Syntheses,Structures, Luminescent Properties and Photocatalytic Activities of Two Lead（II） Compounds

Two lead（ll） compounds, [Pb（qlc）（phen）2（NO3）]e-H20 （1） and [Pb（qlc）z（phen）]-3H20 （2） （Hqlc = quinoline-3-carboxylic acid, phen = 1,10-phenanthroline）, were synthesized and charac- terized by elemental analysis, single-crystal X-ray diffraction, IR and thermogravimetric analysis. Crystal 1 is of monoclinic, space group C2/c with a = 25.246（5）, b = 12.543（3）, c = 18.917（4） A, β = 105.77（3）°, V= 5765（2） A3, Z = 4, C68H46N12OllPb2, Mr = 1621.53, Dc = 1.886 g.cm-3,/.t（MoKa） = 5.912 mm-1, F（000） = 3152, GOOF = 1.080, the final R = 0.022 and wR = 0.0571 for 4822 observed reflections （1 〉 2a（/））. Crystal 2 is oftriclinic, space group Pi with a = 8.7883（10）, b = 11.7031 （13）, c = 15.9320（17） A, a = 69.9400（10）, fl = 78.9780（10）, 7 = 79.1650（10）°, V = 1497.4（3） A3, Z = 2, C32H26NaO7Pb, Mr. = 785.71, Dc = 1.729 g.cm-s, p（MoKa） = 5.688 mm-1, F（000） = 756, GOOF = 1.106, the final R = 0.0313 and wR = 0.088 for 59i5 observed reflections （1 〉 2σ（I））. Single-crystal X-ray diffraction analysis reveals that 1 exhibits a two-dimensional （2D） layer based on π-π stacking interactions between phen. Simultaneously, the adjacent 2D layers are assembled via π-π stacking interactions between phen and quinoline tings into a 3D supramolecular structure. The zero- dimensional structure of 2 is also further extended by π-π interactions to form a 2D supramolecular layer. Furthermore, these two compounds exhibit photoluminescence at room temperature in the solid state and their photocatalytic activities have been studied by degradation methylene blue.     

A New Sandwiched-type Polyoxotungstate Containing {Cd4} Transition-metal Cluster： Synthesis,Structure and Luminescent Property

A new sandwiched polyoxometalate [HK11Cd4Cl2（PW9034）2]·18H2O （1）, incor- porating a unique hybrid tetranuclear cadmium cluster （abbreviated to {Cd4}） with two trivacant polyanions [B-α-PW9O34]9-, has been hydrothermally synthesized and structurally characterized by elemental analyses, IR spectroscopy, UV-vis, and single-crystal X-ray diffraction analysis. Crystal data for 1： monoclinic, space group C2/c, a = 19.2997（4）, b = 13.8014（3）, c = 31.9819（8） A, β = 102.764（2）°, V= 8308.3（3） A3, Z = 4, P2O86Cl2K11Cd4W18H37, Mr = 5735.13, Dc = 4.584 mg-mm-3, F（000） = 10084, μ = 26.579 mm-1, the final R = 0.0378 and wR = 0.0989 for 6558 observed reflections （I〉 2σ（I））. X-ray crystallographic study shows that the molecular structure of 1 contains four cadmium atoms. Two CdO6 distorted octahedra and two CdOsC1 distorted octahedra combine with each other in turn via edge-sharing, resulting in a regular rhomb-like cluster sandwiched between two {B-a-PW9034} units. Further, the sandwich-type polyoxoanions were connected by K＋ ions to form a complicated 3-D open-framework through connecting with each terminal O atom of the [Cd4C12（PW9O34）2]12- polyoxoanions. In addition, compound 1 exhibits photoluminescence property at room temperature and the band gap can be assessed at 3.25 eV.     

Decatungstate Incorporated Metal-organic Framework for Degradation of Rhodamine B under Sunlight Irradiation

A new decatungstate incorporated metal-organic framework {[Co2（bpdo）5（H2O）n- W10O32]}n·nbpdo·2nH2O（1, bpdo = 4,4＇-bis（pyridine-N-oxide） has been synthesized through a one-step hydrothermal reaction and characterized by elemental analyses, IR, solid UV-vis absorption spectra, and single-crystal X-ray diffraction. The structural analysis indicates that 1 displays a one-dimensional ladder structure with [W10O32]4- as guest incorporated by electrostatic interaction. The photocatalytic property of the framework toward a rhodamine B （RhB） solution was also investigated. The results indicated that compound 1 possesses high photocatalytic activity in heterogeneous system under sunlight irradiated.     

