Ag1+xTlO2 (0.03 ≤ x ≤ 0.18), novel adaptations of the delafossite structure type featuring subvalent silver

Article abstract of DOI:10.1002/zaac.201400050

A family of novel variations of the delafossite type of structure, Ag _1+xTlO₂, was synthesized and characterized. For three members the crystal structures were solved and refined on single crystal data: Ag_1+αTlO₂ [α = 0.18, P{3}m1, Z = 1, a = 3.40427(9), c = 6.1296(1) A, R₁ = 0.033, 126 independent reflections]; Ag_1+βTlO₂ [β = 0.09, R{3}m, Z = 6, a = 3.40685(8), c = 37.5953(9) A, R₁ = 0.039, 214 independent reflections]; Ag_1+γTlO₂ [γ = 0.03, R{3}m, Z = 9, a = 3.403(2), c = 56.67(3) A, R₁ = 0.038, 397 independent reflections]. Different from the conventional delafossite structure, part of the silver layers accommodate an excess of ca. 0.18 silver atoms per layer, thus generating a subvalent bonding state of silver. In accordance with the structural findings, the new silver oxthallates(III) are metallic conductors, and show reduced binding energies for the silver 3d_5/2 states, compared to silver(I) oxide. Copyright

Full text of DOI:10.1002/zaac.201400050

ARTICLE
DOI: 10.1002/zaac.201400050
Ag TlO (0.03 Յ x Յ 0.18), Novel Adaptations of the Delafossite Structure
1+x
2
Type Featuring Subvalent Silver
[a]
[a]
[a]
[a]
Jürgen Nuss, Volker Dietrich, Jan Curda, and Martin Jansen*
Dedicated to Professor C. N. R. Rao on the Occasion of His 80th Birthday
Keywords: Metallic oxides; Subvalent compunds; Silver; Crystal structure; High oxygen pressure synthesis
Abstract. A family of novel variations of the delafossite type of struc-
ture, Ag1+xTlO , was synthesized and characterized. For three mem-
bers the crystal structures were solved and refined on single crystal
1
3.403(2), c = 56.67(3) Å, R = 0.038, 397 independent reflections].
2
Different from the conventional delafossite structure, part of the silver
layers accommodate an excess of ca. 0.18 silver atoms per layer, thus
generating a subvalent bonding state of silver. In accordance with the
structural findings, the new silver oxthallates(III) are metallic conduc-
tors, and show reduced binding energies for the silver 3d5/2 states,
¯
data: Ag1+αTlO
2
[α = 0.18, P3m1, Z = 1, a = 3.40427(9), c =
= 0.033, 126 independent reflections]; Ag1+βTlO
β = 0.09, R3m, Z = 6, a = 3.40685(8), c = 37.5953(9) Å, R = 0.039,
6
.1296(1) Å, R
1
2
¯
[
1
¯
2
14 independent reflections]; Ag1+γTlO [γ = 0.03, R3m, Z = 9, a = compared to silver(I) oxide.
2
Introduction
does not follow the otherwise generally valid linear increase
with increasing cation (3+) radius. Sheets et al. published an
I
III
[1]
The A M O delafossite type of structure can be realized
[27]
2
alternative hydrothermal synthesis route in 2006,
reacting
virtually for any main group or transition metal M in the oxi-
dation state +3 that tolerates octahedral coordination by oxy-
gen, and the coinage metals A (Cu or Ag) in their monovalent
states. Oxides featuring this structure continue to attract sig-
Ag O with Tl O in an aqueous solution of 2.5 m NaOH at
2
2 3
2
10 °C. The yield of AgTlO was about 50% and the sample
2
contained unreacted Tl O and elemental silver.
2
3
Herein we report on new silver delafossites Ag1+xTlO , sys-
2
[2–6]
nificant interest, among others as catalysts,
inorganic phos-
tematically accommodating an excess of silver.
