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Journal
Soft-Chemistry Synthesis and Characterization of Bismuth Oxyfluorides
and Ammonium Bismuth Fluorides
M. Bervas,w,z,y B. Yakshinskiy,z L. C. Klein,y and G. G. Amatucciz,y
Rutgers, The State University of New Jersey, Piscataway, New Jersey 08854
Two bismuth oxyfluorides, BiOF and BiO0.5F2, have been pre-
pared by soft chemistry. These two compounds are of interest
for application as new type of positive electrode active materials
in secondary lithium battery. BiOF was obtained directly from
the fluorination of Bi2O3 by a saturated aqueous solution of
NH4F. BiO0.5F2 was obtained by the hydrolysis of b-NH4BiF4
at 701C. The ammonium bismuth fluoride b-NH4BiF4, which is
a new orthorhombic form of NH4BiF4, was obtained by reacting
BiF3 in a saturated aqueous solution of NH4F. Two other
ammonium bismuth fluorides, (NH4)0.5BiF3.5 and NH4Bi3F10,
were also prepared by annealing b-NH4BiF4 at a relatively low
temperature under inert atmosphere. The existence of the fluo-
rite (NH4)0.5BiF3.5 is reported for the first time in this paper.
I. Introduction
A S a continuation of the work carried out by our group
on iron fluoride/carbon nanocomposite, where it was
shown for the first time that reversible conversion reactions
with lithium were possible at high voltage for energy storage,1
we investigated conversion reactions in other metal fluorides.
We have recently reported that a reversible conversion reaction
occurs at high voltage in the bismuth fluoride/carbon nano-
composite.2,3 To gain a better understanding of the system
and to show the influence of the ionicity of the metal fluoride
bond on the output voltage we also came to study bismuth
oxide and oxyfluorides. We have demonstrated that reversible
conversion was also possible in those compounds, and that
BiOF and BiO0.5F2 are very interesting active materials as
they combine the good electrochemical activity of the oxide
with the high voltage of the fluoride.4 This paper relates
the synthesis of these two bismuth oxyfluorides compounds
through soft chemistry and the investigation of new ammoni-
um bismuth fluorides intermediates formed during the fabrica-
tion process.
BiOF is tetragonal, space group P4/nmm. Aurivillus was the
first to study this compound, which he prepared by annealing
BiF3 at 6701C in air, and provided a thorough description of
its structure.5 Other groups have worked on BiOF and usually
prepared it by solid-state synthesis from Bi2O3 and BiF3.6,7
Only a few solution techniques have been used to prepare
BiOF and they required either moderate temperatures or an
HF treatment.8
BiO0.5F2 has a cubic fluorite structure, space group Fm3m. It
has been studied by several groups over the years7,9,10 but, from
what we have found, has been prepared exclusively from solid-
V. A. Hackley—contributing editor
Manuscript No. 20659. Received June 9, 2005; approved August 3, 2005.
Supported by U.S. Government.
w
Author to whom correspondence should be addressed. e-mail: bervas_mathieu@
hotmail.com
z
Energy Storage Research Group.
y
Department of Ceramic and Materials Engineering.
z
Laboratory for Surface Modification.
645
J. Am. Ceram. Soc., 89 [2] 645–651 (2006)
