American Mineralogist, Volume 94, pages 771–776, 2009

Inverse spinel structure of Co-doped gahnite

Jasminka PoPović,1,* EmiliJa TkalčEc,2 BisErka GržETa,1 sTanislav kuraJica,2 and
Boris rakvin3
1
Division of Materials Physics, Ruđer Bošković Institute, P.O. Box 180, HR-10002 Zagreb, Croatia
2
Faculty of Chemical Engineering and Technology, University of Zagreb, Marulićev trg 19, HR-10000 Zagreb, Croatia
3
Division of Physical Chemistry, Ruđer Bošković Institute, P.O. Box 180, HR-10002 Zagreb, Croatia

aBsTracT
Powder ZnAl2O4 (gahnite) samples doped with 0–100 at% Co were obtained by a sol-gel technique.
X-ray powder diffraction was used to characterize the samples. Gahnite samples are cubic with the
normal spinel structure, space group Fd3m. Cobalt doping caused a nonuniform increase of unit-cell
parameter. The structure of the gahnite samples was refined by the Rietveld method. The location of
Co2+ was determined by EPR spectroscopy. Cobalt doping of gahnite induces the inverse spinel structure
at only 4 at% Co, and the inversion parameter increases with Co2+ doping level. Metal-oxide distances
in the (Al,Co)O6 octahedra dominantly influence the unit-cell parameter of Co-doped gahnite.
Keywords: Co-doped gahnite, spinel structure, X-ray powder diffraction, Rietveld method

inTroducTion voids match the radii of constituent cations. As u increases from

Zinc aluminate (ZnAl2O4), known by the mineral name gah- its ideal value, anions move along the [111] direction away
nite, is a semiconductor with a wide energy band gap of ~3.9 from the tetrahedraly coordinated cations, which increases the
eV. It is transparent for wavelengths greater than 320 nm, but volume of each tetrahedral site, while octahedral sites become
shows large absorbance in the UV region. Due to its properties, correspondingly smaller. Spinels can demonstrate some degree of
zinc aluminate can be used for various ultraviolet photoelectronic cation disorder, which Verwey and Heilmann (1947) described by
devices (Sampath and Cordaro 1998; Omata et al. 1994). Fur- introducing an inversion parameter, δ. This parameter is defined
thermore, it is used as a catalytic material in various chemical as a fraction of trivalent metal cation B3+ on tetrahedral cation
and petrochemical industries (El-Nabarway et al. 1995; Valen- sites (or a fraction of divalent metal cations A2+ on octahedral
zuela et al. 1997), and also as a ceramic material (Roesky et al. cation sites). In this way, the structural formula for spinels may
1990). When doped with Co2+, Mn2+, and rare earth cations, it be written as IV[A1–δBδ] VI[B2–δAδ] X4. Some of the principal fac-
exhibits luminescence and can be used as a cathodoluminescent tors that influence cation inversion are temperature, cation radii,
material (Müller 2002). Zinc aluminate possesses a normal spi- cation charge, electrostatic contribution to the lattice energy, and
nel structure (O’Neill and Dollase 1994; Sickafus et al. 1999) crystal-field effects.
that can be described with the general formula AB2X4. Spinels O’Neill and Dollase (1994) performed a detailed structural
crystallize in the cubic system, in the space group Fd3m. The study of zinc aluminate powder samples annealed in the tem-
unit cell contains 32 X2– anions in a face-centered cubic packing perature range from 700 to 1400 °C and then rapidly quenched
(fcc). Inside the anion lattice, cations have 32 octahedral and 64 in water. It was found that the unit-cell parameter a slightly
tetrahedral interstices available. In normal spinel structures, 1/8 increased and oxygen positional parameter u slightly decreased
of the tetrahedral interstices are occupied by divalent cations A2+, in annealing, reflecting a small increase of inversion parameter
while 1/2 of the octahedral interstices are occupied by trivalent δ (0.01–0.06 depending on the temperature of annealing). Also,
cations B3+. The conventional choices for the unit-cell origin in the unit-cell parameter a of the powder sample annealed at 1200
spinel are either on the A-site cation (43m symmetry) or on the °C was found to be equal (within the standard deviation) to the
octahedral vacancy (3m symmetry) as reported by Sickafus et al. unit-cell parameter of single-crystal sample annealed at the same
(1999). Regardless of origin setting, anions are always located temperature. From these investigations, it could be concluded that
on position 32e. The coordinates of the anions at equipoint 32e gahnite generally possesses a normal spinel structure regardless
are not special: they vary according to a single parameter, the of temperature.
anion positional parameter, u. For a perfect fcc anion arrange- In contrast to the structure of zinc aluminate, the structure
ment, u(43m) = 3/8 and u(3m) = 1/4, respectively. Depending on the of cobalt aluminate (CoAl2O4) displays a pronounced inversion
A/B cation radii ratio, the anion sublattice expands or contracts even at room temperature (δ = 0.155) as found by Toriumi et
by varying u until the volume of the tetrahedral and octahedral al. (1978). Nakatsuka et al. (2003) performed a structural study
by means of X-ray powder diffraction and Rietveld structure
* E-mail: [email protected] refinement of CoAl2O4 samples, which were annealed at various

