Synthesis and characterization of dendrimer templated supported bimetallic Pt-Au nanoparticles

Bimetallic dendrimer-stabilized nanoparticles (DSNs) were used to prepare supported Pt-Au catalysts within the bulk miscibility gap for this binary system. Hydroxy-terminated generation 5 PAMAM dendrimers were used to prepare Cu(0) nanoparticles (NPs). The Cu(0) NPs were subsequently used to reduce K(2)PtCl(4) and HAuCl(4), preparing stabilized bimetallic Pt-Au NPs with a 1:1 stoichiometry. The stabilized NPs were adsorbed onto a high surface area silica support and thermally activated to remove the dendrimers. Transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS), and infrared spectroscopy of adsorbed CO showed that this preparation route resulted in NPs in which the two metals are intimately mixed and that the majority of the bimetallic NPs were smaller than 3 nm. Further, the bimetallic NPs were highly active for CO oxidation catalysis near room temperature and showed evidence of CO induced restructuring at ambient temperatures.     

Catalytic activity in water-gas shift reaction of platinum group metals supported on iron oxides

Summary The activity of systems made of a platinum metal supported on Fe₂O₃ in the water-gas shift reaction (WGSR) has been studied. The iron oxide catalysts activity in WGSR are apparently determined by their redox properties that can be improved by addition of platinum metals.     

Density functional theory of water-gas shift reaction on molybdenum carbide

The density functional theory (DFT) of the water-gas shift (WGS) reaction over molybdenum carbide was studied with the aim of understanding the dissociation of H(2)O, the OH group, and CO to determine on what sections of molybdenum carbide CO(2) and H(2) formed and whether they played a role in the reaction. The energy diagram of each elementary step, the reaction of the hydrogen and oxygen atoms with CO, and the transition state for this elementary step were also studied. The IR spectra of the CO adsorption was experimentally analyzed for the identification of several candidates of the CO adsorption modes. The adsorptions of the threefold Mo site (a) with and (b) without the underlying C atom of the second layer have the second and highest adsorption energies of -281.59 and -321.00 kJ/mol, respectively. The IR data showed that the bands at 1626 cm(-1) from the IR experiments are (a) the nearest adsorption of the threefold Mo site with the underlying C atom at the calculated/corrected band of 1621 cm(-1). The calculated/corrected threefold adsorption (b) had the highest adsorption energy but exhibited an IR band at 1147 cm(-1) which was not observed in the experimental data. The C-O bond length increased to 1.49 from 1.36 after the H(2)O adsorption (b), suggesting the dissociation of C-O after the H(2)O coadsorption. The WGS reaction on the beta-Mo(2)C(001) slab carbide was calculated and took place as follows: H(2)O was dissociated into OH and H on the Mo(2)C surface and the OH subsequently dissociated into H and O atoms. CO approached the O atom to form CO(2).     

Effect of anions on the structure and catalytic properties of a La-doped Cu-Mn catalyst in the water-gas shift reaction

Effects of the anion type on the structure, thermal stability, and catalytic performance of La-doped Cu-Mn catalysts prepared by co-precipitation were characterized by X-ray diffraction, Brunauer-Emmett-Teller, temperature-programmed reduction, temperature-programmed reduction of oxidized surfaces, and temperature-programmed desorption. The Cu-Mn catalyst was tested for the water-gas shift (WGS) reaction. The main crystalline phase of samples prepared with sulfate, acetate, chloride, and nitrate as the starting materials was a Cu_1.5Mn_1.5O₄ spinel structure, following the WGS reaction, the main crystalline phases were transformed into Cu and MnO. The sample prepared with acetate as the starting material showed the most obvious MnCO₃ characteristic diffraction peaks, with better synergistic effects of Cu and MnO, increased adsorption of CO₂ and improved dispersion of Cu on the catalyst surface; also, the best thermal stability and the highest low temperature catalytic activity were observed. The sample prepared with nitrate as the starting material maintained high thermal stability and catalytic performance in the range of 400°C to 450°C, but CO conversion decreased below 350°C. Catalytic performance of the sample prepared with sulfate and chloride as the starting materials was poor, ranging from 200°C to 450°C.     

Synthesis and activity measurement of some water-gas shift reaction catalysts

The effect of calcination temperature on the activity and some properties of low temperature water gas shift reaction catalysts has been investigated. The activities of catalysts have been determined using a fixed bed catalytic reactor. The following results may be deduced from the present study. 1. The catalysts' total surface area decreased with increasing calcination temperature, presumably due to the partial sintering of the catalysts particles. 2. The presence of an amorphous CuO phase within the structure of some catalysts may be related to the desirable conditions prevailing during synthesis of the latter. 3. Observation of a similar trend between the increase in copper crystallite particle size and enhancement of catalyst activities with increasing calcination temperature demonstrates the important contribution made by the copper crystallite phase to the overall activities of water gas shift reaction catalysts. This revised version was published online in June 2006 with corrections to the Cover Date.     

