Layered double metal hydroxides

Dutta, P. K. and Robins, D. S. (1994). Pyrene sorption in organic layered double-metal hydroxides. Langmuir 10, 1851. 

Jakupca, M. and Dutta, P. K. (1995). Thermal and spectroscopic analysis of a fatty acid-layered double-metal hydroxide and its application as a chromatographic stationary-phase. Chem. Mater. 7, 989. 

Complex precipitates, such as layered double hydroxides, are frequently prepared as precursors of oxide catalysts. Hydrotalcite is a hydrated hydroxy-carbonate mineral with the formula Mg,sAl2(0H)i6C03-4H20. It represents the better known and most popular member of a family of layered double metal hydroxide com-... 

Layered double metal hydroxides consist of positively charged bruclte-type layers In which part of the divalent cations are substituted by trivalent cations. This results in a net positive charge In the layers which Is balanced by charge compensating anions In the Interlayer. Upon heating, the hydroxides undergo... 

Cavalcanti, F. A. P., Schutz, A., and Biloen, P. 1987. Interlayer accessibility in layered double-metal hydroxides. (Prep. Catal. 4). Stud. Surf. Sci. Catal. 

Kopka, FI., Beneke, K. and Lagaly, G. (1988). Anionic surfactants between double metal hydroxide layers. J. Colloid Interface Sci. 123, 427. 

The layered hydroxides by themselves are catalytically inactive, probably due to a lack of accessible sites. Upon calcination up to 450°C, materials intercalated with COj or NO3-anions have been found active for aldol condensation ( ), olefin isomerization and 8-propiolactone polymerization (9). Although many elimination reactions have been studied over decomposed double metal hydroxides, the nature of the sites involved is still unclear. 

Scheinost AC, Sparks DL (2000) Formation of layered single- and double-metal hydroxide precipitates at the mineral/water interface. A multiple-scattering XAFS analysis. J Colloid Interface Sci 223 167-178 Scheinost AC, Abend S, Pandya KI, Sparks DL (2001) Kinetic controls on Cu and Pb sorption by ferrihydrite. Environ Sci Technol 35 1090-1096... 

Zinc hydroxy double salts are layered materials similar to layered double hydroxides which show intercrystalline reactivity and incorporate organic compounds between layers.337 Hydroxy double salts of high crystallinity can be obtained by reacting ZnO with organic metal salts in water. Zinc oxide crystals could then be prepared by thermal treatment of hydroxy zinc acetate.338... 

Similar methods of encapsulation are also observed in pillared clays, which were also introduced as catalysts as long ago as the early 1980s. The field has been thoroughly reviewed up to 2000 [65], Layered double hydroxide structures have also been used for the entrapment of metal coordination compounds [66],... 

Layered metal hydroxides can be categorized into several classes according to their structure (Figure 13.1). Layered double hydroxides (LDHs), which have a hydrotalcite-like structure [27-34], can be expressed as [M2+1 xM3+x(0H)2] (Am )x/m,nH20,... 

Hydrotalcitelike compounds (HTs) are layered double hydroxides with the general formula Mm2 Mm3 (OH)2(j Ax m/r V H20, where M2 and M3 are divalent and trivalent metal cations, re-... 

Hydrotalcites are layered double hydroxides with the general formula Mg6Al2(0H)i6[C03].4H20. Loading these compounds with potassium carbonate strongly increases their C02 uptake [25, 35], Notably, the hydrotalcite structure already breaks down below 400 °C [26] into a mixed metal oxide. 

The selective intercalation of guests into solid hosts offers the potential for application in catalysis and separation science. An excellent case in point is zeolites, which exhibit shape and size selective inclusion properties and are used for an enormous variety of processes [44,45]. Additionally, a munber of layered materials have been reported to possess selective intercalation properties, including layered metal phosphonates [46,47], montmorUlonite [48], magnesium aluminum oxide [49], and layered double hydroxides [50-59]. 

