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941.
Dai W Chen X Wang X Liu P Li D Li G Fu X 《Physical chemistry chemical physics : PCCP》2008,10(22):3256-3262
The catalytic oxidation of CO was performed over Au/TiO(2) under UV irradiation in the presence of H(2) in different reaction systems. It was found that the introduction of H(2) enhanced the CO thermocatalytic oxidation in a CO pre-introduced system (CO/O(2)vs. CO/H(2)/O(2)), but suppressed that in an O(2) pre-introduced (O(2)/CO vs. O(2)/H(2)/CO) system. Although the CO oxidation in both CO/H(2)/O(2) and O(2)/H(2)/CO systems could be remarkably enhanced under UV irradiation, the oxidation of H(2) was suppressed under UV irradiation. It was proposed that the dissociative chemisorption H ([triple bond]Ti-H) at surface oxygen vacancy sites of TiO(2) could act as both the electron-acceptors for the photogeneration electrons and the electron-donors for the chemisorbed O(2) at TiO(2), and thus enhance the CO oxidation during the coinstantaneous process of thermocatalysis and photocatalysis. The suppression of H(2) thermocatalytic oxidation under UV irradiation might be ascribed to the electron transfer effect, i.e., the dissociative chemisorption H on Au (Au-H) could be desorbed at the H(2) molecule via accepting the photogenerated electrons from TiO(2). 相似文献
942.
Well-dispersed high-loading pt nanoparticles supported by shell-core nanostructured carbon for methanol electrooxidation 总被引:1,自引:0,他引:1
Wu G Li D Dai C Wang D Li N 《Langmuir : the ACS journal of surfaces and colloids》2008,24(7):3566-3575
Shell-core nanostructured carbon materials with a nitrogen-doped graphitic layer as a shell and pristine carbon black particle as a core were synthesized by carbonizing the hybrid materials containing in situ polymerized aniline onto carbon black. In an N-doped carbon layer, the nitrogen atoms substitute carbon atoms at the edge and interior of the graphene structure to form pyridinic N and quaternary N structures, respectively. As a result, the carbon structure becomes more compact, showing curvatures and disorder in the graphene stacking. In comparison with nondoped carbon, the N-doped one was proved to be a suitable supporting material to synthesize high-loading Pt catalysts (up to 60 wt %) with a more uniform size distribution and stronger metal-support interactions due to its high electrochemically accessible surface area, richness of disorder and defects, and high electron density. Moreover, the more rapid charge-transfer rates over the N-doped carbon material are evidenced by the high crystallinity of the graphitic shell layer with nitrogen doping as well as the low charge-transfer resistance at the electrolyte/electrode interface. Beneficial roles of nitrogen doping can be found to enhance the CO tolerance of Pt catalysts. Accordingly, an improved performance in methanol oxidation was achieved on a high-loading Pt catalyst supported by N-doped carbon. The enhanced catalytic properties were extensively discussed based on mass activity (Pt utilization) and intrinsic activity (charge-transfer rate). Therefore, N-doped carbon layers present many advantages over nondoped ones and would emerge as an interesting supporting carbon material for fuel cell electrocatalysts. 相似文献
943.
A number of difluorophenyl benzoxazole (DB) monomers and 4,4′-difluorobenzophenone (DFB) were subjected to fluoro-displacement with two different phenoxides in a polar aprotic solvent. A series of novel poly(ether-ketone benzoxazole) copolymers (PAEKBOs) were more readily prepared, in which the generation of aryl-ether linkages was the copolymer forming reaction. The effects of monomer structure and polymerization conditions on the polymerization results and polymer solubility were analyzed. Copolymers 1, 2-X, 4 and 6 were obtained with high molecular weight. Copolymers 2-X and 4 showed organic solubility, especially the copolymers 2-X could dissolve in many usual organic solvents at the solid concentration of up to 20 wt%. TGA and DSC measurements confirmed that the copolymers 2-X, 4 and 6 were thermally stable up to 500 °C, and showed single enhanced Tgs and an amorphous morphology. The copolymers behaved in many respects as engineering thermoplastics. The properties and the processability of several members of the PAEKBOs offer the prospect of being candidates to substitute poly(ether-ether-ketone) (PEEK) using in a wider usage temperature range and being high performance materials for many applications as films, coatings for optical and electronic devices and gas separation membranes. 相似文献
944.