DOI: 10.1111/j.1551-2916.2005.00721.x
r 2005 The American Ceramic Society
state synthesis using Bi2O3 and BiF3 as precursors. As demon-
strated by Livshits et al.,11 who have conducted an 19F NMR
study on the compound, BiO0.5F2 is an excellent fluorine ion
conductor. The fluorite structure of BiO0.5F2 is considerably
defective as fluorites have an MX2 stoichiometry, but a complete
structural analysis has never been performed.
We were interested in preparing BiOF and BiO0.5F2 via a so-
lution synthesis technique, at room temperature without the use
of HF. As described in this paper, this was made possible by the
fluorination of Bi2O3 or BiF3 by a saturated aqueous solution of
NH4F. Our preference for NH4F over HF is justified by the
facts that, although great caution is also necessary, NH4F is
much safer to use than HF (MSDS Health rating ‘‘High’’ for
NH4F and ‘‘Extreme’’ for HF12) and easier to handle as it is a
solid rather than a liquid. Moreover, the use of NH4F as pre-
cursor allowed us to isolate new compounds of the ammonium
bismuth fluoride and oxyfluoride families.13
During the preparation of BiOF and BiO0.5F2, we also iso-
lated a variety of ammonium bismuth fluorides compounds,
some of them previously unknown. These compounds are also
reported in this paper. These compounds were characterized by
means of combined X-ray diffraction (XRD), Fourier transform
infrared spectroscopy (FT-IR), thermal gravimetric analysis
(TGA), differential scanning calorimetry (DSC), and X-ray
photoelectron spectroscopy (XPS).
II. Experimental Procedure
(1) Physical Characterization
XRD was performed on a Scintag X2 (Cupertino, CA) with
CuKa radiation. All the patterns presented in this paper were
obtained under the identical conditions of 0.81/min in continu-
ous scan, between 101 and 651 in 2y.
FT-IR analyses were conducted on a Thermo Nicolet Avatar
360 (Waltham, MA). Transmittance spectra were obtained with
the KBr pellet technique with a dilution of about 1/100. Atten-
uated total reflectance (ATR) experiments were performed on
the Smart Endurance accessory of the Avatar 360. A back-
ground was collected before each sample spectrum. Fifty scans
were taken for the background and each spectrum in the ATR
mode and 100 in the transmittance mode.
TGA and DSC analyses were conducted on the Q50 and
Q100 instruments from TA (TA Instruments, New Castle, DE),
respectively. The experiments were conducted under argon
between room temperature and 4201C at a scanning rate of
101C/min. The sample pans were in aluminum in both cases.
XPS quantitative analyses were performed using an XSAM
800 KRATOS apparatus (Manchester, U.K.) with a 127 mm
radius concentric hemispherical analyzer (CHA). An AlKa
source with a photon energy of 1486.6 eV is used for exciting
X-ray photoemission, and photoelectrons are detected by the
CHA operated in the fixed retarding ratio mode FRR5 (survey
scans), and in the fixed analyzer transmission mode FAT40 with
a pass energy of 40 eV (detail scans). One scan was conducted to
record the survey spectra, and two to six scans to record the
detail spectra. The XPS quantification method, based on the
comparison of relative intensities of photoelectron peaks, ena-

