Homogeneous precipitation of layered Ni(II)-Cr(III) double hydroxides.
An adequate account of the hydrolytic properties of Cr3+ and Ni2+ allows setting the conditions for homogeneous nucleation of layered Ni(II)-Cr(III) double hydroxides; water exchange and hydrolysis rate constants indicate that, at very high rates of base dosing, formation of heteronuclear Cr(III)-Ni(II) hydroxo species should prevail over precipitation of active Cr(OH)3. This is realized by the urea method under microwave-assisted hydrothermal conditions. This approach yields crystalline Ni1-xCrx(OH)2(CO3)x/2nH2O (x approximately 0.32-0.36) in less than 5 min at 453 K; higher degrees of crystallinity are obtained at higher temperatures and/or longer aging times. Formation of Ni(II)-Cr(III) LDHs upon microwave-assisted hydrothermal aging of freshly coprecipitated Ni(OH)2+Cr(OH)3 mixtures takes longer, due to a different operating mechanism. The implications of the advanced rationale for the design of synthesis procedures are stressed. It is proposed that homogeneous nucleation of Ni(II)-Cr(III) LDHs involves the edge-on condensation of planar heteronuclear Cr(III)-Ni(II) hydroxo trimers. Ordered aggregation of primary particles leads to the final platelet crystals, a process that involves the exchange of CO2-(3) ions dangling at the crystallites' edges by bridging OH-.
Jobbágy
Matías
M
INQUIMAE, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Pabellón II, Ciudad Universitaria, C1428EHA Buenos Aires, Argentina.
Blesa
Miguel A
MA
Regazzoni
Alberto E
AE