N-乙基-1，10-菲罗啉-2-甲胺镍(Ⅱ)配合物的合成、晶体结构及性质研究(英)

A novel ligand N-ethyl-1,10-phenanthroline-2-methanamine and its Ni(Ⅱ) complex have been synthesized. The crystal structure of the complex has been determined by X-ray diffraction method. The Ni(Ⅱ) is five-coordinated by three nitrogen atoms from the ligand and two Cl^- anions in a distorted trigonal bipyramidal environment: the N(2), Cl(1) and Cl(2) in equatorial plane; the N(1) and N(3) in axial positions. The UV-spectra and IR-spectra of the ligand and its Ni(Ⅱ) complex were recorded and discussed. The thermodynamic properties of the ligand with various bivalent metals were studied by potentiometric titrations and the order of the stability constants is in agreement with the Irving-Williams order in coordination chemistry. CCDC: 221750.     

DEACTIVATION OF P_2O_5-MgO/RE_2O_3 CATALYST FOR OXIDATIVE COUPLING OF METHANE

Techniques including TPD,XPS,XRD and spectrophotometry have been applied to theinvestigation of the deactivation of a highly active P_2O_5-MgO/RE_2O_2 catalyst during a 100-h test.The results of the studies have shown that there is little difference in various properties between thefresh and the deactivated catalyst except for the surface acid-base property which is demonstrated to becontrolled by the presence of phosphorus on the catalyst surface.The deactivation of the catalyst ismainly due to the heavy loss of phosphorus on the surface that causes an increase of the surface basiccenters and a decrease of the surface acid centers,and the coordination between the acid and basiccenters is considerably weakened with a subsequence of the drop of the C_2 selectivity.     

Molecular design and theoretical investigation into one-and two-photon absorption properties of two series of cyclometalated platinum(Ⅱ) complexes

We have theoretically investigated two series of cyclometalated Pt(Ⅱ) complexes,a series [Pt(C,N,N) Cl] and b series [Pt(C,N,Npyrazolyl) Cl].The geometrical and electronic structures are calculated at the ECP60MWB//6-31G*(H,C,Cl,N,S) basis set level using DFT method;one-photon absorption(OPA) properties are calculated by using both TDDFT and ZINDO methods and two-photon absorption(TPA) properties are obtained with the ZINDO/SOS method.The resonance integrals parameters(βsp and βd) for Pt are adjusted to -1 and -28.5 eV,respectively,to make max OPA wavelength calculated by ZINDO closest to the experimental data and TDDFT results.The calculated results indicate the molecule 2b([Pt(Cnaphthyl,N,Npyrazolyl) Cl]) has the biggest potential as outstanding TPA materials because(i) the TPA properties of b series are more outstanding in IR wavelength range,the molecules in b series have good transparencies and possess 1-pyrazolyl-NH that is also available for another metal coordination(e.g.,dimerization) and chemical interactions;(ii) when C is Cnaphthyl in the C,N,N ligand of cyclometalated Pt(Ⅱ) complexes,the molecules have the best conjugation effect and the best TPA properties.     

Synthesis and structural characterization of a novel dimolybdenum(Ⅰ) compound with mixed-tribridging ligands:[Bu_4N][Mo_2(μ-SPh)_2(μ-Cl)(CO)_6]

A novel mixed-trib ridged dimolybdenum(Ⅰ) compound [Bu4N][Mo2(n-SPh)2(u-Cl)(CO)6] (1) has been synthesized from the reaction of Mo2 (CO)8 (SPh)2 with ButNCl.Compound 1 was characterized by IR,UV-Vis and 1H,13C,95Mo NMR spectroscopic analyses.The electrochemical behavior was measured by cyclic voltammetry,indicating a quasi-reversible two-electron transfer in one step.The crystal structure determined by X-ray crystallography shows that 1 contains a [Mo2(u-S)2(u-Cl)]- core with a planar Mo2S2 unit and a Cl bridge.The Mo-Mo distance is 0.28709(7) nm,and the Mo-Cl-Mo angle is 66.44(4).A newface-sharing bioctahedral structure is discussed.     

