Electronic transitions in layered hydroxides: Consequences of trigonal distortion of octahedral symmetry.

This work describes the assignment of the electronic spectra of metal ions in D3d coordination symmetry. Layered hydroxides are a class of materials that host transition metal ions such as Ni2+, Co2+, and Cr3+ in D3d coordination symmetry. The electronic spectra of these ions in the layered hydroxides exhibit significant fine structure which is assigned to transitions arising from D3d coordination symmetry. Towards this end, the correlation diagrams- complete or partial, and the resultant Tanabe-Sugano like diagrams for D3d symmetry are obtained from first principles and supported by DFT based computations. The approach engendered here helps in better understanding of the electronic transitions arising due to lower symmetry.

Interaction of Pristine Hydrocalumite-Like Layered Double Hydroxides with Carbon Dioxide.

The layered double hydroxides (LDHs) of Ca2+ and trivalent cations, Al3+ and Fe3+, are single-source precursors to generate supported CaO, which picks up CO2 from the gas phase in the temperature range 350-550 °C. The supports are ternary oxides, mayenite, and Ca2Fe2O5. The uptake capacity of the Fe3+-containing LDH at 1.9 mmol g-1 is two times the capacity of the Al3+-containing LDH. The product of CO2 uptake is calcite CaCO3. It is observed that the intercalated chloride ions reduce the thermal penalty by inducing the early decomposition of CaCO3. In the case of the chloride-intercalated LDHs of Ca2+ and Fe3+, the CaCO3 formed is completely decomposed at 900 °C. This is in contrast with the CaCO3 formed from bare CaO, which shows no sign of decomposition at 900 °C under similar conditions. This work shows that the hydrocalumite-like LDHs are candidate materials for CO2 mineralization.

Synthon Approach to Structure Models for the Bayerite-Derived Layered Double Hydroxides of Li and Al.

The Br- ion intercalated layered double hydroxide (LDH) of Li and Al obtained from the bayerite-Al(OH)3 precursor crystallizes in a structure different from that of the gibbsite-Al(OH)3 derived counterpart. Additionally, it undergoes temperature- and humidity-induced reversible interpolytype transformations. The dehydrated LDH (T ≈ 120 °C) adopts a structure of hexagonal symmetry (space group P3̅1m) and comprises a stacking of the metal hydroxide layers arranged one above another. On cooling and rehydration, the LDH adopts a structure of monoclinic symmetry with a stepwise increase in the stacking angle, ß. Using the structural synthon approach, based on the systematic elimination of the principal symmetry elements of the hexagonal crystal, structure models were generated for each of the two hydration steps (relative humidity ∼50%, >70%) and the structures refined (space group C2/m). The refined structures show that the interpolytype transitions are a result of rigid translations of successive metal hydroxide layers relative to one another by translation vectors (1/6, 0, 1) and (1/3, 0, 1), respectively.

Structure models for the hydrated and dehydrated nitrate-intercalated layered double hydroxide of Li and Al.

Imbibition of LiNO3 into gibbsite results in the formation of a single phase layered double hydroxide of the composition LiAl2(OH)6(NO3)·1.2H2O. This phase undergoes reversible dehydration along with the compression of the basal spacing accompanied by the reorientation of the nitrate in the interlayer gallery. The hydrated phase is a solid solution of two lattices: (i) a hexagonal lattice defining the ordering of atoms within the metal hydroxide layer, and (ii) a lattice of orthorhombic symmetry defining the ordering of atoms within the interlayer. DFT calculations of the hydration behaviour show that there is no registry between the two sublattices. In the dehydrated phase, the nitrate ion is intercalated with its molecular plane parallel to the metal hydroxide layer and the crystal adopts a structure of hexagonal symmetry.

Layered Double Hydroxides: Proposal of a One-Layer Cation-Ordered Structure Model of Monoclinic Symmetry.