Hydrodesulfurization and hydrogenation activities of carbon supported bimetallic catalysts

Carbon-supported noble metals are tailored for hydrodesulfurization reaction by adding iron, in such a manner that undesirable hydrogenation reactions are prevented without decrease of the catalytic activity.

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Synthesis,characterization and catalytic activities of bimetallic modified MCM-41 for epoxidation of styrene

Mesoporous molecular sieves MCM-41 modified by bimetal (Zr and Ti) ions with ordered hexagonal arrangement were prepared by direct synthesis under microwave–hydrothermal conditions at 403 K. FT-IR, N₂ adsorption–desorption, scanning electron microscope, high-resolution transmission electron microscope, element mapping, X-ray photoelectron spectroscopy, diffuse Reflectance UV–Visible Spectra etc. were used to characterize as-prepared materials. The results showed that Zr and Ti were introduced into MCM-41 and bonds of Zr–O–Si and Ti–O–Si were formed in framework of the MCM-41. Moreover, their structures with ordered arrangement were still retained. The microwave–hydrothermal method might shorten the synthesis time from days to hours and the as-prepared catalyst had a high catalytic activity and selectivity for the liquid-phase epoxidation of styrene.     

CeO_2-Al_2O_3负载金催化剂用于水煤气变换反应的催化活性

采用浸渍法和沉积-沉淀法制备了CeO2-Al2O3复合氧化物,比较了复合氧化物负载纳米金催化剂对水煤气变换反应的催化活性。通过N2物理吸附、XRD、TEM、H2-TPR等表征手段对复合氧化物及其负载金催化剂的物相和结构进行分析,发现复合氧化物的制备方法及其焙烧温度对其比表面积、孔结构及水煤气变换反应活性有明显的影响。与沉积-沉淀法相比,浸渍法制备的CeO2-Al2O3复合氧化物具有较大的CeO2晶粒尺寸,经500℃焙烧后再负载金,所得催化剂具有更高的活性,250℃时CO转化率可达78.1%。     

Simultaneous determination of kinetic and diffusion parameters for the water-gas shift reaction

The water-gas shift reaction was studied at 563–638 K over an industrial ferrochrome catalyst. The reaction rate data could be described by first order kinetics coupled to a diffusional resistance model for isothermal pellets. The model parameters were determined by simultaneous nonlinear regression.

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助剂对低温水煤气变换反应Au/α-Fe2O3催化剂性能的影响

采用共沉淀法制备了系列Au/αFe2O3 MOxM=Zr、Al、Mg、Ca、Ba)催化剂,通过N2物理吸附、XRD、H2-TPR和CO2-TPD-MS等手段对催化剂的物化性质进行表征,考察了富氢下低温水煤气变换（WGS）反应中助剂对Au/αFe2O3催化剂性能的影响。结果表明,助剂ZrO2能有效提高Au/α Fe2O3催化剂在富氢气氛下低温WGS反应活性和稳定性,反应温度150℃时CO转化率可达88.45%,且催化剂具有较高的稳定性。研究发现,添加ZrO2助剂能抑制载体晶粒的生长,降低载体晶粒度,提高催化剂的比表面积,改善催化剂的还原性能和表面酸碱度,从而提高催化剂的催化活性和稳定性。     

Fabrication of lead titanate single crystalline nanowires by hydrothermal method and their characterization

Single crystalline nanowires of lead titanate (PbTiO₃) were fabricated by hydrothermal method at 200°C using lead acetate and n-tetrabutyl titanate as starting materials, where sodium hydroxide was served as a mineralizer. Crystalline phases, microstructure and optical properties of PbTiO₃ nanowires were investigated. The PbTiO₃ nanowires were uniform and continuous along the long axis, and were composed of single crystalline PbTiO₃ with a tetragonal perovskite structure. The diameter of a single nanowire was around 12 nm and the length reached up to 3 μm. The chemical composition of the samples and the valence states of elements were determined by X-ray photoelectron spectroscopy (XPS). The ultraviolet/visible absorption spectroscopic investigation suggested that the absorption edge of optical transition of the first excitonic state occurred at around 320 nm. A blue-green light emission peaking at about 471 nm (2.63 eV) is observed at room temperature, and the intensity of this emission increased with increasing excitation wavelength. Oxygen vacancies are responsible for the light emission of PbTiO₃ nanowires.     

Catalysts of new generation and microstructured heat-exchanger reactors for the water-gas shift reaction

The catalytic systems of new generation and microstuctured heat-exchanger reactors for the water-gas shift reaction have been considered.     

Preparation of mesoporous silica-alumina derived from FSM-16 and its catalytic activity for cumene cracking

Mesoporous silica-alumina catalysts with different alumina contents were prepared by impregnation of a mesoporous silica (FSM-16) with an alcohol solution of aluminium isopropoxide. The resulting mesoporous silica-alumina catalysts possess protonic acid sites, and exhibit activities for cumene cracking, though the activities are lower than that of an amorphous silica-alumina catalyst. The maximum activity as well as the maximum amount of protonic acid sites were observed for the sample with a Si/Al ratio of 4.1.     