[7,8]
[9]
[10–
phors,
battery materials, transparent semiconductors,
1
2]
[13,14]
or in general for special properties.
The basic struc-
tural variation encountered so far is related to the stacking se- Experimental Section
quences characterizing the trigonal structure, and is resulting
Syntheses: Ag1+βTlO
and Tl (both freshly precipitated), adding an aqueous solution of
m KOH.
2 2 2
and Ag1+γTlO can be synthesized from Ag O
in the formation of 2H and 3R polymorphs.[ Only recently
variants of this apparently quite robust structure type have
been reported. Among them are the first examples of quater-
15]
2 3
O
1
[
16]
nary delafossites Ag LiM O (M = Rh, Ir),
and Ag Ni O
2 4
Phase pure Ag1+βTlO
2 2
was obtained by reacting Ag O (266 mg,
3
2
6
3
as a new stage-2 intercalation compound of 2H AgNiO2.[17]
1.15 mmol) and Tl O (457 mg, 1 mmol) in stainless steel autoclaves
2 3
[
28]
at elevated oxygen pressure and temperature.
starting materials were placed in gold tubes and reacted at p(O
8 MPa and T = 400 °C, for 200 h. Addition of small amounts
0.2 mL) of an aqueous 1 m KOH solution resulted in enlarged crystal-
lite sizes. Alternatively Ag1+βTlO was synthesized by ion exchange
reaction in nitrate melts. Therefore a mixture of β-NaTlO
excess of AgNO and KNO (ratio 2:1) were heated in sealed glass
Ag O and Tl O , in aqueous sodium hydroxide (50%) at ampoules in an argon atmosphere for 50 h at 280 °C.
The intimately mixed
Quite a number of conventional 2H and 3R silver delafos-
2
) =
sites AgMO (M = Al, Co, Cr, Fe, Ga, In, Lu, Ni, Rh, Sc, Tm,
2
4
(
Yb) have been reported.[
18–25]
AgTlO was first mentioned by Geßner in 1970 to adopt the
2
2
[26]
3
R delafossite structure.
In 1971 Shannon et al. published
[29]
2
and an
[19]
a hydrothermal synthesis of 3R AgTlO2,
starting from
3
3
2
2 3
5
00 °C. However, except for the lattice parameters no further
For Ag1+γTlO
2 2
, in a typical experiment Ag O (255 mg, 1.1 mmol),
crystallographic details were given. The reported lattice con-
stant a = 3.568(2) Å is significantly larger than expected and
Tl (457 mg, 1 mmol) and KOH (1 m, 15 mL) were combined and
2 3
O
reacted for 14 d at 200 °C in a steel autoclave. The yield after filtration
and elution with water and alcohol was 100% referred to the starting
amount of thallium.
*
Prof. Dr. M. Jansen
Fax: +49-711-689-1502
E-Mail: M.Jansen@fkf.mpg.de
Pure samples of Ag1+αTlO
of mixtures of Ag O (freshly precipitated) and TlNO
Ͼ 99.9%) in stainless steel autoclaves at elevated oxygen pressures
2
were obtained from solid state reactions
[a] Max-Planck-Institut für Festkörperforschung
2
3
(Sigma-Aldrich,
Heisenbergstr. 1
70569 Stuttgart, Germany
Z. Anorg. Allg. Chem. 2014, 640, (6), 1063–1068
© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
1063

J. Nuss, V. Dietrich, J. Curda, M. Jansen
ARTICLE
and temperatures. The starting materials with a silver to thallium ratio Bruker, Cu-Kα1 radiation from primary Ge(111) Johannson-type mono-
of 1.4 were intimately mixed and placed into gold tubes, which were chromator), recorded at room temperature. The powder diffraction data
sealed from one side and mechanically closed from the other side.