Core-shell type multiarm star copolymers with poly(ε-caprolactone) (PCL) as shells and hyperbranched polyethylenimine (PEI) as core have been successfully prepared by the Sn(Oct)2 catalyzed ring-opening polymerization of ε-caprolactone (CL) using high molecular weigh PEIs directly as macroinitiators. The initiation efficiency is in the range of 91-95% for PEI with Mn = 104 (PEI10K) and only around 60% for PEI with Mn = 2.5 × 104 (PEI25K), leading to star polymers with an average arm number in the range of 155-276. The thermal property of the obtained multiarm star polymers were also investigated by DSC. The melting and crystallization temperatures of the star polymers increase as the PCL arm length increases when the PEI core is fixed. The fusion enthalpy, crystalline enthalpy and degree of crystallinity values of the star polymers with PEI10K core are less than those with PEI1.8K core. Due to the polarity difference between PCL arm and PEI core, the resulting multiarm star polymers can act as inverted micellar nanocapsules capable of extracting and encapsulating water soluble guests. Increasing the size and polarity of the hydrophilic PEI core of the star nanocapsules are two effective ways to enhance their hydrophilic guest encapsulation capacity. Increasing the hydrophobic PCL arm length can increase the molar ratio, whereas reduce the weight ratio of the encapsulated hydrophilic guests to the star nanocapsules. Unexpectedly, the obtained nanocapsules can entrap the bigger size hydrophilic congo red guests more than the smaller size methyl orange. 相似文献
945.
The trifluoromethyl containing heterocycles, 2-hydroxy-4-aryl-3-(thien-2-oyl)-2-(trifluoromethyl)-3,4,7,8-tetrahydro-2H-chromen-5(6H)-one derivatives 4, were synthesized via a one-pot three-component reaction of aldehyde 1 with 1,3-cyclohexanedione 2 and 4,4,4-trifluoro-1-(thien-2-yl)butane-1,3-dione 3 in the presence of a catalytic amount of Et3N. The effect of bases and solvents on the reaction efficiency and yield was briefly investigated. Treatment of 4 with an excess amount of NH4OAc in ethanol afforded 2-trifluoromethyl-1H-quinolin-5-one derivatives 5. Refluxing of 4 with TsOH in CHCl3 gave the corresponding dehydrated products 8. 相似文献
946.
947.
948.
949.
Gui‐Ge Hou Li‐Ying Ma Xian‐Ping Dai 《Acta Crystallographica. Section C, Structural Chemistry》2011,67(10):m321-m323
The title compound, [Zn(C9H7N3)2(H2O)4](CF3O3S)2, contains an octahedral [ZnL2(H2O)4]2+ cationic complex with trans geometry (Zn site symmetry ), and each 5‐(3‐pyridyl)pyrimidine (L) ligand is coordinated in a monodentate fashion through the pyridine N atom. In the extended structure, these complexes, with both hydrogen‐bond acceptor (pyrimidine) and donor (H2O) functions, are linked to each other by intermolecular water–pyrimidine O—H...N hydrogen‐bonding interactions, resulting in a double chain along the crystallographic a axis. The trifluoromethanesulfonate anions are integrated into the chains via O—H...O hydrogen bonds between the coordinated water and sulfonate O atoms. These double chains are associated into a novel three‐dimensional network through interchain water–pyrimidine O—H...N hydrogen bonds. The asymmetric ligand plays an important role in constructing this unusual supramolecular structure. 相似文献
950.
本文用a b initio计算法和近似a b initio计算法(PRDDO)研究了质子化硼烷正离子体系的电子结构,给出了一些正离子体系的优化几何构型并讨论了它们的成键情况。计算的硼烷分子质子亲和势与实验值相当吻合。 相似文献