646 Journal of the American Ceramic Society—Bervas et al.
bles us to calculate the atomic fraction for each component, as-
suming their total intensities to be 100% and using the cor-
responding sensitivity factors. The measurements have been
performed under UHV conditions with a residual pressure of
about 10
9 Torr.
(2) Synthesis Approach
A preliminary study on the reactivity of Bi2O3 with NH4F in
solution was first conducted. For that purpose 15 mL of an
aqueous solution of ammonium fluoride was poured into a glass
vial containing 0.5 g of bismuth oxide (Aldrich, Milwaukee,
WI). The NH4F concentration was chosen so that the molar
ratio R 5 [NH4F]/[Bi2O3] varied between 1 and 180. Bi2O3 was
stirred in the NH4F solution for 3 h at room temperature after
which the reaction product was filtered, dried under vacuum
at 701C for 1 day, and characterized. The reaction of Bi2O3
with NH4F occurred within a few minutes and goes to
completion, as attested by the total change of color of the
solid from yellow to white. Stirring periods of 1 day instead of
3 h were tried; however, XRD performed on the reaction prod-
ucts did not reveal any noticeable difference. A molar ratio
R 5 [NH4F]/[Bi2O3] of 180 corresponds to the maximum possi-
ble ratio for a fixed oxide concentration as the NH4F concen-
tration is in that case at, or very close to, the solubility limit of
ammonium fluoride in water.
A larger volume of an aqueous solution of NH4F at the sol-
ubility limit was then prepared by dissolving 73.8 g of crystalline
NH4F into 100 mL of deionized water in a Teflon container. The
dissolution was complete after about 3 hours of vigorous stirring.
BiOF and b-NH4BiF4 were prepared at room temperature from
the reaction of Bi2O3 or BiF3 with this saturated NH4F aqueous
solution. (NH4)0.5BiF3.5 and NH4Bi3F10 were obtained by an-
nealing b-NH4BiF4 under Argon. Finally BiO0.5F2 was prepared
by hydrolyzing b-NH4BiF4 in deionized water heated to 701C.
All the compounds mentioned in this paper were filtered and
dried under vacuum at 701C after precipitation. When the sat-
urated NH4F aqueous solution was utilized the synthesis was
carried out in Teflon vials, otherwise it was conducted in glass
vials. Once the synthesis was completed, the different samples
were then redried overnight at 1201C under vacuum and then
stored in a glove box filled with Helium.
# # α-NH 4 BiF4
# ##
º ## # º # ## #
Intensity (a.u)
º º BiOF
* unid.
* * *
Bi2O3
10.0 16.0 22.0
Fig. 1. Formation of BiOF and NH4BiF4 from the reaction of Bi2O3 with aqueous NH4F solutions.
15512916, 2006, 2, Downloaded from https://ceramics.onlinelibrary.wiley.com/doi/10.1111/j.1551-2916.2005.00721.x by University Auto De San Luis Po, Wiley Online Library on [14/03/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
Vol. 89, No. 2
III. Characterization
(1) BiOF and a-NH4BiF4
The results of a preliminary study on the reactivity of bismuth
oxide with ammonium fluoride in solution as a function of the
molar ratio R 5 [NH4F]/[Bi2O3] are shown in Fig. 1. At low mo-
lar ratio, BiOF precipitates according to the chemical reaction:
Bi2 O3 þ 2NH4 F ! 2BiOF þ 2NH3 þ H2 O (1)
Traces of BiOF can already be seen on the pattern of the sample
made with a ratio as low as 1. A concentration ratio equal to 5 is
enough to fully react Bi2O3. Nonetheless a ratio of 20 is neces-
sary to obtain the pure BiOF. A few unidentified peaks at
2y  121, 271, and 29.51 (marked by a star symbol in Fig. 1)
are present on the patterns of powder prepared from a lower
ratio. The obtained BiOF is identical to the one first described
by Aurivillus, which he prepared by solid-state oxidation.5
It crystallizes in the tetragonal system (space group P4/nmm).
The values of the lattice parameters are a 5 3.7417.002 Å
and c 5 6.2107.004 Å, in good agreement with the values of
a 5 3.7469 Å and c 5 6.226 Å given by Aurivillus.
A large batch of BiOF was prepared by stirring 6 g of Bi2O3
into 3 mL of a saturated aqueous NH4F solution and 8 mL of
deionized water at room temperature for 1 day. The indexed
XRD pattern of the resulting BiOF is shown in Fig. 2. It reveals
a successful formation of the phase pure BiOF. FT-IR was per-
formed on BiOF and the results, not shown here, exhibited very
weak bands characteristic of ammonium ions. However, from
the intensity ratio of those bands with the inorganic band it was
clear that the residual NH1 4 ions were only present as traces.
The XRD patterns of Fig. 1 indicate that at higher NH4F
concentration a compound different than BiOF is produced.
The XRD pattern of this new compound matches almost per-
fectly the reported diffraction pattern of the monoclinic form of
NH4BiF4.14 The chemical reactions involved can be either one,
or both, of the following, depending on whether or not BiOF is
formed as a reaction intermediate:
Bi2 O3 þ 8NH4 F ! 2NH4 BiF4 þ 6NH3 þ 3H2 O (2)
BiOF þ 3NH4 F ! NH4 BiF4 þ 2NH3 þ H2 O (3)
#
# #
º # # # ## #º #### # ## # R=180
º
R=100
R = 75
R = 50
R = 45
R = 40
ºº º º º º º º R = 20
º º ºº º º
R = 10
R=5
*
R=1
28.0 34.0 40.0 46.0 52.0 58.0 64.0
Degrees 2θ (°)