Layered double hydroxides are obtained by partial isomorphous substitution of divalent metal ions by trivalent metal ions in the structure of mineral brucite, Mg(OH)2. The widely reported three-layer polytype of rhombohedral symmetry, designated as polytype 3R1, is actually a one-layer polytype of monoclinic symmetry (space group C2/m, a = 5.401 Å, b = 9.355 Å, c = 11.02 Å, ß = 98.89°). This structure has a cation-ordered metal hydroxide layer defined by a supercell a = √3 × a0; b = 3 × a0 (a0 = cell parameter of the cation-disordered rhombohedral cell). Successive layers are translated by (1/3, 0, 1) relative to one another. When successive metal hydroxide layers are translated by (2/3, 0, 1) relative to one another, the resultant crystal, also of monoclinic symmetry, generates a powder pattern corresponding to the polytype hitherto designated as 3R2. This structure model not only removes all the anomalies intrinsic to the widely accepted cation-disordered structure but also abides by Pauling's rule that forbids trivalent cations from occupying neighboring sites and suggests that it is unnecessary to invoke rhombohedral symmetry when the metal hydroxide layer is cation ordered. These results have profound implications for the correct description of polytypism in this family of layered compounds.

Observation of cation ordering and anion-mediated structure selection among the layered double hydroxides of Cu(II) and Cr(III).

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.

Polytypism in sulfate-intercalated layered double hydroxides of Zn and M(III) (M = Al, Cr): observation of cation ordering in the metal hydroxide layers.

The as-precipitated sulfate-intercalated layered double hydroxide of Zn and Al crystallizes in the structure of the 3R1 polytype. On hydrothermal treatment, this 3R1 polytype transforms into the somewhat rare 3H and 3R2 polytypes at different temperatures. Observation of the 3R2 polytype distinct from the 3R1 polytype is evidence for the lack of cation ordering in the [Zn-Al-SO4] system. The layered double hydroxide of Zn and Cr (polytype, 1H) on hydrothermal treatment in mother liquor yields a cation-ordered phase also having the structure of the 1H polytype. Direct evidence of cation ordering is found by the appearance of weak supercell reflections corresponding to a = √3 × a(o) (a(o) is the a parameter of the cation-disordered phase). The same precursor under other conditions yields the cation-disordered 3R1 polytype. In this work, the structures of both the cation-ordered and the cation-disordered phases with similar states of hydration are refined and compared.

Anion exchange reaction potentials as approximate estimates of the relative thermodynamic stabilities of Mg/Al layered double hydroxides containing different anions.

Coatings of hydrotalcite-like nitrate-intercalated Mg/Al layered double hydroxides are electrochemically deposited on a Pt electrode by electrogeneration of base by reduction of a mixed metal nitrate aqueous solution. As-prepared coatings are stable to workup and function as rugged electrodes. The voltammetric response generated by anion exchange of intercalated nitrate for dissolved anions from solution under equilibrium conditions is employed to estimate the thermodynamic stabilities of the Mg/Al layered double hydroxides comprising different anions relative to the nitrate-containing phase. Among monovalent anions, the most stable is the fluoride-containing LDH (ΔG° = -48.7 kJ mol(-1)) relative to the nitrate-containing LDH. The stability in aqueous phase decreases as F(-) > Cl(-) > Br(-) > NO(2)(-) > NO(3)(-), whereas, among divalent anions, SO(4)(2-) (ΔG° = -8.7 kJ mol(-1)) > CO(3)(2-) (ΔG° = 14.3 kJ mol(-1)). The results of monovalent ions match well with the Miyata series, whereas the divalent anion series is at variance with the commonly held belief that carbonate-LDHs are more stable than sulfate-LDHs.

Polytypism in the lithium-aluminum layered double hydroxides: the [LiAl2(OH)6]+ layer as a structural synthon.

The [LiAl(2)(OH)(6)](+) layer obtained from gibbsite-Al(OH)(3) belongs to the layer group symmetry P-312/m. This layer satisfies the defining characteristics of a synthon in that it predicts all the polymorphic modifications of the layered double hydroxides of Li and Al. The various possible ways of stacking these layers can be derived by the systematic elimination of the principal symmetry elements comprising the layer group. This approach yields the complete universe of possible structures. When the 3 axis of the layer is conserved in the stacking, the resultant crystal adopts the structure of the 1H, 2H, or 3R polytypes (H, hexagonal; R, rhombohedral). When the 3 axis is destroyed and the 2/m axis is retained, the crystal adopts monoclinic symmetry and crystallizes in the structures of the 1M(1) or 1M(2) (M, monoclinic) polytypes; the two polytypes differ only in their translational component. Experimentally, gibbsite-based precursors yield the 2H polytype, and bayerite-based precursors yield the 1M polytype. Faulted structures incorporating differently oriented 1M(1) motifs or a mixture of 1M(1) and 1M(2) motifs are also obtained. These stacking faults result in cation disorder along the c axis and produce signature effects on the line shapes of select reflections in the powder X-ray diffraction patterns. This symmetry-guided approach is general and can be extended to other classes of layered solids.