Preparation, Properties and Mechanism of Inhomogeneous Calcium Alginate Ion Cross-linking Gel Microspheres

Inhomogeneous calcium alginate ion cross-linking gel microspheres,a novel ion absorbent,were prepared by dropping a sodium alginate solution to a calcium chloride solutioin via an electronic droplet generator.Calcium alginate microspheres have uniform particle sizes.a smooth surface and a microporous structure.The electrode probe reveals the inhomogeneous distribution of calcium ions with the highest concentration on the surface,and the lowest concentration in the cores of the spheres.As a novel ion adsorbent,calcium alginate gel microspheres have a lower limiting adsorption mass concentration,a higher enrichment capacity and a higher adsorption capacity for Pb^2 than usual ion exchange resins.The highest percentage of the adsorption is 99.79%.The limiting adsorption mass concentration is 0.0426mg/L.The adsorption capacity for Pb^2 is 644mg/g,Calcium alginate gel microspheres have a much faster ion exchange velocity than D418 chelating resin and D113 polyacrylate resin.The moving boundary model was employed to interpret the ion exchange kinetics process,which indicates that the ion exchange process is controlled by intraparticle diffusion of adsorbable ions.So the formation of inhomogeneous gel microspheres reduces the diffusion distance of adsorbable ions within the spheres and enhances the ion exchange velocity.Alginate has a higher selectivity for pb^2 than for Ca^2 and the selectivity coefficient KCa^Pb is 316. As an ion cross-linking gel,calcium alginate inhomogeneous microspheres can effectively adsorb heavy metal Pb^2 at a higher selectivity and a higher adsorption velocity.It is a novel and good ion adsorbent.     

CRYSTALLOGRAPHIC STRUCTURE AND MAGNETIC PROPERTIES OF R_(2)Fe_(17)N_(2.4)

By a proper thermal treatment, the nitrogen atoms can enter the R2Fe17 structure. The crystallographic and intrinsic magnetic properties as well as their relationship have been studied by magnetic measurements, X-ray and neutron diffraction techniques. The neutron data indicate that the nitrogen atoms occupy the interstitial sites in the Th2Zn17-type rhom-bohedral structure. The inserting nitrogen atoms are found to dilate the cell volume, increase the Curie temperature and enhance the saturation moment by raising the difference in the electron number between the spin-up and spin-down 3d subbands of the Fe atoms. Furthermore, the nitrogen atoms have an important effect on the magnetocrystallic anisotropy, which results in an easy axis with Sm2Fe17N2.4. All these make Sm2Fe17N2.4 favorable for permanent magnet applications.     

PPC-based Reactive Hot Melt Polyurethane Adhesive(RHMPA)——Efficient Glues for Multiple Types of Substrates

Tens of billion metric tons of anthropogenic CO_2 discharged from the burning of fossil fuels lead to an enormous environmental and resource burden. It is charming to transform CO_2 to desirable, economical chemicals and materials. Poly(propylene carbonate)(PPC) is an emerging CO_2-based material. Herein, we report the design, synthesis and characterization of the reactive hot melt polyurethane adhesive(RHMPA) based on PPC polyol. The resultant RHMPAs exhibit good adhesion properties to multiple substrates including plastics(PC, PMMA, ABS) and metals(aluminium, steel), which is comparable to or even better than conventional RHMPAs prepared from petro-based polyol. Furthermore, the PPC-based RHMPAs have tunable mechanical properties, and are thermally stable in the typical working range of bonding process(up to 270 °C). The study is expected to expand the applications of PPC and provide a new type of CO_2-based renewable and eco-friendly materials.     

Theoretical Study of N_2O Adsorption and Decomposition on the InN （0001） Surface

The adsorption and decomposition of N2O on the InN (0001) surface have been explored employing density functional theory method. To study the most favorable N2O adsorption model, ten typical adsorption cases (four for the parallel style and six for the vertical style) were proposed. The calculated results indicate that the parallel models are energetically preferred over the vertical models. The parallelly adsorbed N2O prefers to be dissociated on the surface, the dissociated O atom is combined at the fcc site, and the N-N piece is desorbed from the surface and forms N2 molecules. The comparison of the density of states of InN (0001) surface before and after N2O adsorption is analyzed in detail. Through the searching for transition state of decomposition reaction, a very low energy barrier of 45.0 KJ/mol is derived.     

