Ni/MgO/Al_2O_3催化剂中Ni前体对甲烷-二氧化碳重整反应活性的影响

考察了以硝酸镍、氯化镍、硫酸镍、醋酸镍及硝酸六氨合镍 5种 Ni盐制备的 Ni/Mg O/Al2 O3 催化剂在CO2 与 CH4重整制合成气反应中的催化活性 .发现 Ni前体对活性有明显的影响 .以硝酸镍、醋酸镍、硝酸六氨合镍为前体制备的 Ni催化剂 ,反应活性较高 ;以硫酸镍为前体制备的 Ni催化剂 ,可能由于硫中毒等原因而显示出很低的活性 ;以氯化镍为前体制备的 Ni催化剂 ,其活性与制备方法有关 ,未经焙烧而直接还原的催化剂显示出较好的活性 .X-射线粉末衍射 (XRD)、BET比表面积及反应后的积炭量测定结果表明 ,以硝酸镍、醋酸镍、硝酸六氨合镍为前体制备的 Ni催化剂 ,表面分散性好 ,比表面积大 。

Thermodynamic analysis on synthesis of fibrous Ni-Co alloys precursor and Ni/Co ratio control

According to the principles of simultaneous equilibrium and mass equilibrium, a series of thermodynamic equilibrium equations in Ni（II）-Co（II）-C2O4^2--NH3-NH4^＋-H2O system at ambient temperature were deduced. The diagrams of logarithm ion concentrations versus pH values at different solution compositions were drawn. The results show that Ni^2＋ and Co^2＋ can completely precipitate at pH less than 5.0 and the predefined Ni/Co ratios can be well kept in the precursor. The precursor morphology is granular aggregation. However, rod aggregation precursor is obtained in the pH range of 5.0-8.0, and fibre-shape precursor is got at pH value higher than 8.0. The Ni/Co ratios in the above two precursors are not reproduced as that in the feed due to the formhtion of multi-coordinated Ni（NH3）n^2＋ and Co（NH3）n^2＋ （n=1-6）. Modification of precipitation medium is favorable for the precursors to keep the predefined Ni/Co ratios of the feed in the pH range of 2.0-8.6. Meanwhile, the precursors with fibrous morphology can be obtained.

Preparation of ultra-fine fibrous Fe-Ni alloy powder by coordinated co-precipitation-direct reduction process

The precursor prepared by coordinated co-precipitation was direct reduced by hydrogen to ultra-fine fibrous Fe-Ni alloy powder. The effects of concentrations of reactants, pH value, reaction temperature and additive on the preparation of precursor were systematically investigated. The structures, thermal decomposition processes and morphologies of the precursors were characterized by X-ray diffraction (XRD), thermal gravity-differential thermal analysis (TG-DTA) and scanning electron microscoy (SEM). The results show that using 2% polyvinylpyrrolidone (PVP) (in mass fraction) as additive, a well-dispersed precursor with a uniform morphology can be obtained in a solution with Fe2+ and Ni2+ total concentration (1:1) of 0.8 mol/L, pH value of 6.2 at 60 °C, and a pure and well dispersed fibrous iron-nickel powder can be prepared by direct reduction of this precursor in a mixed atmosphere of nitrogen and hydrogen at the temperature of 420 °C.

Shape-controlled synthesis of novel precursor for fibrous Ni-Co alloy powders

A novel precursor of nickel-cobalt alloy powders with an appropriate Ni to Co molar ratio was prepared under selectively synthetic conditions. The composition and morphology of the precursor were characterized by X-ray diffractometry （XRD）, scanning electron microscopy （SEM）, Fourier transform infrared spectrometry （FT-IR） and energy dispersive spectrometry （EDS）. The effects of pH value, reaction temperature, metal ion concentrations and surfactant on the morphology and the dispersion of precursor were investigated. The results show that the morphology of precursor depends on ammonia content in the precursor. A fibriform precursor is a complicated ammonia-containing nickel-cobalt oxalate. The uniform shape-controlled fibrous precursor is obtained under the following optimum conditions： ammonia as complex agent as well as pH adjustor, oxalate as coprecipitator, 50-65 °C of reaction temperature, 0.5-0.8 mol/L of total concentration of Ni2＋ and Co2＋, PVP as dispersant, and pH 8.0-8.4.