Polytypism, disorder, and anion exchange properties of divalent ion (Zn, Co) containing bayerite-derived layered double hydroxides.

Incorporation of Zn(2+) into bayerite results in the formation of a cation-ordered layered double hydroxide (LDH) of monoclinic symmetry in which about half the vacancies of Al(OH)(3) are occupied by Zn(2+) giving rise to positively charged layers. Charge compensation takes place by the incorporation of sulfate ions in the interlayer region. Structure refinement reveals that the adjacent layers in the crystal are related by a 2(1) axis (we call it 2M(1) polytype) with sulfate coordinating in the D(2d) symmetry in the interlayer region. Another polytype in which adjacent layers are related by a 2-fold axis (2M(2) polytype) can also be envisaged. Faulted crystals arising from intergrowths of the 2M(2) polytype within the 2M(1) structure were also obtained. These bayerite-based LDHs have a distinctly different interlayer chemistry when compared to the better known brucite-based LDHs, in that they have a strong affinity for tetrahedral ions such as SO(4)(2-), CrO(4)(2-), and MoO(4)(2-) and a poor affinity for CO(3)(2-) ions. These observations have implications for the use of LDHs in applications related to chromate sorption.

Homogeneous precipitation by formamide hydrolysis: synthesis, reversible hydration, and aqueous exfoliation of the layered double hydroxide (LDH) of Ni and Al.

Homogenous precipitation by formamide hydrolysis results in the formation of a formate-intercalated layered double hydroxide (LDH) of Ni(II) and Al(III). The formate-LDH is sensitive to the atmospheric humidity and reversibly exchanges its intercalated water with atmospheric moisture. The hydration/dehydration cycle is complete within a narrow range of 0-30% relative humidity with significant hysteresis and involves a randomly interstratified intermediate phase. When immersed in water, the formate ion grows its hydration sphere (osmotic swelling), eventually leading to the exfoliation of the metal hydroxide layers into lamellar particles having in-plane dimensions of 100-200 nm and a thickness of 9-12 nm. These nanoplatelets restack to thicker tactoids again upon evaporation of the dispersion. The intercalated formate ion can be exchanged with nitrate ions in solution but not with iodide ions. These observations have implications for many applications of LDHs in the area of carbon dioxide sorption and catalysis.

Interlayer structure of iodide intercalated layered double hydroxides (LDHs).

The iodide-containing layered double hydroxides (LDHs) of Mg and Zn with Al crystallize by the inclusion of extensive positional disorder of I(-) ions in the interlayer region. I(-) ion given its poor charge to size ratio can neither screen effectively the positive charge nor participate in H-bonding with the metal hydroxide layers. Thereby the I(-) ions are not stabilized in sites close to the seat of positive charge of the metal hydroxide layers (6c), nor in sites that facilitate H-bonding (3b or 18h). On the other hand, OH(-) from water can do both and effectively displaces I(-) from the interlayer.

Structure of bayerite-based lithium-aluminum layered double hydroxides (LDHs): observation of monoclinic symmetry.

The double hydroxides of Li with Al, obtained by the imbibition of Li salts into bayerite and gibbsite-Al(OH)(3), are not different polytypes of the same symmetry but actually crystallize in two different symmetries. The bayerite-derived double hydroxides crystallize with monoclinic symmetry, while the gibbsite-derived hydroxides crystallize with hexagonal symmetry. Successive metal hydroxide layers in the bayerite-derived LDHs are translated by the vector ( approximately -1/3, 0, 1) with respect to each other. The exigency of hydrogen bonding drives the intercalated Cl(-) ion to a site with 2-fold coordination, whereas the intercalated water occupies a site with 6-fold coordination having a pseudotrigonal prismatic symmetry. The nonideal nature of the interlayer sites has implications for the observed selectivity of Li-Al LDHs toward anions of different symmetries.

Synthesis and characterization of arsenate-intercalated layered double hydroxides (LDHs): prospects for arsenic mineralization.