February 2006
(101)
Intensity (a.u)
(002)
(110)
(001)
(102)
10.0 16.0 22.0 28.0 34.0 40.0 46.0
Degrees 2θ (°)
Fig. 2. X-ray diffraction pattern of BiOF prepared by stirring Bi2O3 in
a saturated aqueous solution on NH4F.
NH4BiF4 crystallizes in the monoclinic system (space group
P21/c). As will be discussed in the next paragraphs, NH4BiF4 is
actually a polymorphic compound, just like KBiF4, RbBiF4,
and TlBiF4.15–17 For this reason we will now call the monoclinic
phase a-NH4BiF4. The unit cell dimensions, calculated from 33
peaks between 101 and 651 in 2y, are a 5 8.2797.041 Å,
b 5 7.6057.044 Å, c 5 6.4157.034 Å, and b 5 93.0251. Within
error, they match the values of a 5 8.317 Å, b 5 7.597 Å,
c 5 6.486 Å, and b 5 93.51 given by Aurivillus well,14 except
for the c lattice parameter that is slightly contracted.
XRD reveals that a molar ratio R 5 [NH4F]/[Bi2O3] of 180 is
not sufficient to eliminate the residual BiOF altogether. From an
estimate of the XRD intensity ratio the amount of residual
BiOF is approximately 10%. The NH4F concentration utilized
for the synthesis of this sample is at, or very close to, the sol-
ubility limit of NH4F in water. This molar ratio is thus the
highest possible at room temperature for the fixed volume and
fixed amount of oxide of this study. Therefore, we have not been
able to prepare a batch of completely pure monoclinic a-
NH4BiF4 with this low-temperature synthesis technique. It is
known that a-NH4BiF4 readily decomposes into BiOF when
exposed to water.18 The BiOF second phase may partially come
from atmospheric H2O-induced decomposition of a-NH4BiF4
post synthesis. However, we did not notice any increase in the
amount of BiOF with the exposure time in air.
(2) b-NH4BiF4
Instead of stirring Bi2O3 in an increasingly concentrated NH4F
solution as we did in the study reported in the previous section
of this paper, we stirred Bi2O3 several consecutive times in a
saturated aqueous NH4F solution. As illustrated in the XRD
patterns of Fig. 3, a phase transformation occurs when Bi2O3 is
stirred for 1 day in 10 or 15 mL of an aqueous solution saturated
in NH4F, filtered and dried at 701C for approximately 1 day
° ° ° ° β-NH 4BiF4
° ×8
° ° °° ° °
° ° ° ° ° °° ° °°
Intensity (a.u)
BiOF
10.0 16.0 22.0 28.0 34.0 40.0 46.0
Degrees 2θ (°)
Fig. 3. Preparation of b-NH4BiF4 from Bi2O3 and a saturated aqueous
solution of NH4F. BiOF remains as a second phase.
15512916, 2006, 2, Downloaded from https://ceramics.onlinelibrary.wiley.com/doi/10.1111/j.1551-2916.2005.00721.x by University Auto De San Luis Po, Wiley Online Library on [14/03/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
Bismuth Oxyfluorides and Ammonium Bismuth Fluorides 647
under vacuum and this routine is repeated several consecutive
times. The compound formed has an orthorhombic symmetry
with lattice parameters a 5 7.7577.022 Å, b 5 13.2127.040 Å,
and c 5 14.8297.062 Å. As will be shown shortly, this
compound is a new ammonium bismuth fluoride, b-NH4BiF4.
BiOF remains as a minor second phase in the ammonium
bismuth fluoride even after the eighth stirring in solution A.
(211)
(112)
Its amount has been estimated at 5% from the intensity ratio of
(200)
the XRD pattern.
(103)
(202)
(113)
As will be described below, b-NH4BiF4 was utilized as a pre-
(212)
(003)
(201)
cursor for the low-temperature synthesis of a variety of other
(004)
bismuth fluorides and we were interested in preparing with a