0003-004X/09/0506–771$05.00/DOI: 10.2138/am.2009.3173 771

772 POPOVIć ET Al.: INVERSE SPINEl STRUCTURE IN Co-DOPED GAHNITE

temperatures between 700 to 1350 °C and then rapidly quenched Methods

in water. They noticed that the unit-cell parameter a increased Structural changes due to Co incorporation in the zinc aluminate lattice were
and the oxygen positional parameter u decreased with increasing studied by X-ray diffraction (XRD) at room temperature using a Philips MPD 1880
annealing temperature up to 1250 °C, as a consequence of the counter diffractometer with CuKα radiation. Two data sets were collected for each
prepared gahnite sample: (1) XRD pattern of the sample mixed with a standard
increase in structure inversion with temperature. The inversion reference material, silicon powder (Koch-light lab. ltd., 99.999% purity), scanned
parameter δ reached a maximum value of 0.23 at 1250 °C. The in steps of 0.02 °(2θ) in the 2θ range from 10 to 100° with fixed counting time of
decrease in the inversion parameter value for the sample an- 7 s per step, for the purpose of precise determination of unit-cell parameters; and
nealed at 1350 °C was explained by the authors as a possible (2) XRD pattern of the pure sample scanned in the 2θ range from 10 to 140° also
in steps of 0.02 °(2θ) and with fixed counting time of 7 s per step, for the purpose
redistribution between the IVA and VIB site occupation during the
of the Rietveld structure refinement (Rietveld 1969). Precise determination of the
quenching process of the annealed samples. unit-cell parameter a of prepared samples was performed by the method proposed
To the best of our knowledge, structural studies of Co-doped by Toraya (1993). Bragg angle positions (2θ) of several diffraction lines of the
ZnAl2O4 are not abundant in the literature. Duan et al. (2005) examined sample and three diffraction lines of silicon were determined by individual
investigated microstructure and spectroscopic properties of profile-fitting method (program PROFIT: Toraya 1986) and taken as input data for
the program UNITCEll (Toraya 1993). Initial unit-cell parameters were refined by
Co2+:ZnAl2O4/SiO2 nanocomposite glasses containing nanocrys- the whole-powder-pattern decomposition method (program WPPF: Toraya 1986)
talline Co-doped ZnAl2O4 dispersed in a silica glass matrix. The using the split-type pseudo-Voigt profile function and the polynomial background
samples were prepared by the sol-gel technique. The gels were model. Crystal structures of the prepared samples were refined by the Rietveld
of composition 89SiO2-6Al2O3-5ZnO-xCoO (x = 0.2, 0.4, 0.6, method with the program X’Pert HighScore Plus, version 2.1 (PANalytical 2004),
using a pseudo-Voigt profile function and also the polynomial background model.
0.8, 1). The absorption spectra of the prepared samples consisted
Isotropic vibration modes were assumed for all atoms.
of two bands: a strong absorption band centered at 590 nm and EPR spectroscopy was performed for examining the Co position in the Co-
a broad absorption band centered at 1400 nm. The observed doped gahnite structure. Investigation was carried out with standard X-band EPR
visible and near-infrared absorption bands are characteristic of spectrometer Bruker Elexys FT/CW 580 at low temperatures (10 to 70 K). All