Modulating the Electronic Structures of Single-walled Carbon Nanotubes by Filling with Electron Acceptors and the Effect on Their Reactivity with Aryl Diazonium Salts

The electronic structures of single-walled carbon nanotubes （SWCNTs） were modulated by filling with tetracyanoquinodimethane （TCNQ）, a strong electron acceptor. The structures of TCNQ-filled SWCNTs were checked by X-ray diffraction analysis, high-resolution transmission electron microscopy and Raman spectroscopy. Optical absorption spectroscopy demonstrated an enhanced reactivity between aryl diazonium and semiconducting SWCNTs.     

Synthesis and Crystal Structure of （E）-2-phenyl-6,7dihydrobenzofuran-4（5H）-one O-cyanomethyl Oxime

A pair of E/Z-isomers of 2-phenyl-6,7-dihydrobenzofuran-4（5H）-one O-cyanomethyl oxime,C16H14N2O2,as potential drugs for treating peptic ulcer and other acid-related diseases have been synthesized and characterized by IR,MS and NMR spectra.Meanwhile,the crystal of IIIa was obtained and determined by X-ray single-crystal diffraction.Crystal data： monoclinic system,space group P21 /c,a = 8.423（8）,b = 19.596（16）,c = 8.770（8）,β = 107.750（12）°,V = 1379（2）3,Z = 4,F（000） = 560,Dc = 1.283 g/cm3,μ = 0.086 mm 1,R = 0.0681 and wR = 0.2029 for 14472 independent reflections（Rint = 0.0782） and 2428 observed ones（I 2σ（I））.     

Three Isomeric Chiral Metal-organic Frameworks Determined by Different Halogen Ions

Three isomeric metal-organic frameworks,[Cd2（X）（btc）（DMA）3]n（X = Cl（1）,Br（2）,I（3）,H3btc =1,3,5-benzenetricarboxylic acid and DMA = N,Nˊ-dimethylacetamide）,have been synthesized and characterized by elemental analysis,infrared spectra（IR）,thermogravimetric（TG） analyses and single-crystal X-ray diffraction.Single-crystal X-ray analysis reveals that compounds 1–3 crystallize in the orthorhombic P212121 space group,and feature a three-dimensional（3D） extended framework containing dinuclear [Cd2（COO）3] units as the secondary building units（SBUs）.Topological analysis reveals that compounds 1–3 can be simplified into a 3-connected srs topological network.     

Synthesis and Crystal Structure of a B-H Activated Compound Containing a Furan Ring and an ortho-Carborane Cage

A new compound [CpCo（Se2C2BIoH9）CH2C（O）C4H30] has been synthesized and characterized by elemental analysis, IR spectroscopy, NMR, MS and single-crystal X-ray diffraction. The complex crystallizes in the monoclinic system, space group P21/c with a = 10.9481（10）, b = 24.6600（12）, c = 25.7430（14） A, β = 100.863（3）°, C42H57B30Co306Se6＂CH2C12＂0.25H20, Mr = 1722.16, V = 6825.6（8） A3, Dc= 1.676 g/cm3, Z = 1 and F（000） = 3346. The molecular structure shows a 1：1 ratio product of the two reactants of 16e half-sandwich complex CpCo（Se2C2B10H10） and alkyne 1-（2-furyl）-2-propyn-l-one. The hydrogen atom in the B（3） position of CpCo（Se2C2B10HIo） has been activated and migrated to the terminal carbon of 1-（2-furyl）- 2-propyn-l-one to form the B-CH2 unit. The title compound molecules are linked and extended further into a one-dimensional chain through atypical hydrogen bonds.     

Synthesis and photocatalytic properties of core–shell TiO~2@ZnIn_2S_4 photocatalyst

A novel core–shell TiO2@ZnIn2S4composite has been synthesized successfully by a simple and flexible hydrothermal route using TiO2as precursors.The as-synthesized samples were characterized by X-ray diffraction,UV–vis diffuse reflectance spectra and transmission electron microscopy.The photocatalytic properties of samples were tested by degradation of aqueous methylene blue（MB）under visible light irradiation.It was found that the as-synthesized TiO2@ZnIn2S4photocatalyst was more effcient than TiO2and ZnIn2S4in the photocatalytic degradation of MB.Moreover,TEM images confrmed the TiO2@ZnIn2S4nanoparticles possessed a well-proportioned core–shell morphology.     