52.0 58.0 64.0 high purity. This turned out to be possible when BiF3, instead
of Bi2O3, was used as bismuth precursor. The XRD pattern of
b-NH4BiF4 prepared by stirring 2 g of BiF3 two successive times
in 10 mL of solution A, each one followed by a filtering and
drying at 701C in vacuum sequences, is presented in Fig. 4. This
XRD pattern is devoid of BiOF, or any other second phase,
reflections. A quantitative XPS analysis has been conducted on
this sample. The results, presented in Table I, clearly confirm
our proposed stoichiometry.
Several reports on the synthesis of NH4BiF4 exist in the lit-
erature,8,18,19 most of which use solution techniques, but we
could not find any account of this orthorhombic form. This
material is isomorphic to the orthorhombic a form of RbBiF4
prepared by Matar et al.17 by a 5 days annealing at 2701C of
RbF and BiF3 in a sealed gold tube. The published lattice pa-
rameters for a-RbBiF4 were a 5 13.2667.030 Å, b 5 7.7837
.030 Å, and c 5 14.9427.030 Å, very close to the one we
obtained for b-NH4BiF4. The intensities of the different Bragg
reflections are however much different in b-NH4BiF4 and
a-RbBiF4. For instance the most intense reflection on the
pattern of b-NH4BiF4 is (002), whereas in a-RbBiF4 the most
intense reflection is (040) and the intensity of (002) is only 30%
of I040. This is not surprising as this orthorhombic structure is
ordered and NH1 1
4 and Rb have almost the same ionic radius
but very different X-ray scattering factors.
For all the other results presented in the rest of this paper,
b-NH4BiF4 will refer to the compound prepared using BiF3
as precursor.
(3) (NH4)0.5BiF3.5 and NH4Bi3F10
The TGA and DSC plots of b-NH4BiF4 collected under Argon
at a scanning rate of 101C/min for temperatures up to 4201C are
presented in Fig. 5. The important weight loss occurring be-
tween 1501 and 3201C is attributed to the decomposition of
NH4F in the form of ammonia and HF. The corresponding
chemical reaction is:
DT
b-NH4 BiF4
! NH3 þ HF þ BiF3 (4)
The total experimental weight loss in that range of temper-
ature is 12.5%, very close to the theoretical value of 12.2%
for reaction 4. XRD was conducted on the powder after the
DSC scan and the pattern obtained, shown in Fig. 6 (pattern c),
could as expected clearly be identified as the pure orthorhombic
° ° BiF3 phase. This result also supports our previous experimental
° °°° °° °° °° °° ° °° ° °
data regarding the composition of the new phase, b-NH4BiF4.
×6 As we have not been able to prepare a-NH4BiF4 with a good
×5 purity, we could not verify whether or not its thermal decom-
position was similar.
×4
As can be observed on the TGA plot in Fig. 5, the weight loss
×3 in b-NH4BiF4 happens in three separate steps. These steps are
×2 coupled with three endothermic peaks on the DSC plot. These
results show that NH4F does not evolve from b-NH4BiF4 in one
×1 single step but rather in three distinct ones. To assess the nature
of the intermediate compounds formed after the different steps,
52.0 58.0 64.0
b-NH4BiF4 was annealed under Ar. The DSC and TGA plots of
the powders obtained after 2 h annealing at 250 and 2901C are
presented in Figs. 7 and 8, respectively, and the corresponding
XRD patterns are shown in Fig. 6.
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648 Journal of the American Ceramic Society—Bervas et al. Vol. 89, No. 2