tetrahedrally coordinated Co2+ cations. The absorbance of the spectra were obtained with the magnetic field amplitude of 0.3 mT at 100 KHz.
The microwave power used was about 0.6 mW and spectra were detected at the
spectra increased with an increase in the Co content indicating first harmonic of the modulation frequency.
pronounced incorporation of Co2+ on tetrahedral sites in the
ZnAl2O4 structure. The lattice constant of Co-doped ZnAl2O4 rEsulTs and discussion
increased with an increase in Co-doping level, which the authors XRD characterization of samples
explained by a simple Co2+ substitution for Zn2+, obviously disre-
garding the fact that the mentioned substitution would lead to a XRD patterns of the prepared samples S0–S10 indicated that
decrease of unit-cell parameter (cation radii for tetrahedral Zn2+ all prepared gahnite samples had a characteristic cubic spinel
and Co2+ being 0.60 and 0.58 Å, respectively). structure. No impurities were detected in the samples. Refined
The present paper reports the preparation of Co-doped gahnite values of unit-cell parameter a for prepared gahnite samples are
samples by a sol-gel technique and their structural characteriza- listed in Table 1. The unit-cell parameter of gahnite increased
tion. The structural location of Co2+ cations has been proposed with Co-doping level. A pronounced increase of the unit-cell
on the basis of EPR spectroscopy and the Rietveld structure parameter was noticed for gahnite samples doped with 0–25
refinement of XRD powder data. and 75–100 at% Co in comparison with those containing 25–75
at% Co, as presented in Figure 1. With Co doping, the decrease
ExpErimEntal mEthods of unit-cell parameter should be expected considering that ionic
Sample preparation radius of 4-coordinated Co2+ is smaller than that of 4-coordinated
Zn2+. However, the opposite trend was noticed. The observed lat-
Powder samples of zinc aluminate doped with 0, 4, 8, 12, 25, 40, 50, 60, 75,
90, and 100 at% Co (substituted for Zn) were prepared by a sol-gel technique. tice expansion is an indication of a considerable level of structure
Aluminum-sec-butoxide, zinc nitrate hexahydrate [Zn(NO3)2·6H2O], and cobalt inversion in gahnite due to Co doping. That means that only a
nitrate hexahydrate [Co(NO3)3·6H2O] were dissolved in 2-butanole by vigorous
stirring. Prepared gels were dried at room temperature during few days, then ad-
ditionally annealed at 800 °C for 2 h and slowly cooled to RT in the furnace. The
prepared samples were denoted as S0 to S10 (Table 1). Sample S0 was white, while
other samples were blue, from light blue (S1) to dark blue (S10).

Table 1. Refined unit-cell parameter a for samples S0–S10

Sample Co content (at%) Rp Rwp a (Å)
S0 0 0.048 0.063 8.0854(3)
S1 4 0.036 0.057 8.0863(5)
S2 8 0.035 0.052 8.0883(4)
S3 12 0.039 0.056 8.0897(4)
S4 25 0.039 0.059 8.0914(3)
S5 40 0.033 0.050 8.0924(4)
S6 50 0.034 0.050 8.0928(5)
S7 60 0.040 0.056 8.0931(7)
S8 75 0.038 0.053 8.0945(6)
S9 90 0.032 0.049 8.0973(6)
S10 100 0.030 0.051 8.1005(5)
Note: Rp and Rwp are the discrepancy factors that characterize a quality of the FigurE 1. Relationship between unit-cell parameter a of Co-doped
fit (Young et al. 1982). gahnite and Co2+ content.
 POPOVIć ET Al.: INVERSE SPINEl STRUCTURE IN Co-DOPED GAHNITE 773

