ABSTRACT
Titanomagnetite (Fe(3-x)Ti(x)O(4)) nanoparticles were synthesized by room temperature aqueous precipitation, in which Ti(IV) replaces Fe(III) and is charge compensated by conversion of Fe(III) to Fe(II) in the unit cell. A comprehensive suite of tools was used to probe composition, structure, and magnetic properties down to site-occupancy level, emphasizing distribution and accessibility of Fe(II) as a function of x. Synthesis of nanoparticles in the range 0≤x≤0.6 was attempted; Ti, total Fe and Fe(II) content were verified by chemical analysis. TEM indicated homogeneous spherical 9-12 nm particles. µ-XRD and Mössbauer spectroscopy on anoxic aqueous suspensions verified the inverse spinel structure and Ti(IV) incorporation in the unit cell up to x≤0.38, based on Fe(II)/Fe(III) ratio deduced from the unit cell edge and Mössbauer spectra. Nanoparticles with a higher value of x possessed a minor amorphous secondary Fe(II)/Ti(IV) phase. XANES/EXAFS indicated Ti(IV) incorporation in the octahedral sublattice (B-site) and proportional increases in Fe(II)/Fe(III) ratio. XA/XMCD indicated that increases arise from increasing B-site Fe(II), and that these charge-balancing equivalents segregate to those B-sites near particle surfaces. Dissolution studies showed that this segregation persists after release of Fe(II) into solution, in amounts systematically proportional to x and thus the Fe(II)/Fe(III) ratio. A mechanistic reaction model was developed entailing mobile B-site Fe(II) supplying a highly interactive surface phase that undergoes interfacial electron transfer with oxidants in solution, sustained by outward Fe(II) migration from particle interiors and concurrent inward migration of charge-balancing cationic vacancies in a ratio of 3:1.
ABSTRACT
The crystal structure of a hydrothermally synthesized leucite analogue Cs(2)CuSi(5)O(12) has been determined and refined using the Rietveld method from high-resolution synchrotron X-ray and neutron powder diffraction data. This structure is based on the topology and cation-ordering scheme of the Pbca leucite structure of Cs(2)CdSi(5)O(12), and exhibits five ordered Si sites and one ordered Cu tetrahedrally coordinated (T) site. This structure for Cs(2)CuSi(5)O(12) is topologically identical to other known leucite structures and is different from that originally proposed by Heinrich & Baerlocher [(1991), Acta Cryst. C47, 237-241] in the tetragonal space group P4(1)2(1)2. The crystal structure of a dry-synthesized leucite analogue Cs(2)CuSi(5)O(12) has also been refined; this has the Ia3d cubic pollucite structure with disordered T sites.
ABSTRACT
The crystal structures of the leucite analogues Cs(2)MgSi(5)O(12), Cs(2)ZnSi(5)O(12) and Rb(2)MgSi(5)O(12) have been determined by synchrotron X-ray powder diffraction using Rietveld refinement in conjunction with (29)Si MAS NMR spectroscopy. These leucites are framework structures with distinct tetrahedral sites (T sites) occupied by Si and a divalent cation (either Mg or Zn in these samples); there is also a monovalent extra-framework cation (either Cs or Rb in these samples). The refined crystal structures were based on the Pbca leucite structure of Cs(2)CdSi(5)O(12), thus a framework with five ordered Si T sites and one ordered Cd T site was used as the starting model for refinement. (29)Si MAS NMR shows five distinct Si T sites for Cs(2)MgSi(5)O(12) and Rb(2)MgSi(5)O(12), but six Si T sites for Cs(2)ZnSi(5)O(12). The refined structures for Cs(2)MgSi(5)O(12) and Rb(2)MgSi(5)O(12) were determined with complete T-site ordering, but the refined structure for Cs(2)ZnSi(5)O(12) was determined with partial disorder of Mg and Si over two of the T sites.
ABSTRACT
The distribution of cations between tetrahedral (A) sites and octahedral (B) sites in ferrite spinels has been studied using K-edge x-ray absorption spectroscopy. The samples include natural and synthetic end-member magnetites (Fe3O4), a natural Mn- and Zn-rich magnetite (franklinite) and synthetic binary, ternary and quaternary ferrites of stoichiometry M(²+)M2(³+)O4, where M(²+) = Mg, Co, Ni, Zn and M(³+) = Fe, Al. XAS data were obtained for all metals. Complete, unfiltered, EXAFS spectra were refined to determine the percentage distribution of each element over the A and B sites and these data were combined with microprobe analyses to quantify the tetrahedral occupancy for each element in each sample. Measured site occupancies and an internally consistent set of (M-O)(A) and (M-O)(B) bond lengths were used to calculate unit-cell parameters, which show excellent agreement with measured values, pointing to the reliability of the measured occupancy factors. The average occupancies determined for the tetrahedral sites in ferrites are (atoms per formula unit) Mg 0.44, Co 0.24, Ni 0.11, Zn 0.76, Al 0.11 and Fe(³+) 0.92-0.19. The wide range found for Fe(³+) is consistent with it playing a relatively passive role by making good any A-site deficit left by the other competing cations.
