Adsorption and dissociation of carbon trioxide on Ag(100)

Using density functional theory methods, we have studied carbon trioxide, its adsorption and dissociation on Ag(100). In the gas phase, two isomers are found, D_3h and C_2v, with the latter of 2.0 kcal mol^?1 lower in energy at the PW91PW91/6?31G(d) level. For CO₃ on Ag(100), the calculated adsorption energy is 91.2 and 89.1 kcal mol^?1 for the bi‐coord perpendicular and tri‐coord parallel structures, respectively. Upon the adsorption, 0.50 ～ 0.56 electron is transferred from silver to CO₃, indicative of significant ionic characters of the adsorbate‐surface bonding. In addition, the geometry of CO₃ is largely changed by its strong interaction with silver. For CO_3(ad) → O_(ad) + CO_2(gas), the energy barrier is calculated to be 19.8 kcal mol^?1 through the bi‐coord path. The process is endothermic with an enthalpy change of +17.3 ～ +26.7 kcal mol^?1 and the weakly chemisorbed CO₂ is identified as an intermediate on the potential energy surface. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010     

Chemoselective reduction of azides catalyzed by molybdenum xanthate by using phenylsilane as the hydride source

A chemoselective, neutral, and efficient strategy for the reduction of azides to corresponding amines catalyzed by dioxobis(N,N,-diethyldithiocarbamato) molybdenum complex (1, MoO₂[S₂CNEt₂]₂) in the presence of phenylsilane is discovered. This chemoselective reduction strategy tolerates a variety of reducible functional groups.     

Deoxybenzoins from Stille carbonylative cross-couplings using molybdenum hexacarbonyl

Stille-type carbonylative cross-couplings, employing palladium catalysis and Mo(CO)₆ as the carbon monoxide carrier, were used for the preparation of deoxybenzoins. Straightforward transformations were conveniently performed in closed vessels at 100 °C, providing the products in good yields. Benzyl bromides and chlorides were used as coupling partners with aryl and heteroaryl stannanes. This mild three-component carbonylation employs the destabilizing agent DBU to promote smooth release of carbon monoxide from Mo(CO)₆, which made this protocol operationally simple and minimized the formation of Stille diarylmethane products.     

Synthesis,crystal structure and reactivity of a new pentacoordinated chiral dioxomolybdenum(VI) complex

The novel tridentate chiral ligand 2,6-bis{[(1R,2S,4R)-2-hydroxy-1,3,3-trimethyl-bicyclo[2.2.1]hept-2-yl]}pyridine (1) was readily prepared by reaction of 2,6-dilithiopyridine with (R)-(−)-fenchone. Reaction of 1 with [MoO₂(acac)₂] resulted in the formation of the new metal-oxo five-coordinated complex [MoO₂(ONO)] (2) [ONO = (1 – 2H)]. The reactivity of 2 has been studied and the derivatives [MoS₂(ONO)] (3) and [MoO(O₂)(ONO)] (4) were prepared. The compounds 1–4 have been characterised by ¹H and ¹³C{¹H} NMR, microanalysis and IR spectroscopy. Furthermore, the molecular structures of 1 and 2 have been determined by single-crystal X-ray diffraction. The behaviour of 2 as catalyst in oxotransfer and in nucleophilic substitution of propargylic alcohols reactions has been tested.     

Pressure‐Induced Structural Transition in WO3 Nanowires

Raman spectroscopic analysis is performed on WO₃ nanowires at room temperature at pressures from ambient conditions to 45 GPa. Linear dependence of the first‐order Raman signal on various high‐pressure (HP) sections is observed. Upon increasing the applied pressure, the WO₃ nanowires undergo four phase transitions at pressures around 1.7, 4.6, 21.5, and 26.2 GPa, which are all less than that reported for bulk WO₃. When the pressure is up to 42.5 GPa, a new high‐pressure phase (HP5) appears. This phase has never been reported and is not reversible while unloading the pressure.     