part of Co2+ substitutes for Zn2+ on tetrahedral cation sites, and centration of Co2+ centers. The amount of splitting between these
the remaining Co2+ substitutes for Al3+ on octahedral cation sites lines is 11.5 mT (insert in Fig. 2) and corresponds to eight lines
in the ZnAl2O4 lattice, causing the increase of unit-cell parameter of hyperfine splitting of 59Co nuclear spin (I = 7/2). The effec-
(ionic radii of octahedrally coordinated Al3+ and high-spin Co2+ tive g value of this spectral component is g = 7.79. To elucidate
being 0.535 and 0.745 Å, respectively). A nonuniform increase a possible character of the obtained EPR spectra, the additional
of unit-cell parameter with increase of Co-doping level (Fig. 1) spectra for sample S1 were taken at 35 and 70 K (Fig. 3). With
suggests a nonuniform Co2+ substitution mechanism. the increase in temperature, the intensity of EPR components
decreased. At 70 K, the spectrum became dominated by two
EPR spectroscopy broad components at g = 5.30 and g = 2.0 indicating that these
EPR spectra of the samples S1, S2, and S3 collected at 10 K components had a slightly slower relaxation than other spectrum
are shown in Figure 2. The spectra display a typical distorted axial components seen at lower temperatures. This evidently showed
pattern for high-spin Co2+ centers with three major resonance that the EPR spectra of Co-doped gahnite have the composite
features. These spectra are in agreement with expectation for character. The components can be identified as contributions to
molecules with S = 3/2 subjected to zero-field splitting where the spectra from Co2+ cations in more than one local environment.
only the (±1/2) Kramer’s doublet, identified from the effective Indeed, in accord with the previous EPR studies (Sellin et al.
g values, is resonant (Weil et al. 1994). An additional multiple 1983) the values g = 7.79, g = 2.22, and g = 1.84 and hyperfine
splitting with low intensity is incorporated in the broad low-field splitting are consistent with Co2+ center on distorted octahedral
resonance signal, as clearly seen for the sample with lowest con- cation site. On the other hand, the spectral components at g =
5.30 and g = 2.0 are characteristic of Co2+ centered on the tet-
rahedral cation site (Pountney and Vašak 1992). Based on these
results, a general formula for Co-doped gahnite can be written
as IV[Zn1–xCox–δAlδ] VI[Al2–δCoδ] O4, where x represents the level
of incorporated Co2+ cations in the gahnite structure, and δ is the
inversion parameter of the spinel structure.

Rietveld structure refinement

The crystal structures of the samples S0, S1, S2, S3, S4, S6,
S8, and S10 were refined by the Rietveld method. The structure
of undoped gahnite reported by O’Neill and Dollase (1994) was
used as the starting structure model for our undoped gahnite
(sample S0). For the Co-doped samples, a gahnite structure model

FigurE 2. EPR spectra of Co-doped samples S1, S2, and S3

(containing 4, 8, and 12 at% Co, respectively) taken at 10 K. Solid
arrows denote g values for Co2+ cation on the octahedral site, while
dashed arrows denote g values for tetrahedrally coordinated Co2+ cation.
The small sharp peaks near 180, 390, and 405 mT correspond to the
resonance cavity signals.