LDH LEU LIBD LAW LET LILW LIP LLNL LLW LMA LMFBR LOI LREE L/S LTA LWR Layered double hydroxide Low enriched uranium Laser-induced breakdown detection Low-activity waste Linear energy transfer Low- and intermediate-level nuclear waste Lead-iron phosphate Lawrence Livermore National Laboratory Low-level nuclear waste Law of mass action Liquid-metal-cooled fast-breeder reactor Loss on ignition Light rare earth elements (La-Sm) Liquid-to-solid ratio (leachates) Low-temperature ashing Light water reactor... 

In the example in Figure 2.24, a clay (a layered double hydroxide [LDH]) was intercalated with a transition metal complex (NH4)2MnBr4. The EXAFS data in Figure 2.24(a) shows the Mn K-edge EXAFS of the pure complex, and we see one coordination sphere of four Br atoms at a distance of 2.49 A, corresponding well to the tetrahedral coordination found in the X-ray crystal structure. However, after intercalation, the complex reacts with the layers in the clay, and the coordination changes to distorted octahedral where Mn is now surrounded by four 0 atoms at a distance of 1.92 A and two Br atoms at a distance of 2.25 A. 

Layered double hydroxides (LDHs), with a hydrotalcite-like structure, are a class of materials which have received considerable attention in the last decade. The structure of LDHs is based on the stacking of metal cation hydroxide (brucite-like) layers, with a positive charge on the layers resulting from the isomorphous substitution of some of the bivalent... 

It is well known that hydrolyzed polyvalent metal ions are more efficient than unhydrolyzed ions in the destabilization of colloidal dispersions. Monomeric hydrolysis species undergo condensation reactions under certain conditions, which lead to the formation of multi- or polynuclear hydroxo complexes. These reactions take place especially in solutions that are oversaturated with respect to the solubility limit of the metal hydroxide. The observed multimeric hydroxo complexes or isopolycations are assumed to be soluble kinetic intermediates in the transition that oversaturated solutions undergo in the course of precipitation of hydrous metal oxides. Previous work by Matijevic, Janauer, and Kerker (7) Fuerstenau, Somasundaran, and Fuerstenau (I) and O Melia and Stumm (12) has shown that isopolycations adsorb at interfaces. Furthermore, it has been observed that species, adsorbed at the surface, destabilize colloidal suspensions at much lower concentrations than ions that are not specifically adsorbed. Ottewill and Watanabe (13) and Somasundaran, Healy, and Fuerstenau (16) have shown that the theory of the diffuse double layer explains the destabilization of dispersions by small concentrations of surfactant ions that have a charge opposite to... 

As mentioned previously, the role of the metal is not specific. Even transition metal free layered double hydroxides are suitable catalysts for the olefin epoxidation with O2 and a sacrificial aldehyde (205). Leaching of the metal from the solid catalyst is a serious problem since organic acids that are potential metal ligands accumulate during the reaction. Leaching occurs, for example, with the polybenzimidazole-supported Ni2+ catalyst (199). 

The 0-d nanoparticles can be nano-metal oxides (such as silica,1 titania,2 alumina3), nano-metal carbide,4 and polyhedral oligomeric silsesquioxanes (POSS),5 to name just a few the 1-d nanofibers can be carbon nanofiber,6 and carbon nanotubes (CNT),7 which could be single-wall CNTs (SWCNT) or multiwall CNTs (MWCNT) etc. the 2-d nano-layers include, but are not limited to, layered silicates,8 layered double hydroxides (LDH),9 layered zirconium phosphate,10 and layered titanates,11 etc. 3-d nano-networks are rarely used and thus examples are not provided here. 

New developments in the use of silicates to improve flame retardancy have arisen from the use of synthetic anionic clays that correspond to the family of lamellar mixed metal hydroxides, commonly named layered double hydroxides (LDH) or hydrotalcite-like compounds.17... 

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