CeO2-Al2O3负载金催化剂用于水煤气变换反应的催化活性

采用浸渍法和沉积 沉淀法制备了CeO₂-Al₂O₃复合氧化物,比较了复合氧化物负载纳米金催化剂对水煤气变换反应的催化活性。通过N2物理吸附、XRD、TEM、H₂-TPR等表征手段对复合氧化物及其负载金催化剂的物相和结构进行分析,发现复合氧化物的制备方法及其焙烧温度对其比表面积、孔结构及水煤气变换反应活性有明显的影响。与沉积 沉淀法相比,浸渍法制备的CeO₂-Al₂O₃复合氧化物具有较大的CeO₂晶粒尺寸,经500℃焙烧后再负载金,所得催化剂具有更高的活性,250℃时CO转化率可达78.1%。     

Strong metal-support interactions between highly dispersed Cu+ species and ceria via mix-MOF pyrolysis toward promoted water-gas shift reaction

The modulation of metal-support interfacial interaction is significant but challenging in the design of high-efficiency and high-stability supported catalysts.Here,we report a synthetic strategy to upgrade Cu-CeO₂ interfacial interaction by the pyrolysis of mixed metal-organic framework(MOF) structure.The obtained highly dispersed Cu/CeO_2- MOF catalyst via this strategy was used to catalyze water-gas shift reaction(WGSR),which exhibited high activity of 40.5 μmol_CO     

Surface structure and reaction performances of highly dispersed and supported bimetallic catalysts

Surface structures of Pt-Sn and Pt-Fe bimetallic catalysts have been investigated by means of Mssbauer spectroscopy, Pt-L_Ⅲ-edge EXAFS and H_2-adsorption. The results showed that the second component, such as Sn or Fe, remained in the oxidative state and dispersed on the γ-Al_2O_3 surface after reduction, while Pt was completely reduced to the metallic state and dispersed on either the metal oxide surface or the γ-Al_2O_3 surface. By correlating the distribution of Pt species on different surfaces with the reaction and adsorption performances, it is proposed that two kinds of active Pt species existed on the surfaces of both catalysts, named M_1 sites and M_2 sites. M_1 sites are the sites in which Pt directly anchored on the γ-Al_2O_3 surface, while M_2 sites are those in which Pt anchored on the metal oxide surface. M_1 sites are favorable for low temperature H_2 adsorption, and responsible for the hydrogenolysis reaction and carbon deposition, while M_2 sites which adsorb more H_2 at higher tem     

Fabrication of hexaphenylsilole nanowires and their morphology-tunable photoluminescence.

Immersion of nanoporous alumina membranes into saturated solutions of hexaphenylsilole with subsequent solvent evaporation affords aligned organic nanowires. The luminescent properties of the hexaphenylsilole nanowires can be manipulated by varying their morphologies, which were controlled by changing the channel sizes of the alumina templates.     

Synthesis of chitosan derivatives supported palladium complexes and their catalytic behavior in the Heck reaction

Two kinds of chitosan derivatives, crosslinked chitosan and crosslinked chitosan condense with salilylaldehyde, supported palladium complexes (CL‐CTS‐Pd and CL‐S‐CTS‐Pd) were synthesized and characterized by X‐ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), differential thermal analysis (DTA), etc. These complexes are efficient catalysts for the Heck reaction under atmospheric conditions and can be easily recovered and reused. The detailed studies show that the catalyst CL‐S‐CTS‐Pd is much more efficient than CL‐CTS‐Pd under the same conditions. CL‐S‐CTS‐Pd keeps its catalytic activity in the Heck reaction of acrylic acid with iodobenzene even at a low temperature (60°C) or with tiny amounts of the catalyst (0.05 mol%Pd). Yields of making cinnamic acid were even as high as 75.3% in the Heck reaction of acrylic acid with iodobenzene using CL‐S‐CTS‐Pd that was recovered 10 times. Copyright © 2005 John Wiley & Sons, Ltd.     

Hydrothermal synthesis and their catalytic properties of manganite nanowires

La_0.5Sr_0.5MnO₃ nanowires and nanoparticles were synthesized by the hydrothermal and citrate methods, respectively. The samples were characterized by TEM, HRTEM, XRD, ICP and N₂ adsorption, etc. The formation mechanism of the nanowires was proposed and discussed. Further, the stabilities and catalytic activities of La_0.5Sr_0.5MnO₃ nanowires for CH₄ combustion were evaluated and compared with those of the nanoparticles. The results showed that the particle morphology had a significant effect on the properties of the catalysts. After running at a high temperature for a long duration, the nanowires showed a higher stability and a higher activity, compared with the nanoparticles. Their different stabilities were ascribed to the different surface energies (particle sizes), as well as to the different geometric packing models.