(002)
3342
β-NH 4BiF4
3000 obtained by stirring BiF3
in a saturated NH 4 F aqueous solution
2657

2314
Intensity (cps)

1971

1628

(040)
(221)
(212)
1285 (022)

942

(245) (261)
(053)
(113)
600 (201)

(042)
(202)

(204)

(343)
(241)

(341)

(065)
(322)

(046)

(164)
(108)
(213)

(301)

(036)
(062)
(312)

(045)
257

10.0 16.0 22.0 28.0 34.0 40.0 46.0 52.0 58.0 64.0
Degrees 2θ (°)
Fig. 4. Preparation of pure b-NH4BiF4 from BiF3 and a saturated aqueous solution of NH4F.

Table I. Quantitative X-ray photoelectron spectroscopy cal weight losses necessary to transform (NH4)0.5BiF3.5 into
(XPS) Results for b-NH4BiF4. The C Peak comes From the BiF3 and (NH4)0.33BiF3.33 into BiF3, respectively. Hence, the
Substrate and the O Peak is from Surface Contamination thermal decomposition of b-NH4BiF4 under Argon can be sum-
marized as follows:
Position Raw Sensitivity Atomic Normalized atomic
Peak (eV) area factor concentration (%) concentration
250 C
b-NH4 BiF4
! ðNH4 =FÞ0:5 BiF3:5
F 1s 684.01 4437 1.000 32.3 4
ð1=2Þ
(5)
O 1s 531.90 1098 0.660 12.1 290 C 330 C
N 1s 402.00 470 0.420 8.1 1
! ðNH4 =FÞ0:33 BiF3:33
! NH4 F

ð1=6Þ
ð1=3Þ
C 1s 285.00 1354 0.250 39.4
Bi 4f 160.80 8226 7.400 8.1 1 If a (NH4)1
xBixF1
2x type of notation is adopted, as pro-
posed by Laborde and Réau20 for the solid solution M1
x
BixF1
2x (where M 5 K, Rb, and Tl), NH4BiF4, (NH4)0.5BiF3.5,
The experimental total weight losses on the TGA plots and (NH4)0.33BiF3.33 can be rewritten as (NH4)1/2Bi1/2F2,
of the two powders obtained after annealing b-NH4BiF4 (NH4)1/3Bi2/3F7/3, and (NH4)1/4Bi3/4F10/4, respectively.
at 2501 and at 2901C are 6.4% and 4.3%, respectively. As can be seen in Fig. 6 (pattern a), (NH4)0.5BiF3.5 is a pure
These values are very close to 6.11% and 4.29%, the theoreti- fluorite compound, space group Fm3m, of lattice parameter
a 5 5.9897.001 Å. This is to the best of our knowledge the first
time that the existence of this compound is being reported.
102 2 (NH4)0.5BiF3.5 is isostructural with b-KBiF4 and g-RbBiF4,21–23
(NH 4) 0.5 BiF3.5 which remain to this day two of the best solid-state fluorine ions
to NH 4 Bi 3 F10 conductors ever discovered.24
100 The XRD pattern of (NH4)0.33BiF3.33 (or NH4Bi3F10), pre-
0
sented in Fig. 6 (pattern b), can also be indexed in the Fm3m
98 space group with a lattice parameter a 5 11.9467.012 Å. The
Heat Flow (W/g) exo up

partial unit cell of NH4Bi3F10, which is isomorphic with

−2 KBi3F10 and RbBi3F10,22,25 is presented in Fig. 9. It is com-
Weight loss (%)

96
posed of an alternation of two subcells [NH4Bi3F8]21 and
[NH4Bi3F12]2
. The former has a fluorite structure in which
94 −4 the anions occupy all the tetrahedral sites of the (NH1 31
4 , Bi )
FCC and hence form a cube, while in the latter they occupy the
92 48i interstitial sites and are organized in a cubo-octahedron.
−6 Ninzansky and Rehspringer25 were the first to synthesize
NH4Bi3F10 from a solid-state reaction between Bi2O3 and
90 NH4F. These authors reported a lattice parameter
NH 4 Bi 3 F10 −8
a 5 11.9747.001 Å slightly larger than the one we have found,
88 β-NH 4BiF4 to BiF3 possibly because of the presence of some residual oxygen anions
to (NH 4) 0.5 BiF3.5 on the fluorine lattice of their compound.13
Contrary to the pure fluorite (A1,VA1)Bi31(F
, VF
)4 com-
86 −10 pounds that have a fully disordered cation sub-lattice,26 all the
0 200 300 400 500 600
cubic ABi3F10-type compounds reported in the literature have
Temperature (°C) an ordered structure in which the A1 cations occupy all the
Fig. 5. Thermogravimetric analysis and differential scanning calorime- corner positions of the subcells and the Bi31 ions occupy the
try plot of b-NH4BiF4 up to 4201C. The experiment was conducted centers of each face.22,25 However, the ordering of the cations
under Argon at a scanning rate of 101C/min. seems to be only partial in our NH4Bi3F10 as the fluorite reflec-
 15512916, 2006, 2, Downloaded from https://ceramics.onlinelibrary.wiley.com/doi/10.1111/j.1551-2916.2005.00721.x by University Auto De San Luis Po, Wiley Online Library on [14/03/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
February 2006 Bismuth Oxyfluorides and Ammonium Bismuth Fluorides 649