Characterization and performance of Cu/ZnO/Al_2O_3 catalysts prepared via decomposition of M(Cu,Zn)-ammonia complexes under sub-atmospheric pressure for methanol synthesis from H_2 and CO_2

Methanol synthesis from hydrogenation of CO2 is investigated over Cu/ZnO/Al2O3 catalysts prepared by decomposition of M(Cu,Zn)-ammonia complexes (DMAC) at various temperatures.The catalysts were characterized in detail,including X-ray diffraction,N2 adsorption-desorption,N2O chemisorption,temperature-programmed reduction and evolved gas analyses.The influences of DMAC temperature,reaction temperature and specific Cu surface area on catalytic performance are investigated.It is considered that the aurichalcite phase in the precursor plays a key role in improving the physiochemical properties and activities of the final catalysts.The catalyst from rich-aurichalcite precursor exhibits large specific Cu surface area and high space time yield of methanol (212 g/(Lcat·h);T=513 K,p=3MPa,SV=12000 h-1).     

Properties of alkylbenzimidazoles for CO2 and SO2 capture and comparisons to ionic liquids

To date, few reports have been concerned with the physical properties of the liquid phases of imidazoles and benzimidazoles-potential starting materials for a great number of ionic liquids. Prior research has indicated that alkylimidazole solvents exhibit different, and potentially advantageous physical properties, when compared to corresponding imidazolium-based ionic liquids. Given that even the most fundamental physical properties of alkylimidazole solvents have only recently been reported, there is still a lack of data for other relevant imidazole derivatives, including benzimidazoles. In this work, we have synthesized a series of eight 1-n-alkylbenzimidazoles, with chain lengths ranging from ethyl to dodecyl, all of which exist as neat liquids at ambient temperature. Their densities and viscosities have been determined as functions of both temperature and molecular weight. Alkylbenzimidazoles have been found to exhibit viscosities that are more similar to imidazolium-based ILs than alkylimidazoles, owed to a large contribution to viscosity from the presence of a fused ring system. Solubilities of CO2 and SO2, two species of concern in the emission of coal-fired power generation, were determined for selected alkylbenzimidazoles to understand what effects a fused ring system might have on gas solubility. For both gases, alkylbenzimidazoles were determined to experience physical, non-chemically reactive, interactions. The solubility of CO2 in alkylbenzimidazoles is 10%-30% less than observed for corresponding ILs and alkylimidazoles. 1-butylbenzimidazole was found to readily absorb at least 0.333 gram SO2 per gram at low pressure and ambient temperature, which could be readily desorbed under an N2 flush, a behavior more similar to imidazolium-based ILs than alkylimidazoles. Thus, we find that as solvents for gas separations, benzimidazoles share characteristics with both ILs and alkylimidazoles.     

Metathesis of Butylene-2 and Ethylene to Propylene over 3.0Mo/(Hβ+ γ-Al203) Catalysts with Different γ-Al203 Contents

A series of 3. 0Mo/(Hβ γ-Al2O3) samples with γ-Al2O3 contents in the range of 0-100% (mass fraction) was studied by means of XRD, NH3-TPD, TPR and BET determinations for characterizing their structures. The Hβ zeolite structure in the 3. 0Mo/Hβ sample can be effectively stabilized by adding some γ-Al2O3to Hβ zeolite. γ-Al2O3 mainly favors the formation of polymolybdate or multilayered Mo oxide, while Hβmainly forms the Al2(MoO4)3 species, as evaluated by the TPR technique. When used as the catalyst for the metathesis of butylene-2 and ethylene to propylene, there exists a close correlation between the specific surface area and stability of the catalyst. The specific surface area of the catalyst shows the maximum when (Hβ γ-Al2O3) contains 30%γ-Al2O3, which is in agreement with that of the time needed for the reaction stablization. In the case of maximum surface area, the rate of coke deposition is the minimum.     

