W. Michael Chance

2H-PEROVSKITE RELATED OXIDES: SYNTHESIS, STRUCTURES AND PREDICTIONS

The ability to synthesize new complex oxide materials that belong to any of the large number of known oxide structural families relies typically on a general understanding of the relationship between the specific structure type and the chemical composition of its members. However, before one can create such a structure-composition relationship that enables the synthesis of new members, one needs structural information about a sizable number of existing compositions belonging to this structural family, somewhat of a “chicken or the egg” problem. In this Highlight we will use one family of oxides, specifically oxides related to the hexagonal perovskite structure, to illustrate how exploratory crystal growth methods have been used successfully to synthesize enough diverse compositions to enable the formulation of a general structural description. Furthermore, by now it appears that enough members with different compositions have been synthesized so that one can attempt to create a structure-composition relationship that has predictive powers.

Crystal growth of new hexahydroxometallates using a hydroflux.

A series of seven compounds, Sr2Mn(OH)6, Ba2Mn(OH)6, Sr2Co(OH)6, Ba2Co(OH)6, Sr2Ni(OH)6, Ba2Ni(OH)6, and Ba2Cu(OH)6, were synthesized using a low-melting hydroflux, a hybrid approach between aqueous hydrothermal and molten hydroxide flux techniques. Crystals of the hexahydroxometallates were obtained by dissolving appropriate amounts of alkaline-earth nitrates or hydroxides and transition-metal oxides, acetates, or chlorides in the hydroflux and reacting at 180-230 °C. The isostructural compounds all crystallize in the monoclinic space group P2(1/n). The monoclinic structure consists of isolated transition-metal octahedra within a three-dimensional framework of corner- and edge-shared eight-coordinate, alkaline-earth polyhedra. Magnetic susceptibility data show that all compounds are simple paramagnets. Thermogravimetric analysis indicates that these hydroxides lose water between 215 and 350 °C and transform into oxide products, the identity of which depends on the metal cations present in the parent hexahydroxometallates.

A5RE4X[TO4]4 crystal growth and photoluminescence. Hydroflux synthesis of sodium rare earth silicate hydroxides

Single crystals of Na5RE4(OH)[SiO4]4 (RE = Pr, Nd, Sm, Eu, Tb–Yb, Y) were grown using the hydroflux synthetic method. All compositions adopt the tetragonal I space group with lattice parameter ranges of a = 11.5275(4)–12.0588(3) A and c = 5.3951(4)–5.4846(13) A. Intense photoluminescent properties were observed for Na5Eu4(OH)[SiO4]4, Na5Gd4(OH)[SiO4]4, and Na5Tb4(OH)[SiO4]4. The magnetic susceptibility was measured for the magnetic rare earth containing compositions, where the terbium analogue displayed antiferromagnetic order at T = 2.8 K.

Investigation of the high-temperature redox chemistry of Sr2Fe1.5Mo0.5O6−δvia in situ neutron diffraction

Crystallographic structural changes were investigated for Sr2Fe1.5Mo0.5O6−δ, an electrode material for symmetric solid oxide fuel cells. The samples of this material were heated and cooled in wet hydrogen and wet oxygen atmospheres, to simulate the reducing and oxidizing conditions experienced under actual fuel cell operating conditions, and their structures and oxygen contents were determined using in situ powder neutron diffraction. The existence of a reversible tetragonal to cubic phase transition was established to occur between room temperature and 400 °C, both on heating and cooling in either oxygen or hydrogen. The oxygen content reaches a low value of 5.50(2) at 850 °C in wet hydrogen. Excellent correlations are observed between the oxygen content of the structure and the conductivities reported in the literature.

Synthesis of a Ferrolite: A Zeolitic All-Iron Framework

Crystals of the first sodalite-type zeolite containing an all-iron framework, a ferrolite, Ba8 (Fe12 O24 )Nay (OH)6 ⋅x H2 O, were synthesized using the hydroflux method in nearly quantitative yield. Ba8 (Fe12 O24 )Nay (OH)6 ⋅x H2 O crystallizes in the cubic space group Pm3‾m with a=10.0476(1) Å. Slightly distorted FeO4 tetrahedra are linked to form Fe4 O4 and Fe6 O6 rings, which in turn yield channels and internal cavities that are characteristic of the sodalite structure. Barium, sodium, and hydroxide ions and water molecules are found in the channels and provide charge balance. Magnetic measurements indicate that the ferrolite exhibits magnetic order up to at least 700 K, with the field-cooled and zero-field-cooled curves diverging. Analysis of the 57 Fe Mössbauer spectra revealed two spectral components that have equal spectral areas, indicating the presence of two subsets of iron centers in the structure. Dehydrated versions of the ferrolite were also prepared by heating the sample.