In a typical experiment phase pure samples of black, polycrystalline of the powder pattern, the program TOPAS was used.
were collected in the range of 5 to 100 degrees in 2θ. For refinement
[
30]
Ag1+αTlO
TlNO (532 mg, 1 mmol) at the p(O
and 420 °C, respectively.
2
were obtained by reacting Ag
2
O (325 mg, 1.4 mmol) and
The single crystal diffraction data were collected with a Bruker AXS
Smart-CCD diffractometer (Mo-K radiation, graphite monochroma-
tor). Data reductions, including corrections for the Lorentz and polar-
3
2
) and T conditions of 135 MPa
α
[
31,32]
ization effect as well as absorption, were carried out.
The struc-
All silver thallates are black crystalline solids with hexagonal plate-
like morphology. They are stable towards air and water.
tures were solved with direct methods and refined by using full-matrix
[
33]
least-squares techniques using the program package SHELXTL. For
X-ray Investigations: X-ray investigations on powder samples were the technical details of data acquisition and selected crystallographic
performed using high-resolution X-ray powder diffraction data (D8, data, see Table 1 and Table 2.
Table 1. Crystal data, data collection, and refinement details for Ag1+αTlO
Ag1+αTlO
2
, Ag1+βTlO
Ag1+βTlO
2
, and Ag1+γTlO
2
at 25 °C.
Ag1+γTlO
2
2
2
Formula unit
Formula weight
Space group (no.), Z
Lattice constants
a /Å
Ag1.18TlO
363.66
P3m1 (164), 1
2
Ag1.09TlO
351.97
R3m (166), 6
2
Ag1.03TlO
347.84
R3m (166), 9
2
¯
¯
¯
3.430(1)
3.4007(5)
3.40685(8)
3.4037(5)
a)
a)
a)
3.40427(9)
3.403(2)
c /Å
6.153(4)
37.52(2)
37.5953(9)
375.8(1)
9.332
56.734(9)
56.67(3)
569.2(2)
9.132
a)
a)
a)
6.1296(1)
V /Å3
62.70(4)
9.631
0.12ϫ0.10ϫ0.08
ρ
xray /g·cm–3
3
Crystal size /mm
Diffractometer
X-ray radiation, λ /Å
0.08ϫ0.06ϫ0.04
0.08ϫ0.06ϫ0.04
SMART APEX I, Bruker AXS
Mo-K , 0.71073
Multi-scan, SADABS
α
[
32]
Absorption correction
2
θ range /°
6.62 Յ 2θ Յ 68.14
–5 Յ h Յ 5
9.72 Յ 2θ Յ 64.60
–5 Յ h Յ 5
–4 Յ k Յ 5
–54 Յ l Յ 54
3001
214, 0.061
18
0.160, 0.069
0.039
2.16 Յ 2θ Յ 69.56
–5 Յ h Յ 5
–5 Յ k Յ 5
–90 Յ l Յ 90
2848
397, 0.038
23
0.163, 0.070
0.038
Index range
–
–
5 Յ k Յ 5
9 Յ l Յ 9
Reflection collected
Data, Rint
No. of parameters
Transmission: tmax, tmin
R [F Ͼ 2σ(F )]
1
wR (F )
874
126, 0.062
11
0.068, 0.041
0.033
0.077
2
2
2
0.084
0.092
Extinction coefficient
CSD no.
–
0.0012(3)
427303
–
427302
427304
a) Lattice constants calculated from powder data by LeBail-fits.[30]
–
4
2
Table 2. Atomic coordinates, occupation factors, and displacement parameters Uij /10 ·Å at 25 °C.
Atom
Site
x
y
z
Occ.