二氧化铈促进钴氧化物表面氧化一氧化碳的原位表征研究

CO氧化由其广泛的应用而成为催化领域中研究的重要反应,Co_3O_4催化剂具有价格低廉、催化活性高等优点而引起研究者的关注,其中,催化剂的结构、表面特性及反应机理等是研究的重点.催化剂的原位研究对观察相变过程,理解相应的表面化学反应和反应机理起着重要的作用.本文采用煅烧法制备了Ce O_2掺杂的Co_3O_4,并对其催化CO氧化反应性能进行了研究.通过扫描电镜、高分辨率透射电镜、拉曼光谱和X射线光电子能谱对催化剂的微观结构和形态进行了表征.通过原位X射线衍射(原位XRD)和原位漫反射红外傅立叶变换光谱(原位DRIFTS)表征了Ce O_2掺杂Co_3O_4对CO氧化的效果.原位XRD测试是在氢气气氛中进行,借以评估催化剂的氧化还原特性.结果表明,由于Ce O_2的补氧能力,CeO_2掺杂可以提高Co~(2+)的还原能力,并促进了Co~(3+)-Co~(2+)-Co~(3+)循环.采用原位DRIFTS对CeO_2改性的Co_3O_4表面吸附的碳酸盐物种进行了探究.结果表明,吸附碳酸盐物种的CeO_2掺杂Co_3O_4催化剂的红外峰与纯Co_3O_4相比有所不同.CeO_2掺杂的Co_3O_4上吸附的碳酸盐物种较为活泼,其与催化剂表面的结合作用力比较弱,不会覆盖催化剂表面的活性位点,能有效抑制催化剂的失活.本文揭示了CeO_2掺杂Co_3O_4促进CO氧化的机理,为设计高效氧化CO的催化剂提供了理论支持.原位XRD的结果表明,由于CeO_2的补氧能力,引入CeO_2可以显著提高Co~(2+)的稳定性.换句话说,它可以通过降低Co~(2+)的氧化能力来提高Co~(2+)的还原能力,有利于促进Co~(3+)-Co~(2+)-Co~(3+)循环的稳定性,从而使Co~(2+)更容易转化为Co~(3+).原位DRIFTS表明,在某种程度上,吸附在CeO_2-Co_3O_4表面的碳酸盐物种呈游离态,与催化剂表面的结合作用力较弱.这种类型的碳酸盐更活泼,而且不会像那些强作用在催化剂表面的碳酸盐物种那样使表面钝化.CeO_2-Co_3O_4与Co_3O_4的表面吸附的碳酸盐物种的差异是由于引入的CeO_2对氧化钴表面进行修饰改性的结果.在高温和N_2气氛下进行预处理后,CeO_2表面变得光洁且形成了一些氧空位,其特殊的储氧能力通过弱吸附氧使其表面更加活泼.这些结果证实,经过CeO_2的修饰后,氧化钴表面更加活泼,且更适合CO氧化反应的发生.     

红树林湿地土壤矿物的分析

以湛江湾南海堤典型红树林湿地土壤为研究对象,采用X射线衍射(XRD)和傅立叶变换红外光谱(FTIR)快速批量鉴定土壤中矿物成分,利用扫描电子显微镜(SEM)观察土壤颗粒形貌特征并获得化学成分组成信息;同时采集附近光滩土壤样品进行对比研究,以揭示红树林湿地土壤特殊的生态环境特征。结果表明,红树林湿地土壤矿物主要由高岭石、石英、白云母、埃洛石、地开石和蛇纹石等组成;与光滩土壤相比,红树林湿地土壤矿物类型多样,而光滩土壤矿物相对单一,主要为石英和高岭石;红树林湿地土壤颗粒以片状聚合体为主,主要元素组成为C、O、S、Al、Si、Mg、Fe等,常见含有Cu、Zn、Mo等重金属元素。同时发现红树林湿地土壤颗粒含有较丰富的硫化物;而光滩土壤未发现上述特征,表明红树林湿地处于一个特殊的生态环境,土壤沉积物中富含有机质、Fe、S等,比一般潮滩更易于富集硫化物或重金属。