FigurE 3. EPR spectra of sample S1 taken at 10, 35, and 70 K. FigurE 4. Result of the Rietveld refinement for samples S0 and S4.
774 POPOVIć ET Al.: INVERSE SPINEl STRUCTURE IN Co-DOPED GAHNITE

Table 2. Results of Rietveld refinements: Structural parameters and their standard deviations for samples S0, S1, S2, S3, S4, S6, S8, and S10
Sample δ Rwp Atom site Wyck. position Occupancy x=y=z Biso (Å2)
S0 0 0.059 IV
A 8a 1 Zn 0.125 0.97(2)
VI
B 16d 1 Al 0.5 0.29(3)
O 32e 1O 0.2644(1)* 0.53(5)

S1 0.037(4) 0.068 A
IV
8a 0.003 Co + 0.96 Zn + 0.037 Al 0.125 0.90(1)
B
VI
16d 0.0185 Co + 0.9815 Al 0.5 0.45(2)
O 32e 1O 0.2640(1) 0.48(3)

S2 0.051(3) 0.072 A
IV
8a 0.029 Co + 0.92 Zn + 0.051 Al 0.125 0.90(2)
B
VI
16d 0.0255 Co + 0.9745 Al 0.5 0.47(2)
O 32e 1O 0.2636(1) 0.51(3)

S3 0.055(4) 0.057 A
IV
8a 0.065 Co + 0.88 Zn + 0.055 Al 0.125 0.90(2)
B
VI
16d 0.0275 Co + 0.9725 Al 0.5 0.44(1)
O 32e 1O 0.2634(9) 0.43(3)

S4 0.070(3) 0.054 A
IV
8a 0.18 Co + 0.75 Zn + 0.07 Al 0.125 1.06(6)
B
VI
16d 0.035 Co + 0.965 Al 0.5 0.48(1)
O 32e 1O 0.2631(8) 0.55(2)

S6 0.095(4) 0.056 A
IV
8a 0.405 Co + 0.5 Zn + 0.095 Al 0.125 0.94(3)
B
VI
16d 0.0475 Co+0.9525 Al 0.5 0.64(2)
O 32e 1O 0.2629(1) 0.63(3)

S8 0.150(4) 0.059 A
IV
8a 0.6 Co + 0.25 Zn + 0.15 Al 0.125 0.58(2)
B
VI
16d 0.075 Co + 0.925 Al 0.5 0.68(2)
O 32e 1O 0.2625(1) 0.67(3)

S10 0.248(5) 0.061 A

IV
8a 0.752 Co + 0.248 Al 0.125 0.97(7)
VI
B 16d 0.124 Co + 0.876 Al 0.5 0.37(2)
O 32e 1O 0.2613(1) 0.72(5)
* Coordinate of oxygen at 32e is known as oxygen positional parameter u.

was used that had a portion of tetrahedrally coordinated Zn2+ and

a portion of octahedrally coordinated Al3+ ions substituted by Co2+
ions. In the structure refinement procedure, the site occupancy
parameters for cations (Zn2+, Co2+, and Al3+ on the tetrahedral
site and Al3+ and Co2+ on the octahedral site) were determined
indirectly, namely by varying the inversion parameter δ under
the constrain that maintained the chemical composition of the
sample. Isotropic temperature factors (Biso) for cations sharing the
same cation site were constrained to change identically during
the Rietveld refinement.
The observed and calculated powder patterns for the samples
S0 and S4 are presented in Figure 4. Refined structural parameters
are given in Table 2. The refinement confirmed the spinel-type
structure of the samples. However, only sample S0 possesses the
normal spinel structure. Crystal structures of other samples dis-
play a nonzero inversion parameter δ in the range between 0.054 FigurE 5. Variation of inversion parameter δ with Co content in
(for S1) and 0.248 (for S10). The inversion parameter increased gahnite samples.
with increasing Co content in gahnite as seen in Figure 5. The
value of the inversion parameter for pure CoAl2O4 (sample S10)
is consistent with results obtained by Nakatsuka et al. (2003).
The oxygen positional parameter u decreased with the increase Table 3. Metal-oxygen distances (Å) in structural tetrahedra and
of Co content in gahnite indicating a decrease of the tetrahedral octahedra of gahnite samples
site volume and expansion of the octahedral site volume with Sample Co content Inversion Interatomic distances M-O (Å)
Co doping. This is a consequence of both Zn2+ substitution by (at%) parameter δ tetrahedra octahedra
smaller IVCo2+ cations on the tetrahedral site and Al3+ substitu- S0 0 0 1.953 1.913
S1 4 0.037 1.948 1.917
tion by larger VICo2+ cations on the octahedral site. Table 3 lists S2 8 0.051 1.943 1.920
metal-oxygen distances in tetrahedra and octahedra for gahnite S3 12 0.054 1.940 1.921
samples. In Figure 6, it can be seen that metal-oxygen distances in S4 25 0.070 1.937 1.925
S6 50 0.095 1.932 1.926
tetrahedra decrease almost linearly with the increase of inversion S8 75 0.150 1.929 1.929
parameter, while metal-oxygen distances in octahedra simultane- S10 100 0.248 1.914 1.939
 POPOVIć ET Al.: INVERSE SPINEl STRUCTURE IN Co-DOPED GAHNITE 775