U
11
U
22
U
33
U
12
U
13
U
23
U
eq
Ag1+αTlO
Tl
Ag
O
Ag1+βTlO
Tl
2
2
1a
3f
2d
0
½
1/3
0
0
2/3
0
½
1
75(3)
U
11
372(6)
U11/2
U22/2
U11/2
0
0
174(3)
0.393(8)
1
1321(53) 4236(193) 832(39)
141(35)
861(37) 1722(75) 1806(71)
0
0.809(2)
U
11
194(55)
0
158(24)
6c
3b
9e
6c
6c
0
0
½
0
0
0
0
0
0
0.08194(2)
½
0
0.4449(5)
0.7169(5)
1
1
82(4)
283(9)
U
U
11
144(5)
84(10)
U11/2
U11/2
U22/2
U11/2
U11/2
0
0
0
0
103(4)
217(6)
Ag1
Ag2
O1
11
0.390(11) 1214(60) 3543(206) 364(32)
1
1
–496(29) –992(57) 1448(72)
0
0
123(46)
131(48)
U
11
105(69)
119(72)
0
0
117(31)
127(32)
O2
0
U
11
Ag1+γTlO
Tl1
Tl2
Ag1
Ag2
O1
2
3a
6c
6c
9d
6c
6c
6c
0
0
0
½
0
0
0
0
0
0
0
0
0
0
0
1
1
1
134(3)
128(2)
312(6)
1194(48)
161(38)
147(38)
192(42)
U
U
U
11
11
11
178(4)
187(3)
126(6)
U11/2
U11/2
U11/2
U22/2
U11/2
U11/2
U11/2
0
0
0
0
0
0
149(2)
148(2)
250(4)
0.44471(1)
0.27707(3)
½
0.2404(2)
0.3135(2)
0.1333(2)
0.367(6)
3359(164) 393(24)
504(24) 1007(48) 1407(57)
1
1
1
U
11
U
11
U
11
105(48)
141(54)
135(52)
0
0
0
0
0
0
142(25)
145(25)
173(27)
O2
O3
1
064
www.zaac.wiley-vch.de
© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2014, 1063–1068

Novel Adaptations of the Delafossite Structure Type Featuring Subvalent Silver
Further details of the crystal structures investigations may be obtained Crystal Structures
from the Fachinformationszentrum Karlsruhe, 76344 Eggenstein-
Leopoldshafen, Germany (Fax: +49-7247-808-666; E-Mail:
For the three cases mentioned, single crystals were grown
crysdata@fiz-karlsruhe.de, http://www.fiz-karlsruhe.de/request for de- and the crystal structures were solved and refined on single
posited data.html) on quoting the depository number CSD-427302 crystal data. All structures are constructed of the same building
(
(
Ag1+αTlO
Ag1+γTlO
2
),
).
CSD-427303
(Ag1+βTlO
2
)
and
CSD-427304
units, which are combined in different ratios and stacking se-
–
2
quences. The anionic partial structure (TlO ) is the same in
2
all three cases, the very common slab of edge sharing [TlO6]
octahedra. It is representing a cut out of the rock salt structure,
Energy Dispersive X-ray Spectoscropy: EDX analyses were carried
out on single crystals of different samples, with a Philips XL 30 TMP,
equipped with an energy dispersive unit for microanalysis (Phönix,
EDAX).
[34]
[1]
and is found e.g. in the α-NaFeO ,
CuFeO (delafossite),
2
2
and β-RbScO
types of structure.[
35,36]
Usually, these 2D poly-
2
anions are arranged on trigonal lattices, stacking along the re-
spective c directions. The spacings in between are occupied by
the monovalent cations in octahedral, trigonal or linear sur-
roundings. The group 11 elements, Cu and Ag, always adopt
Conductivity Measurements: Measurements of the electrical conduc-
tivity were performed by the four-point-probe method (Van-der-Pauw)
on pressed pellets (diameter: 6 mm, thickness: 1 mm).
a linear coordination. Within the resulting 3R and 2H delafos-
formed on powder samples, with an Axis ULTRA spectrometer (Al- sites the O–A –O dumbbells are oriented parallel to the c axis,
X-ray Photoelectron Spectroscopy: XPS measurements were per-
+
K
α
radiation: hϫυ = 1486.58 eV, resolution ca. 0.1 eV). As an external while they are inclined to the c axis direction in the related
[37,38]
standard, the binding energy of the C-1s- band was used.