The arsenate-intercalated layered double hydroxide (LDH) of Mg and Al is synthesized by coprecipitation. The higher thermodynamic stability and the consequent lower solubility of the unitary arsenates preclude the formation of arsenate-intercalated LDHs of other metals directly from solution. However other M/Al-AsO(4) (M=Co, Ni, Zn) LDHs could be prepared by anion exchange, showing that arsenate intercalation proceeds topotactically. The intercalation of various species of As(V) into the interlayer of LDHs and the subsequent arsenate carrying capacity are dependent upon the pH of the solution. Upon thermal decomposition, the intercalated arsenate ion undergoes reductive deintercalation to give a mixture of As(III) and As(V) oxides. The product oxides revert back to the LDH upon soaking in water on account of the compositional and morphological metastability of the former. This is in contrast with the phosphate-intercalated LDHs, in which the reversibility is suppressed, consequent to the formation of stable metal phosphates.

Solution decomposition of the layered double hydroxide of Co with Fe: phase segregation of normal and inverse spinels.

The nitrate-intercalated layered double hydroxide of Co with Fe decomposes on hydrothermal treatment to yield an oxide residue at a temperature as low as 180 degrees C. The oxide product is phase segregated into a Co(3)O(4)-type normal spinel and a CoFe(2)O(4)-type inverse spinel. Phase segregation is facilitated as decomposition in a solution medium takes place by dissolution of the precursor hydroxide followed by reprecipitation of the oxide phases. In contrast, thermal decomposition takes place at 400 degrees C. This temperature is inadequate to induce diffusion in the solid state whereby phase segregation into the thermodynamically stable individual spinels is suppressed. The result is a single-phase metastable mixed spinel oxide. This is rather uncommon in that a hydrothermal treatment yields thermodynamically stable products where as thermal decomposition yields a metastable product.

Suppression of the reversible thermal behavior of the layered double hydroxide (LDH) of Mg with Al: stabilization of nanoparticulate oxides.

The layered double hydroxide of Mg with Al decomposes below 600 degrees C with the loss of nearly 48% mass, resulting in the formation of an oxide residue having the rock salt structure and nanoparticulate morphology. However, this product reconstructs back into the parent LDH, owing to its compositional and morphological metastability. The oxide can be kinetically stabilized within an amorphous phosphate network built up through an ex situ reaction with a suitable phosphate source such as (NH4)H2PO4. This oxide transforms into a thermodynamically more stable phase with a spinel structure on soaking in an aqueous medium. The oxide residue has a nanoparticulate morphology as revealed by the Scherrer broadening of the Bragg reflections as well as by electron microscopy. This work shows that the hydroxide reconstruction reaction and spinel formation are competing reactions. Suppression of the former catalyzes spinel formation as the excess free energy of the metastable oxide residue is unlocked to promote the diffusion of Mg2+ ions from octahedral to tetrahedral sites, which is the essential precondition to the formation of a normal spinel. This reaction taking place as it does at ambient temperature and in solution helps in the retention of a nanostructured morphology for the spinel. Another way of stabilizing the oxide is by incorporating the thermally stable borate anion into the LDH. This paves the way for an in situ reaction between the cations of the host LDH and the borate guest. The in situ reaction directly leads to the formation of an oxide with a spinel structure.

Conservation of order, disorder, and "crystallinity" during anion-exchange reactions among layered double hydroxides (LDHs) of Zn with Al.

Carbonate and chloride ions mediate an ordered stacking of metal hydroxide slabs to yield ordered layered double hydroxides (LDHs) of Zn with Al, by virtue of their ability to occupy crystallographically well-defined interlayer sites. Other anions such as ClO(4)- (T(d)), BrO(3)- (C(3v)), and NO(3)- (coordination symmetry C(2v)) whose symmetry does not match the symmetry of the interlayer sites (D(3h) or O(h)) introduce a significant number of stacking faults, leading to turbostratic disorder. SO(4)(2-) ions (coordination symmetry C(3v)) alter the long-range stacking of the metal hydroxide slabs to nucleate a different polytype. The degree of disorder is also affected by the method of synthesis. Anion-exchange reactions yield a solid with a greater degree of order if the incoming ion is a CO3(2-) or Cl-. Incoming NO(3)- ions yield an interstratified phase, whereas incoming SO(4)(2-) ions generate turbostratic disorder. Conservation or its converse, elimination, of stacking disorders during anion exchange is the net result of several competing factors such as (i) the orientation of the hydroxyl groups in the interlayer region, (ii) the symmetry of the interlayer sites, (iii) the symmetry of the incoming ion, and (iv) the configuration of the anion. These short-range interactions ultimately affect the long-range stacking order or "crystallinity" of the LDH.

