title: Observation of cation ordering and anion-mediated structure selection among the layered double hydroxides of Cu(II) and Cr(III).
abstract: Highly ordered Cl(-) and SO4(2-)-intercalated layered double hydroxides (LDHs) of Cu(II) and Cr(III) are obtained when coprecipitation is carried out at low pH ~ 5 and elevated temperature (60-80 °C). Precipitation under other conditions results in the formation of a gel. The SO4(2-)-LDH exhibits weak reflections which could be indexed to the 100 and 101 planes of a supercell corresponding to a = √3 ×a(o), providing direct evidence for cation ordering among LDHs by X-ray diffraction. The ordering of the M(II) and M'(III) in the metal hydroxide layer has been a subject of considerable debate in the LDH literature for the past several years and was earlier probed using short-range techniques such as NMR and EXAFS. Rietveld refinement indicates that the cation-ordered LDH adopts the structure of the 1H polytype (space group P3] a = 5.41 Å, c = 11.06 Å). In contrast the Cl(-)-intercalated LDH adopts the cation-disordered structure of the 3R1 polytype (space group R3[combining macron]m, a = 3.11 Å, c = 23.06 Å). The Cl(-)-LDH was used as a precursor to synthesize LDHs with other anions. While Br(-) and CO3(2-) (molecular symmetry, D3h) select for the 3R1 polytype, the XO3(-) (X = Br, I) ions (molecular symmetry, C3v) select for the rare 3R2 polytype. This work demonstrates the role of the intercalated anion in structure selection of the LDH.
authors.affiliation: Department of Chemistry, Central College, Bangalore University, Bangalore 560 001, India. vishnukamath8@hotmail.com.
authors.forename: K
authors.initials: K
authors.lastname: Jayanthi
authors.forename: P Vishnu
authors.initials: PV
authors.lastname: Kamath