(111)

(210)
(020)

(301)
(101)

(131)

(230)
(212)
(121)

(321)
(200)

(112)
(221)
(002)

(311)

(232)
(141)
(040)

(400)

(113)
(c) BiF3

(211)

(312)
(222)

(b) NH 4 Bi 3 F10
Intensity (a.u.)
(440) (611)
(400)
(200) (220)
(640)
(420) (422) (600) (620) (444) (642) (800)
(111)

(a) (NH 4) 0.5 BiF3.5 (220)

(200) (311)

(222)
(400)

10.0 16.0 22.0 28.0 34.0 40.0 46.0 52.0 58.0 64.0
Degrees 2θ (°)
Fig. 6. X-ray diffraction (XRD) patterns of (a) (NH4)0.5BiF3.5 and (b) NH4Bi3F10 prepared by annealing b-NH4BiF4 2 h at 2501C and 2 h at 2901C in
Argon, respectively. The XRD pattern (c), characteristic of the BiF3, collected after a differential scanning calorimetry run in Argon at 4201C on b-
NH4BiF4 is also presented on this figure.

101 1 101 4

100 0 2
100

99 0

Heat Flow (W/g) exo up

−1
Heat Flow (W/g) exo up

99
Weight loss (%)
Weight loss (%)

98
−2
−2
98
97
−4
−3
(NH 4) 0.5 BiF3.5
96 97
to NH 4 Bi 3 F10 −6
−4
95 NH 4 Bi 3 F10
96 to BiF3 −8
94 NH 4 Bi 3 F10 −5
to BiF3
95 −10
93 −6 0 100 200 300 400
0 100 200 300 400 500 Temperature (°C)
Temperature (°C) Fig. 8. Thermogravimetric analysis and differential scanning calorime-
Fig. 7. Thermogravimetric analysis and differential scanning calorime- try plots of NH4Bi3F10 prepared by annealing b-NH4BiF4 2 h at 2901C
try plots of (NH4)0.5BiF3.5, prepared by annealing b-NH4BiF4 2 h at in Argon. The experiment was conducted under Argon at a scanning rate
2501C in Argon. The experiment was conducted under Argon at a of 101C/min.
scanning rate of 101C/min.

tions are much more intense than the reflections brought about
by the formation of the superstructure. Hence, the corner posi-
31
tions of the FCC lattice must be occupied by ‘‘(NH1 4 )xBi1
x’’
1 31
cations and the centers of the face by ‘‘(NH4 )1
xBix ’’ cations,
where 0.5oxo1. Bi 3+
The FT-IR spectra of b-NH4BiF4, (NH4)0.5BiF3.5, and
(NH4)0.33BiF3.33 are compared in Fig. 10. This figure is divid- F−
ed into two parts: (a) that shows the vibrations bands of the NH 4+
ammonium ions on spectra collected in the ATR mode; and (b)
that shows the Bi–F vibration bands on spectra collected in
transmittance mode. The spectrum of the pure macro-ortho-
rhombic BiF3 has been added to serve as a reference. The po-
sitions of the maxima of the different peaks are given in Table Fig. 9. NH4Bi3F10 partial unit cell. The fluorite [NH4Bi3F8]21 subcell is
II. The strong intensity of u1, the totally symmetric mode, and shown on the left and the [NH4Bi3F12]2
subcell is shown on the right.
 15512916, 2006, 2, Downloaded from https://ceramics.onlinelibrary.wiley.com/doi/10.1111/j.1551-2916.2005.00721.x by University Auto De San Luis Po, Wiley Online Library on [14/03/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
650 Journal of the American Ceramic Society—Bervas et al. Vol. 89, No. 2