Ag Pb O structure family.
In the new silver thallates
5
2 6
these building units (see Figure 1) are combined to form dif-
ferent stacking variants, see Figure 2. We had to refine average
structures with respect to the silver atoms located within the
Thermal Analysis: The thermal behavior was measured with the
DTA/TGA equipment STA 409, Netzsch, Selb, coupled with a quadru-
pole mass spectrometer. The samples were heated in a corundum cruci-
ble with a rate of 10 °C·min–1 in a flow of dry argon.
Results and Discussion
Syntheses
The title compounds of general composition Ag1+xTlO em-
2
body novel adaptations of the delafossite structure type. For
their syntheses, diverse combinations of starting materials may
be applied, which are subjected to respective specific modes
of processing. The most obvious approach is to start from the
+
+
binary oxides, Ag O and Tl O . Ion exchange of Ag for Na
2
2 3
in NaTlO , and reacting Ag O and TlNO work as well. In
2
2
3
each case a ratio 1.0 Ͻ Ag/Tl Ͻ 1.4, elevated oxygen pressure
and hydrothermal conditions with degrees of filling ranging
from 1 to 5% of the autoclave volume was applied, with reac-
tion temperatures ranging from 200 to 420 °C. At any of those
conditions members of the new family of silver thallates form
reproducibly. However, it has proven difficult to achieve fully
targeted preparation of individual members of the family con-
sisting of Ag1+αTlO (α ≈ 0.18), Ag TlO (β ≈ 0.09), and
2
1+β
2
Ag1+γTlO (γ ≈ 0.03), which in a wider sense represent poly-
2
types.
Figure 2. Crystal structures of Ag1+αTlO
Ag1+γTlO (c). The viewing direction is [010], with red spheres (oxy-
gen), green (thallium), white (ordered silver atoms), black (disordered
silver positions), blue polyhedra represent the TlO octahedra.
2 2
(a), Ag1+βTlO (b), and
Figure 1. Structural building units encountered in Ag1+xTlO
sites with O–Ag–O dumbbells oriented parallel (a) and inclined (b) to
the c axis. Color code: Tl = green, Ag = white/black, O = red.
2
delafos-
2
6
Z. Anorg. Allg. Chem. 2014, 1063–1068
© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
1065

J. Nuss, V. Dietrich, J. Curda, M. Jansen
ARTICLE
+
+
tilted dumbbells (see Figure 3), while all remaining parts of Ag –Ag distances known (about 2.8 Å), even wider than the
+
+
the structures appear to be fully ordered. Applying split atom sum of the van der Waals radii. Depending on the Ag –Ag
models have resulted in rather good figures of merit for the distances assumed, the space available would allow to accom-
refinements. The site occupation factors for the split silver po- modate by a factor of 1.2–1.4 more silver atoms per layer than
sitions, which should amount to 1/3 for the ideal composition required for the ideal composition. Noteworthy, in all three
AgTlO , converged to significantly higher values ranging from cases the parameters of thermal motion show considerable an-
2
0.367 to 0.393 (see Table 2). This is indicating significant ex- isotropies in the displacements of the silver atoms at the split
cess of silver to be present, which was confirmed by indepen- positions indicating that these are smeared out within the ab
dent analyses. The compositions can be narrowed down to 1.17 plane.
silver atoms per disordered layer. Taking into account the
The refinements of the average structures leave some unre-
stacking sequences the deviations from an ideal composition solved crystallographic implications behind. While the lengths
amount to α = 0.18, β = 0.09, and γ = 0.03 within the respec- of the c axes have been unambiguously determined from the
tive stacking variants given in Figure 2.
diffraction patterns, and comply well with the respective stack-
ing sequences found, within the h,k-space no superstructure
reflections were visible. Thus, based on the structural models
suggested several different real structures may be discussed.