Inversion parameter δ
FigurE 6. Metal-oxygen distances in tetrahedra and octahedra of
gahnite with inversion parameter δ.

FigurE 8. Dependence of Co content of octahedra on total Co

content in gahnite.

caused by Co doping (Fig. 7b) has the same trend as the change
of unit-cell parameter of gahnite (Fig. 1). This is quite under-
standable since the metal-oxygen bonds in octahedra, Moct-O, are
almost parallel to the [100], [010], and [001] axes. The change
of interatomic distances in tetrahedra has much smaller impact
on the unit-cell parameter of gahnite because Mtetr-O bonds make
an angle of ~53° with the [100], [010], and [001] axes. Besides,
in the spinel-type structure there are twice as many structural
octahedra as tetrahedra.
The nonuniform increase in the unit-cell parameter of gahnite
with increasing Co content may be explained by the results of
the Rietveld structure refinements as follows. In doping, a por-
tion of the Co content occupies tetrahedral sites of the gahnite
structure (substituting for Zn), and a portion occupies octahedral
sites (substituting for Al). The portion of Co that occupies the
octahedral sites is given by the ratio of inversion parameter (δ)
FigurE 7. Metal-oxygen distances in (a) structural tetrahedra and and total Co content (x), namely δ/x. Figure 8 presents the de-
(b) structural octahedra as a function of Co content in gahnite. pendence of δ/x on Co content, x, in doped gahnite samples. For
the examined doped gahnite samples, δ/x has a minimum at Co
ously increase almost linearly. The same type of dependence on content x = 0.5, as seen in Figure 8. According to this, at a low
inversion parameter of the metal-oxygen distances was noted for Co-doping level the portion of Co on octahedral sites is a large
CoAl2O4 samples that suffered an increase of structure inversion part of total Co content (almost 93% of total Co content at x =
on annealing (Nakatsuka et al. 2003). 0.04). This induces a pronounced increase of unit-cell parameter
Changes in metal-oxygen distances in structural tetrahedra for low doping levels. In further doping, the portion of Co on
and octahedra of gahnite as a function of Co-doping level are octahedral sites decreases until it reaches 19% of total Co content
shown in Figure 7. Metal-oxygen distances in tetrahedra decrease for doping level x = 0.5, causing a slower increase of unit-cell
with doping level (Fig. 7a), while metal-oxygen distances in parameter with saturation at x = 0.5. After the doping level of
octahedra increase (Fig. 7b). It is obvious that the change of 0.5, the portion of Co on octahedral sites increases, which causes
metal-oxygen distance in the structural octahedra of gahnite a renewed faster increase of unit-cell parameter at x > 0.5.
776 POPOVIć ET Al.: INVERSE SPINEl STRUCTURE IN Co-DOPED GAHNITE

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