100

80 2 υ4
υ1
NH 4 Bi 3 F10
υ3 2 υ4
60 υ4
100
% Transmission

2 υ4
90 υ1
υ3 (NH 4 ) 0.5 BiF3.5

80
υ4
100

80

2 υ4 υ4’ β-NH 4 BiF4

60
υ3
(a) ATR υ1 2 υ4’
40 υ4 υ4’’
4000 3500 3000 2500 2000 1500 1000 500
Wavenumber (cm−1)

100

80 NH 4 Bi3 F10

Bi-F
60
100

90
% Transmission

(NH 4 ) 0.5 BiF3.5

80 Bi-F
100

90
β-NH 4 BiF4
Bi-F
80
100
BiF3 Pnma

80
(b) Trans.
Bi-F
1000 900 800 700 600 500
Wavenumber (cm−1)
Fig. 10. Fourier transform infrared patterns of b-NH4BiF4, (NH4)0.5BiF3.5, and NH4Bi3F10. (NH4)0.5BiF3.5 and NH4Bi3F10 were prepared by
annealing b-NH4BiF4 2 h at 2501C and 2 h at 2901C in Argon, respectively; (a) attenuated total reflectance mode, showing the vibrations of the
(NH4)1 ions and (b) transmittance mode, showing the Bi–F vibrations. The spectrum of orthorhombic BiF3 has been added for reference.

Table II. Positions of the Maxima of the Vibrations Bands of Figure 10

1
1
1
1
1
1
1
1
NH1
4 u3 (cm ) NH1 1 0 1
4 u1 (cm ) NH4 2u4 (cm ) NH4 2u4 (cm ) NH1 0
4 u4 (cm ) NH1
4 u4 (cm ) NH1 00
4 u4 (cm ) Bi–F (cm )

b-NH4BiF4 3205 3061 2916 2848 1463 (shoulder) 1417 (shoulder) 1402 457
(NH4)0.5BiF3.5 3221 3076 2850 1417 464
NH4Bi3F10 3226 3090 2918 2850 1420 457
BiF3 457

the splitting of the bending vibration u4 in three components (4) BiO0.5F2

indicate that the NH1 4 ions do not have a perfect Td symme-
try.27,28 The absence of inorganic vibration bands, other than BiO0.5F2 is formed when 1 g of b-NH4BiF4 is stirred for 1 h in
Bi–F, between 400 and 1000 cm
1 suggests that these com- 20 mL of deionized water heated for 1 h at 701C, followed by
pounds are indeed pure fluorides. two times of 15 min each in 20 mL of water at room temper-
 15512916, 2006, 2, Downloaded from https://ceramics.onlinelibrary.wiley.com/doi/10.1111/j.1551-2916.2005.00721.x by University Auto De San Luis Po, Wiley Online Library on [14/03/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
February 2006 Bismuth Oxyfluorides and Ammonium Bismuth Fluorides 651

first time that the existence of the fluorite (NH4)0.5BiF3.5 is re-

ported. It is isostructural with b-KBiF4 and g-RbBiF4,22,23
(111) which are among the best solid-state fluorine ions conductors
ever discovered.24
Intensity (a.u.)

Finally, an additional bismuth oxyfluoride, BiO0.5F2, has

been also prepared from the hydrolysis of b-NH4BiF4 at 701C.
(220)
(200) (311)
References
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98
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70
b-NH4 BiF4 þ 0:5H2 O
! BiO0:5 F2 þ NH3 þ 2HF
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in Fig. 12.
IV. Conclusion
BiOF and an orthorhombic form of NH4BiF4 have been synthe-
sized at room temperature from the fluorination of Bi2O3 or BiF3
by a saturated aqueous solution of NH4F. This new orthorhom-
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