Starting from the split atom model as refined, one might
derive various ordering patterns. Two are displayed in Fig-
ure 4, whereby both require to shift the silver atoms within the
ellipsoids of displacement from the refined split position and
to delete some of them. However, the resulting models show
too short Ag–Ag separations of only 2.45–2.65 Å, and a too
high silver content. It appears much more reasonable to assume
–
a composite crystal, where the periodicities of the [TlO ] and
2
silver substructures within the ab plane do not comply. So far,
we do not have any evidence that the two substructures men-
tioned are commensurate.
Figure 3. Positions of the silver atoms, ideal delafossite (open circles,
cf. Figure 1a), and disordered layers (black circles, cf. Figure 1b).
The quite sizeable non-stoichiometry as found for the other-
wise rather robust delafossite structure type comes as a sur-
prise, on a first glance. However, in the light of findings during
the recent past the observations appear reasonable. In the wake
of having acquired the capability to react Ag O virtually with
2
any other binary oxide in a solid state reaction, silver-rich
multinary oxides have become generally accessible.[
Many of these compounds show as a common feature cluster-
like arrangements of silver(I) cations, displaying Ag–Ag sepa-
rations partly as short as 2.80 Å, which is substantially below
the sum of the van der Waals radii. This general feature has
encouraged us to suggest some kind of bonding to be active
28,39]
[39,40]
between the equally charged silver atoms,
and to predict
that silver should be able to exist in a subvalent state, i.e. in
an oxidation state smaller than 1+.[ Indeed, several such ex-
amples of “metallic” oxides have been discovered, meanwhile.
41]
[
42–44]
Among them are exotic representatives like Ag GeO ,
5
4
[45,46]
[47]
Ag NiO ,
and Ag OsO .
Against this background,
2
2
13
6
the results presented herein can be well explained: the length Figure 4. Possible ordering patterns of silver layers, (a) corresponds
to a silver layer with Ag–Ag distances of ca. 2.65 Å and a composition
of Ag1.25TlO . In (b) the composition is Ag1.50TlO with Ag–Ag dis-
2 2
tances of ca. 2.45 Å. The ellipses are projections of the displacement
parameters of Ag onto the ab plane (50% probability level), and each
of the a axis of delafossites is determined by the size of the
3
+
3+
M
cation, accordingly Tl features the longest a lattice con-
stant (3.4 Å) for any delafossite known. As a consequence, the
silver spacings on this lattice are much larger than the shortest corner of the grey squares represents an accessible silver position.
066 www.zaac.wiley-vch.de Z. Anorg. Allg. Chem. 2014, 1063–1068
1
© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Novel Adaptations of the Delafossite Structure Type Featuring Subvalent Silver
Analyses and Physical Properties
The results of the crystal structure refinements, indicating
the presence of an excess of silver and thus a subvalence in
silver character for all of the new silver thallates presented,
were corroborated by EDX analyses, electronic conductivity
measurements, and XPS. EDX analyses on single crystals are
in fair agreement with the results of the refinements of the site
occupation factors.
Figure 5 shows the electrical resistance of Ag1+γTlO , which
2
like Ag1+αTlO2 and Ag1+βTlO , is a metallic conductor.
2
The specific resistivities at room temperature are
.21ϫ10–5 Ω·cm–1
(Ag1 TlO2),
6.74ϫ10 Ω·cm–1
–5
2
(
+α
–
2 2
4
–1
Ag1+βTlO ), and 1.03ϫ10 Ω·cm (Ag1+γTlO ), respec-
Figure 6. XPS-spectra of Ag
2 2 2
O (black), Ag1+αTlO (red), Ag1+βTlO
tively. Thus, the resistance increases with the number of or-
dered silver layers, confirming the subvalent character of silver
in the more crowded disordered layers.
(
blue), Ag1+γTlO (purple) and Ag (turquoise).