Preparation of fibrous nickel powder by precipitation transformation coupled with thermal decomposition

Fibrous particulate precursor was obtained by precipitation transformation in the ternary solution system of ammonium oxalate, nickel chloride and ammonia. The composition and morphology of precursor were characterized by XRD, SEM, IR and DTA/TGA analyses. The results show that the chemical composition and morphology of precursor precipitates at pH=8.4？8.8 are different from those of precursor precipitates at pH=6.0, and the mechanisms of the thermal decomposition of the precursors are different. The effects of various conditions in the process of thermal decomposition, including precursor morphology, atmosphere, temperature and time on the morphology and dispersion degree of obtained nickel powders were studied in detail. The final product inherits the morphology of precursor when the thermal decomposition is conducted under a weakly reducing atmosphere at temperature range of 400？440 °C for 30 min. Fibrous nickel powder can be produced with good dispersion, and its shape changes from smooth, straight and compact fiber into loose and curved fiber with rough surface.

Electrocatalytic water oxidation by a nickel oxide film derived from a molecular precursor

In this study,we fabricated a NiOx film by electrodeposition of an ethanediamine nickel complex precursor(pH=11)on a fluorine‐doped tin oxide substrate.The resulting film is robust and exhibits high catalytic activity for electrochemical water oxidation.Water oxidation is initiated with an overpotential of375mV(1mA/cm2)and a steady current density of8.5mA/cm2is maintained for at least10h at1.3V versus the normal hydrogen electrode.Kinetic analysis reveals that there is a2e?/3H+pre‐equilibrium process before the chemical rate‐determining step.The low‐cost preparation,robustness,and longevity make this catalyst competitive for applications in solar energy conversion and storage.

Design of the Metal Precursors Molecular Structures in Impregnating Solutions for Preparation of Efficient Ni Mo/Al_2O_3 Hydrodesulfurization Catalysts

The molecular structures of metal precursors in the impregnating solution were designed so as to prepare efficient Ni Mo/Al_2O_3 hydrodesulfurization(HDS) catalysts. At first, five typical impregnating solutions were designed; the existing metal precursors, such as [Mo4(citrate)2O11]^(4-)-like, [P2Mo18O62]^(6-)-like and [P2Mo5O23]^(6-)-like species in the solutions were confirmed by laser Raman spectroscopy(LRS). The UV-Vis spectra results indicated that the solutions containing both phosphoric acid and citric acid could change the existing form of nickel species. Five corresponding Ni Mo/Al_2O_3 catalysts were prepared by the incipient wetness impregnation method. The LRS analysis results of dried catalysts showed that the above metal precursors could be partly retained on alumina support after impregnation and drying, although the interface reaction between different metal precursors and alumina support unavoidably took place. Then the catalysts were sulfided and characterized by N2 physisorption, TEM and XPS analyses. The results showed that different metal precursors in impregnating solution could mainly result in the difference in both the morphology of(Ni)Mo S2 slabs and the promoting effect of Ni species. The catalyst prepared mainly with [P2Mo5O23]^(6-)-like species used as precursors exhibited worse dispersion of(Ni)Mo S2 slabs and lower ratio of Ni–Mo–S active phases than the one with [Mo4(citrate)2O11]^(4-)-like species. Promisingly, the catalyst prepared with co-existing [Mo4(citrate)2O11]^(4-)-like, [P2Mo18O62]^(6-)-like and [P2Mo5O23]^(6-)-like species showed better hydrodesulfurization activity for 4,6-DMDBT thanks to its more well-dispersed Ni–Mo–S active phases.

Cyanido-bridged one-dimensional systems assembled from [Re~ⅣCl_4(CN)_2]_(2-) and [M~Ⅱ(cyclam)]^(2+) (M=Ni,Cu) precursors

Three new cyanido-bridged heterometallic ReIVNin and ReIVCu one-dimensional systems were synthesized and extensively characterized both structurally and magnetically. Single-crystal X-ray diffraction analysis revealed that these compounds display a common topology, with chains composed of alternating [RetVc14（CN）2]2- and [Mn（cyclam）]2＋ （M = Ni in 1, Cu in 2） or [Cull（N,N＇-dimethylcyclam）]2＋ （in 3） building units. Two different chain orientations with a tilt angle of ca. 51° to 55° are present in the crystal packing of these compounds. The magnetic susceptibility measurements suggest the presence of intrachain ferromagnetic interactions between the S = 3/2 ReTM centers and the 3d metal ions： S = 1 Ni1I or S = 1/2 CuII. At low temperature, a three-dimensional ordered magnetic phase induced by interchain antiferromagnetic interactions （antiferromagnetic for 1 and 2; canted antiferromagnetic for 3） is detected for the three compounds.