Cyanide self-addition, controlled adsorption, and other processes at layered double hydroxides.

Layered double hydroxides (LDH) are anion-exchanging materials of the type M(III)-M(II)x(OH)(2x + 2)Y that occur abundantly in nature, and can concentrate, protect, and activate simple organic anionic species of possible relevance to the earliest organisms. We now wish to report progress in the following areas: 1) Internal vs. external uptake of anions. Ferrocyanide does not displace carbonate from synthetic hydrotalcite (Mg:Al LDH carbonate) but is nevertheless taken up on the outside of the particles. In other cases, anion uptake is controlled by specific hydrogen bonding requirements rather than by charge density alone, a feature that can be used to control whether uptake will be both internal and external, or external only. These two findings taken together have important implications for specific catalysis by LDH, since specific hydrogen bonding will affect the individual and relative conformations of substrate anions, and anions occupying space in the interlayer will be under tighter constraints than those adsorbed externally. 2) Specific reactions catalyzed by LDH. We have found that the LDH Mg2Al(OH)6Cl catalyzes the self-addition of cyanide, to give in a one-pot reaction at low concentrations an increased yield of diaminomaleonitrile and in addition, at higher (> or = 0.05 M) concentrations, a purple-pink material that adheres to the LDH. We are investigating whether this reaction also occurs with hydrotalcite itself, what is the minimum effective concentration of cyanide, and what can be learned about the products and how they compare with those reported at high HCN concentrations in the absence of catalyst.

Layered double hydroxide stability. 2. Formation of Cr(III)-containing layered double hydroxides directly from solution.

Solutions containing divalent metal [M(II) = Mg2+, Zn2+, Co2+, Ni2+, Mn2+] chlorides and CrCl3 6H2O were titrated with NaOH to yield, for M(II) = Zn, Co, and Ni, hydrotalcite-like layered double hydroxides (LDHs), [[M(II)]1-z[Cr(III)]z(OH)2][Cl]z yH2O, in a single step, without intermediate formation of chromium hydroxide. Analysis of the resultant titration curves yields solubility constants for these compounds. These are in the order Zn < Ni approximately Co, with a clear preference for formation of the phase with z = 1/3. With Mg2+ as chloride, titration gives a mixture of Cr(OH)3 and Mg(OH)2, but the metal sulfates give Mg2Cr(OH)6 1/2(SO4) by a two-step process. Titrimetric and spectroscopic evidence suggests short-range cation order in the one-step LDH systems.