2
Ag and Tl O as solid residues behind, which were identified
2
3
by means of X-ray powder diffraction.
Conclusions
We report on the synthesis and characterization of a new
family of silver oxothallates(III), Ag1+xTlO , which represent
2
novel variants of the delafossite type of structure. In contrast
to the conventional 2H and 3R delafossites, silver forms two
distinct kinds of layers on the basic trigonal lattice. One type
(A) features 2D close packed layers of silver fully adapted to
the ab lattice spacings, realizing a Ag/Tl ratio of 1, and with
the resulting O–Ag–O dumbbells aligned parallel to the c axis.
This is the situation commonly encountered in delafossites.
The second type (B) of 2D layers of silver is accommodating
additional silver atoms, with the linear units O–Ag–O inclined
–
against the c axis. Apparently, the [TlO ] slabs can be interca-
2
Figure 5. Temperature dependence of the electrical resistivity (R) of
Ag1+γTlO .
2
lated by the two different kinds of silver layers in any se-
quence. There are two obvious factors of influence that favor,
or admit, to accommodate additional silver atoms in the struc-
ture. One degree of freedom results from the large ab lattice
The 3d binding energies of the title compounds along with spacing (3.4 Å), the second from the capability of silver to
suitable references were monitored by X-ray photoelectron adopt subvalent (Ͻ 1+) bonding states. It is known from clus-
+
spectroscopy (see Figure 6). The energies of the Ag-3d states ter-like arrangements of Ag that the respective homo-ionic
for Ag1+αTlO , Ag TlO , and Ag TlO are between those separations can be as small as 2.8 Å, in respective systems
2
1+β
2
1+γ
2
of elemental silver and Ag O. With the number of over- containing subvalent silver even values of 2.7 Å have been
2
crowded (subvalent) silver layers growing, the binding ener- observed. Given these numbers, the ab lattice base would have
gies approach those of elemental silver. The Ag-3d5/2 band for room for about 1.4 silver atoms per thallium atom. While the
Ag1+γTlO at 367.9 eV is close in energy to 3d for Ag O possible stacking sequences of A and B can be easily enumer-
2
5/2
2
(
367.8 eV), whereas for Ag1+αTlO (368.2 eV) virtually the ated, and thus the possible structures be predicted, the silver
2
same binding energy as for elemental silver was recorded. The content within the B layers may vary from slightly above 1 to
respective binding energies for Ag1+βTlO2 (368.1 eV) were about 1.4. For three individual members of the family,
found to be between Ag1+αTlO and Ag1+γTlO2.
Ag1+xTlO (x = α = 0.18, β = 0.09, γ = 0.03), the crystal struc-
2
2
In 1 atm argon atmosphere, Ag1+αTlO starts decomposing tures were solved and refined applying a split atom model to
2
at 350 °C. The onset of thermal decomposition of Ag1+βTlO2 the B silver layers, from single crystal data. The physical prop-
is at 390 °C, the highest decomposition rate is observed at erties as determined thus far corroborate the subvalent (elec-
4
80 °C with a final weight loss of 2.4% at 510 °C. For tron rich) character of the Ag1+xTlO family, displaying met-
2
Ag1+γTlO the thermal decomposition starts at 370 °C with the allic conductivity, and reduced 3d5/2 binding energies ranging
2
highest degradation rate at 450 °C and a final mass loss of between elemental silver and silver(I) oxide. In order to reveal
2
.2% at 490 °C. In all three compounds the decomposition is the real structure further studies, including HRTM, are re-
+
1
caused by the reduction of Ag to elemental silver, leaving quired.
Z. Anorg. Allg. Chem. 2014, 1063–1068
© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
1067

J. Nuss, V. Dietrich, J. Curda, M. Jansen
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Received: January 31, 2014
Published Online: February 25, 2014
1
068
www.zaac.wiley-vch.de
© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2014, 1063–1068