Suppression of spinel formation to induce reversible thermal behavior in the layered double hydroxides (LDHs) of Co with Al, Fe, Ga, and In.

The layered double hydroxides (LDHs) of Co with trivalent cations decompose irreversibly to yield oxides with the spinel structure. Spinel formation is aided by the oxidation of Co(II) to Co(III) in the ambient atmosphere. When the decomposition is carried out under N2, the oxidation of Co(II) is suppressed, and the resulting oxide has the rock salt structure. Thus, the Co-Al-CO(3)(2-)/Cl- LDHs yield oxides of the type Co(1-x)Al(2x/3) square(x/3)O, which are highly metastable, given the large defect concentration. This defect oxide rapidly reverts back to the original hydroxide on soaking in a Na2CO3 solution. Interlayer NO(3)- anions, on the other hand, decompose generating a highly oxidizing atmosphere, whereby the Co-Al-NO(3)- LDH decomposes to form the spinel phase even in a N2 atmosphere. The oxide with the defect rock salt structure formed by the thermal decomposition of the Co-Fe-CO(3)(2-) LDH under N2, on soaking in a Na(2)CO(3) solution, follows a different kinetic pathway and undergoes a solution transformation into the inverse spinel Co(Co,Fe)(2)O(4). Fe3+ has a low octahedral crystal field stabilization energy and therefore prefers the tetrahedral coordination offered by the structure of the inverse spinel rather than the octahedral coordination of the parent LDH. Similar considerations do not hold in the case of Ga- and In-containing LDHs, given the considerable barriers to the diffusion of M3+ (M=Ga, In) from octahedral to tetrahedral sites owing to their large size. Consequently, the In-containing oxide residue reverts back to the parent hydroxide, whereas this reconstruction is partial in the case of the Ga-containing oxide. These studies show that the reversible thermal behavior offers a competing kinetic pathway to spinel formation. Suppression of the latter induces the reversible behavior in an LDH that otherwise decomposes irreversibly to the spinel.

Order and disorder among the layered double hydroxides: combined Rietveld and DIFFaX approach.

A combined approach using the Rietveld technique of structure refinement and DIFFaX simulations of the powder patterns enables us to not only arrive at the complete structure of the layered double hydroxides (LDHs), but also classify and quantify the nature of structural disorder. Hydrolysis of urea dissolved in mixed-metal salt solutions containing a divalent metal (Mg(2+), Co(2+)) with Al(3+) results in the homogeneous precipitation of the corresponding LDH. The products obtained are highly crystalline enabling a complete structure determination including subsequent refinement by the Rietveld method. In contrast, the LDH of Ni(2+) with Al(3+) crystallizes with the incorporation of stacking faults. A combined Rietveld-DIFFaX approach shows that even ;crystalline' samples of this LDH incorporate up to 9% of stacking faults, which are not eliminated even at elevated temperatures (473 K). These studies have implications for the order, disorder and ;crystallinity' of layered phases in general and metal hydroxides in particular.

Layered double hydroxides as potential chromate scavengers.

The LDH of Ni with Fe, having the formula Ni(1-x)Fe(x)(OH)2(A(n-))(x/n)yH2O (A = NO3-, Cl-; x = 0.25, 0.33), scavenges CrO4(2-) ions from solution throughout the concentration range examined (0.00625-0.25 N). The CrO4(2-) uptake capacity is independent of the anion in the starting LDH but is higher when x = 0.25 (3.60 meq g(-1)) as compared to x = 0.33 (2.40 meq g(-1)). These values are higher than those observed for control compounds beta-Ni(OH)2 (1.86 meq g(-1)) and FeO(OH) (1.26 meq g(-1)), which do not have any interlayer chemistry, showing that chromate uptake takes place by its incorporation in the interlayer region by a stoichiometric anion-exchange reaction, rather than by adsorption. Nevertheless, the interaction between the LDH and the chromate ions is weak. The weak interaction is due to the mismatch between the symmetry of the chromate ions and the symmetry of the interlayer site, which introduces turbostratic disorder in the chromate-intercalated LDHs. The chromate ions can be completely leached out by soaking the LDH in a sodium carbonate solution.