的影响, 结合无生物膜H₂O₂溶液中SDBS的降解实验, 验证了H₂O₂对SDBS降解的作用. 结果表明, 具有生物活性的生物膜可以生成H₂O₂, 而无活性和光合作用受到抑制的生物膜则不能生成H₂O₂; 光照条件下, 生物膜体系中SDBS的降解量明显高于无光照条件下的; 光照和Fe²⁺对H₂O₂降解SDBS有促进作用.     

Pb在锗酸镉基质中的长余辉发光特性

通过高温固相反应在空气中制得单相Cd₂Ge₇O₁₆:Pb²⁺长余辉发光材料.分析了Cd₂Ge₇O₁₆和Cd₂Ge₇O₁₆:Pb²⁺的激发光谱和发射光谱,指出Pb²⁺的发光是该离子的³P₁-¹S₀跃迁产生的;分析了Cd₂Ge₇O₁₆:Pb²⁺的发光存在基质对Pb²⁺的能量传递;并把长余辉性质归结为基质中Cd离子的挥发产生的空穴陷阱.提出了长余辉发光机理模型.     

Highly selective and sensitive near-infrared fluorescent sensors for cadmium in aqueous solution

On the basis of tricabocyanine, two near-infrared fluorescent sensors CYP-1 and CYP-2 have been designed and synthesized. Both of them can selectively and sensitively recognize Cd(2+) from other metal ions, especially the CYP-2, which can distinguish Cd(2+) in neutral buffer solution.