Double perovskite oxides Sr_2Mg_(1-x)Fe_xMoO(6-δ) for catalytic oxidation of methane

The double perovskite oxides Sr2Mg1-xF exMoO6-δ were investigated as catalysts for the methane oxidation.The structural properties of catalysts were characterized in detail by X-ray diffraction,X-ray photoelectron spectroscopy and X-ray absorption spectroscopy.The catalytic property was strongly influenced by the Fe substitution.The relation between catalytic performance and the degree of Fe substitution was examined with regard to the structure and surface characteristics of the mixed oxides.The Fe-containing catalysts exhibited higher activity attributable to the possible(Fe2+,Mo6+) and (Fe3+,Mo5+)valency pairs,and the highest activity was observed for Sr2Mg0.2Fe0.8MoO6-δ.The enhancement of the catalytic activity may be correlated with the Fe-relating surface lattice oxygen species and was discussed in view of the presence of oxygen vacancies.     

ESR Characterization and Activity of V_2O_5/γ-Al_2O_3 Catalysts for Dehydrogenation of Isobutane

IntroductionIsobutene is the raw material for theproduction of many important chemicals.Thedehydrogenation of isobutane to isobutene oncatalysts Cr2 O3/γ- Al2 O3and Pt/γ- Al2 O3have beenextensively studied and successfully applied inindustry[1,2 ] .The dehydrogenation of isobutane to isobuteneis an endothermic reaction and is limited by thechemical equilibrium.Coke is easy formed on thecatalyst surface and the catalyst is frequentlyregenerated in the running.The oxidativedehydrogenation …     

Synthesis and Structure of K_8[P_2W_18Mo_2Co_2O_68(H_2O)_2][MoO_6]·15H_2O

Recently, Many tri-component heteropoly compounds have been synthesized, but tetra-component heteropoly compounds have not been reported. It is known that mixtures of Mo and Co oxides are a promoted hydrodesulphurization catalyst. The title compound is a polyoxophosphate containing Mo, Co and W, the divalent anion possesses two-fused Keggin structure, whereas MoO_6 has been confirmed to be an elementary structure unit of isopoly and heteropoly molybdates, but it, as an idependent anion, has not been reported either.     

Synthesis,crystal structures and spectral properties of cobalt (Ⅱ) complexes:[ CoL (N_3) ] ·ClO_4 and CoL (N_3)_2 [L=tris ((3,5-dimethylpyrazol-1-yl) methyl) amine

Two monomeric cobalt(Ⅱ)complexes,[CoL(N3)] ClO4(1)and CoL(N3)2(2),where L is tris((3,5-dimethylpyrazol-1-yl)methyl)amine,were synthesized and their crystal structures were determined by X-ray diffraction technique.Complex 1 is five coordinated with one azide nitrogen atom and four nitrogen atoms of the tris((3,5-dimethylpyrazol-l-yl)-methyl)amine ligand,and the metal center is in distorted trigonal bipyramidal environment.Complex 2 is six coordinated distorted octahedron with the two azide nitrogen atoms and four nitrogen donors of the tris((3,5-dimethylpyrazol-1-yl)-methyl)amine ligand.The solution behaviors of the title complexes have been further investigated by UV-Vis,and 1H NMR analysis.It is found that the formation of 1 and 2 depends on the molar ratio of the azide ion to metal salt and ligand Complex 1 attached with one azide group is more stable and easy to generate than complex 2 incorporated with two azide groups,and the reasons were well discussed.     

Synthesis of Ag-SiO2 composite nanospheres and their catalytic activity

A simple,mild,and time-saving method is employed to synthesize Ag-SiO2 composite nanospheres with Ag nanoparticles uniformly distributed on the surface of SiO2 nanoparticles.The chemical elements and the morphology of Ag-SiO2 composite nanospheres were analyzed with transmission electron microscopy(TEM),X-ray power diffraction(XRD),and X-ray photoelectron spectroscopy(XPS).On the surface of Ag-SiO2 composite nanospheres,silane coupling agent(KH-550)is introduced as an intermediary to connect the surfaces of SiO2 nanospheres and Ag nanoparticles,which is also helpful for avoiding the aggregation of Ag nanoparticles.It is found that Ag-SiO2 composite nanospheres have very good catalytic properties for the reduction of organic dyes,which may have potential application in wastewater treatment.     

