To investigate the behaviors of Cu^(2+)and Ni^(2+)with the change of conditions in Cu_(2+)−Ni_(2+)−NH_(3)−NH_(4)+−C_(2)O_(4)^(2-)−H_(2)O reaction system,mathematical models of thermodynamics based on the principle of ...To investigate the behaviors of Cu^(2+)and Ni^(2+)with the change of conditions in Cu_(2+)−Ni_(2+)−NH_(3)−NH_(4)+−C_(2)O_(4)^(2-)−H_(2)O reaction system,mathematical models of thermodynamics based on the principle of mass conservation were established.The simulation results indicate that the precipitation of metal ions from the aqueous phase is a complicated dynamic equilibrium process,during which the coordination reactions of Cu^(2+)and Ni^(2+)with NH3 forming[Cu(NH3)n]^(2+)(n=3−5)and[Ni(NH3)m]^(2+)(m=3−6)are predominant under high pH conditions,respectively.The pH ranges for the simultaneous precipitation of Cu^(2+)and Ni^(2+)are 2.0−6.5 and 2.0−5.5 when[NH3]T equals 0.6 and 4.2 mol/L,respectively,with the prefixed[C_(2)O_(4)^(2-)]T of 0.6 mol/L.Due to the fractional precipitation of Cu^(2+)and Ni^(2+),Cu−Ni composite is obtained after the thermal decomposition of Cu−Ni oxalate complex salts prepared in a pure water system when pH>7.0.By applying the mixed solvent(water/ethanol)as the precipitation medium,the Cu−Ni alloy rods can be finally fabricated with high purity and crystallinity.展开更多
基金the financial supports from Natural Science Foundation of Hunan Province,China(No.2020JJ4735)Science and Technology Department of Hunan Province Tackling Key Scientific and Technological Problems and Transformation of Major Scientific and Technological Achievements,China(No.2018GK4001)the Hunan Key Laboratory for Rare Earth Functional Materials,China(No.2017TP1031).
文摘To investigate the behaviors of Cu^(2+)and Ni^(2+)with the change of conditions in Cu_(2+)−Ni_(2+)−NH_(3)−NH_(4)+−C_(2)O_(4)^(2-)−H_(2)O reaction system,mathematical models of thermodynamics based on the principle of mass conservation were established.The simulation results indicate that the precipitation of metal ions from the aqueous phase is a complicated dynamic equilibrium process,during which the coordination reactions of Cu^(2+)and Ni^(2+)with NH3 forming[Cu(NH3)n]^(2+)(n=3−5)and[Ni(NH3)m]^(2+)(m=3−6)are predominant under high pH conditions,respectively.The pH ranges for the simultaneous precipitation of Cu^(2+)and Ni^(2+)are 2.0−6.5 and 2.0−5.5 when[NH3]T equals 0.6 and 4.2 mol/L,respectively,with the prefixed[C_(2)O_(4)^(2-)]T of 0.6 mol/L.Due to the fractional precipitation of Cu^(2+)and Ni^(2+),Cu−Ni composite is obtained after the thermal decomposition of Cu−Ni oxalate complex salts prepared in a pure water system when pH>7.0.By applying the mixed solvent(water/ethanol)as the precipitation medium,the Cu−Ni alloy rods can be finally fabricated with high purity and crystallinity.