Homogeneous precipitation of layered Ni(II)-Cr(III) double hydroxides

An adequate account of the hydrolytic properties of Cr(3+) and Ni(2+) 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 Ni(1-x)Cr(x)(OH)(2)(CO(3))(x/2).nH(2)O (x approximate to 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 CO(3)(2-) ions dangling at the crystallites' edges by bridging OH(-). (c) 2007 Elsevier Inc. All rights reserved.