REACTIVITY OF METAL(O) DITHIOCARBAMATO CARBONYL COMPLEXES [Mo(CO)_4(S_2CNEt_2)]~- (M=Mo, W): SYNTHESIS AND STRUCTURE OF A NEW MIXED-VALENCE DINUCLEAR MOLYBDENUM-SULFUR COMPLEX, [Et_4N]_2[(CO)_4MoS_2MoS_2]

<正> The reaction of [Et4N][Mo(CO)4(S2CNEt2)] with tetraethylam-monium tetrathiomolybdate affords a new mixed-valence dinuclear molybdenum complex [Et4N]2[(CO)4MoS2MoS2] (1). 1 crystallizes in the orthorhombic space group Pbom with a = 18.403(2), b = 11.963(1), c= 13. 482(1)(?) , Z = 4, V = 2986(?)3, Dc=1. 55g/cm3, Mr = 6S2. 69. R =0. 042 and Rw =0. 057 for 1975 independent reflections with I≥3σ(I), F(000) = 1416, μ =11. 2cm-1. The structure of the anion of 1 consists of an octahedron for the lowvalent Mo atom and a tetrahedron for the high-valent Mo atom sharing an S - S edge. The Mo - Mo bond distance is 2. 992 (2) (?) and the bimetallic center MoS2Mo is planar with Mo-S of 2. 517 and 2. 231 A and MoSMo angles of 78. 04° and 77. 67°. The electron delocalization between the two Mo atoms with wide separated oxidation states is also discussed.     

Trihydrated Complex of Tetrabenzimidazole Copper(Ⅱ) Sulfate

A Trihydrated complex of benzimidazole copper(Ⅱ) sulfate [(C7H6N2)4CuSO4]·3H2O was synthesized and structurally characterized. The crystal structure of this compound is built up of six solvated water molecules and two dissimilar copper ions identified as Cu1 and Cu2. The coordination geometry of copper(Ⅱ) is a slightly distorted square pyramid. The four equivalent tertiary nitrogen atoms of the benzimidazole ligand form an equatorial plane, while the oxygen atoms of sulfato occupy the axial site. In the solid state, the title compound forms a three dimensional network structure via hydrogen bonds. The benzimidazole, sulfato ion and H2O moieties are connected by the intermolecular hydrogen bonds. The (EPR) spectrum shows axial symmetry with g⊥=2.039 and g∥=2.285. Variable temperature magnetic susceptibility shows that there is a weak antiferromagnetic interaction between the neighboring copper(Ⅱ) ions.     

溶胶-凝胶新方法合成介孔铁酸铜纳米粉体催化剂上CO低温氧化(英文)

Mesoporous CuFe2O4 solid solution nanopowders with high specific surface areas were synthesized by a novel, very simple and inexpensive sol-gel route using propylene oxide as gelation agent, and used as the catalyst in low temperature CO oxidation. The samples were characterized by X-ray diffraction, N2 adsorption-desorption, thermogravimetric/differential thermal analysis, Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, and temperature-programmed reduction. The results revealed that the samples have a nanocrystalline structure with crystals in the range of 10 to 25 nm, and that all the catalysts have mesoporous pores. The addition of Cu into iron oxide affected its structural and catalytic properties. The sample containing 15 mol% Cu showed the highest specific surface area and catalytic activity, and showed high catalytic stability in low temperature CO oxidation.     

Concise Synthesis of(±)-epi-Chrysotricine

Chrysotricine 1 was isolated from the Chinese herb medicine Hedyotis Chrysotricha and was shown to possess antitumor activity1. Its structure has been elucidated as a novel zwitterionic (-carboline alkaloid containing a 2,2,5-trisubstituted tetrahydrofuranyl group. The (-carboline compounds have attracted considerable attraction in recent years because of their promising and intriguing biological activities2. Recently, we have established the absolute configuration of chrysotricine by the fir…