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.

Evolution of copper species during heat treatment and its effect on CO oxidation reaction on CuCeZrO_(y) catalyst synthesized by a facile solvent-free route

Several ternary oxides CuCeZrO_(y)(CCZ)were synthesized by a facile grinding method followed by calcination at high temperatures,and used as catalysts for CO oxidation at low temperatures.The influences of calcination temperature(400-600℃)on the physicochemical properties of the assynthesized ternary oxides were investigated by thermogravimetric analysis/differential scanning calorimetry(TGA/DSC),X-ray diffraction(XRD),transmission electron microscopy(TEM),Raman,inductively coupled plasma-optical emission spectrometry(ICP-OES),N_(2) adsorption,H_(2)-temperature programmed reduction(H_(2)-TPR),and X-ray photoelectron spectroscopy(XPS)characterizations.The results show that the increase in calcination temperature from 400 to 500℃is conducive to the high dispersion of CuOx on catalyst surface and the incorporation of Cu species into the support to form the Cu-Ce-Zr-O solid solution.Further raising of calcination temperature from 500 to 600℃,however,leads to the segregation of Cu species from the solid solution to aggregate on support surface and growth of highly dispersed CuOx nanoparticles.The highest catalytic activity is acquired over the CCZ calcined at 500℃,which can be ascribed to the largest contents of Cu+species and oxygen vacancies owing to the formation of the maximum amount of Cu-Ce-Zr-O solid solution.