Elaboration and characterisation of a plasticized cellulose triacetate membrane containing trioctylphosphine oxyde (TOPO): Application to the transport of uranium and molybdenum ions

A cellulose triacetate (CTA) membrane containing trioctylphosphine oxyde (TOPO) as carrier and 2-nitrophenyloctyl ether (NPOE) as a plasticizer was prepared. The membrane CTA + NPOE + TOPO was characterised using chemical techniques as well as Fourier Transform InfraRed (FTIR) spectroscopy, X-ray diffraction and Scanning Electron Microscopy (SEM). The CTA membrane is characterised by well-defined pores; these pores are completely filled with the NPOE and carrier. Surfaces of membranes with TOPO are smooth. The systems constituted by the mixture of CTA + NPOE, CTA + NPOE + TOPO do not give any diffraction. This can be due to the absence of crystallization within the membrane. On the other hand, this result should be attributable to the amorphous state of the structure, which permits us to eliminate the mechanism of transfer of the ions by electron jump. A comparative study of transport across a polymer inclusion membrane (PIM) and a supported liquid membrane (SLM) containing the same carrier in chloroform has shown that uranium or molybdenum transport efficiency was increased using PIM instead of SLM. PIM showed higher stability than SLM, the flux of transport remain constant in the former case after 2 weeks.     

Determination of molybdenum(VI) by differential pulse polarographic technique using 4-(2-hydroxy phenyl ethaminodiol), benzene-1,3-diol(4-2-HPEDB-1,3,D)

A novel analytical reagent 4-(2-hydroxy phenyl ethaminodiol), benzene-1,3-diol(4-2-HPEDB-1,3,D) was synthesized for the determination of molybdenum(VI). The present paper reveals the detailed study of electroanalytical behaviour for [Mo-(4-2-HPEDB-1,3,D)] complex under optimized conditions. The peak obtained for [Mo-(4-2-HPEDB-1,3,D)] prevent the interference of foreign ions which shows the sensitivity of the proposed method. The linearity was maintained at the concentration range of 0.5–200 μg/mL at pH 4.5 with correlation factor 0.9997. The present method was successfully applied for the analysis of molybdenum(VI) in biological fluids and plant material. The results obtained from the proposed method show good agreement with reference method.     

钼(Ⅵ)-2-(5-溴-2-吡啶偶氮)-5-二乙氨基苯酚-溴酸钾体系的催化吸附波

在0.046mol/L HAc-NaAc(pH4.84)支持电解质中,Mo(Ⅵ)-2-(5-溴-2-吡啶偶氮-5-二乙氨基苯酚-溴酸钾)[Mo(Ⅵ)-5-Br-PADAP-KBrO3]络合物于-0.72V(vs.SCE)左右产生一个灵敏的络合吸附波,该波的二阶导数峰峰电流与1.5×10-8-2.0×10 -5 mol/...     

Direct current and impedance spectroscopic studies on MoO3 modified ZnPc/ITO Schottky diodes

We use experimental results of direct current and low signal impedance spectroscopy to investigate the conduction mechanism in organic semiconductor ZnPc. The experimental results demonstrate an increase in current and holes mobility by the introduction of a thin MoO₃ film at the ITO/ZnPc interface. This significantly improves the device performance. The improvement is explained in terms of the reduction in the effective barrier for charge transfer from ZnPc to ITO.     

Hexagonal nanorods of tungsten trioxide: Synthesis, structure, electrochemical properties and activity as supporting material in electrocatalysis

Tungsten trioxide, unhydrated with hexagonal structure (h-WO₃), has been prepared by hydrothermal method at a temperature of 180 °C in acidified sodium tungstate solution. Thus prepared h-WO₃ has been characterized by X-ray diffraction (XRD) method and using electrochemical techniques. The morphology has been examined by scanning and transmission electron microscopies (SEM and TEM) and it is consistent with existence of nanorods of 50-70 nm diameter and up to 5 μm length. Cyclic voltammetric characterization of thin films of h-WO₃ nanorods has revealed reversible redox behaviour with charge-discharge cycling corresponding to the reversible lithium intercalation/deintercalation into the crystal lattice of the h-WO₃ nanorods. In propylene carbonate containing LiClO₄, two successive redox processes of hexagonal WO₃ nanorods are observed at the scan rate of 50 mV/s. Such behaviour shall be attributed to the presence of at least two W atoms of different surroundings in the lattice structure of h-WO₃ nanorods. On the other hand, in aqueous LiClO₄ solution, only one redox process is observed at the scan rate of 10 mV/s. The above observations can be explained in terms of differences in the diffusion of ions inside two types of channel cavities existing in the structure of the h-WO₃ nanorods. Moreover, the material can be applied as active support for the catalytic bi-metallic Pt-Ru nanoparticles during electrooxidation of ethanol in acid medium (0.5 mol dm⁻³ H₂SO₄).