Structure of a Gold(III) Hydroxide and Determination of Its Solubility

Daisuke Kawamoto,*1 Hiroaki Ando,1 Hironori Ohashi,2 Yasuhiro Kobayashi,3 Tetsuo Honma,4
Tamao Ishida,5 Makoto Tokunaga,1 Yoshihiro Okaue,1 Satoshi Utsunomiya,1 and Takushi Yokoyama*1

1
Department of Chemistry, Faculty of Science, Kyushu University, 744 Motooka, Nishi-ku, Fukuoka 819-0395
2
Faculty of Symbiotic Systems Science, Fukushima University, 1 Kanayagawa, Fukushima 960-1296
3
Research Reactor Institute, Kyoto University, 2 Asashiro-Nishi, Kumatori-cho, Sennan-gun, Osaka 590-0494
4
Japan Synchrotron Radiation Research Institute (JASRI)/SPring-8, 1-1-1 Kouto, Sayo-cho, Sayo-gun, Hyogo 679-5198
5
Research Center for Gold Chemistry, School of Urban Environmental Sciences, Tokyo Metropolitan University,
1-1 Minami-osawa, Hachioji, Tokyo 192-0397
E-mail: kawamotod@chem.kyushu-univ.jp

Received: June 24, 2016; Accepted: August 23, 2016; Web Released: November 2, 2016

Daisuke Kawamoto
Daisuke Kawamoto graduated from the Department of Chemistry, Faculty of Science, Kyushu University in
2015 and received his Doctorate in Science.

Abstract stability to oxidation. In recent years, gold has been used

A representative gold(III) complex ion ([AuCl4]¹), succes-
sively hydrolyzes to form [AuCl4¹n(OH)n]¹ (n = 0­4) in
aqueous solution as the pH increases and, finally, precipitates.
It has been referred to as “gold(III) hydroxide” for the past fifty
years. However, whether the precipitate is gold(III) hydrox-
ide (Au(OH)3) or hydrous gold(III) oxide (Au2O3¢nH2O) has
remained uncertain. Few studies have been conducted to
determine its chemical and physical properties. The aim of this
investigation is to identify the precipitate and to determine its
solubility. The precipitate was X-ray amorphous. Based on the
transmission electron microscopy (TEM) observation, the shape
was spherical and the particle diameter was approximately 9 nm.
From the results of 197Au Mössbauer spectroscopy, Au L3-edge
X-ray absorption (XA) spectroscopy and thermogravimetry/
differential thermal analysis (TG/DTA) measurements, the pre-
cipitate composition was estimated to be Au(OH)3. Based on
the composition, its structure was proposed to be a linear poly-
mer. Moreover, its solubility at 298 K was determined to be
0.00120 g/100 g of H2O. This chemical and physical properties
information of Au(OH)3 is essential for gold chemistry, for
example, for preparing supported gold catalyst.
1. Introduction
Gold has been used for currencies and ornaments since
ancient times because of its universal value such as chemical
by industry to produce alloys with high corrosion resistance,
specific ductility and high conductivity. Moreover, gold nano-
particles and/or gold alloy nanoparticles have been used as
catalysts.1,2 The precipitate from alkaline solution of [AuCl4]¹,
which has been believed to be gold(III) hydroxide, is used as
a precursor to prepare these catalysts.3,4 However, it has re-
mained uncertain whether the precipitate is gold(III) hydroxide
(Au(OH)3) or hydrous gold(III) oxide (Au2O3¢nH2O). Although
Johnston and Leland attempted to measure the solubility of the
precipitate,5 no investigation of the physical and chemical
properties has been performed. In this study, we first identified
the precipitate using X-ray powder diffraction (XRD), trans-
mission electron microscopy (TEM), 197Au Mössbauer spec-
troscopy, X-ray absorption (XA) spectroscopy and thermog-
ravimetry/differential thermal analysis (TG/DTA). Based on
the results, we concluded finally that the precipitate is Au(OH)3.
Secondly, we determined the solubility of Au(OH)3.
2. Experimental
2.1 Chemicals. The reagents used in this study were
of analytical reagent grade. Solutions were prepared with
deionized-distilled water. H[AuCl4]¢4H2O was purchased from
Tanaka Kikinzoku Kogyo K. K.
2.2 Precipitate Preparation from H[AuCl4] Solution.
The precipitate was prepared according to a previous work.6
Na2CO3 solution and H[AuCl4] solution were prepared by
dissolving anhydrous Na2CO3 (2 g) into water (100 cm3) and by

Bull. Chem. Soc. Jpn. 2016, 89, 1385–1390 | doi:10.1246/bcsj.20160228 © 2016 The Chemical Society of Japan | 1385
dissolving H[AuCl4]¢4H2O (4 g) into water (50 cm3), respec-
tively. The H[AuCl4] and Na2CO3 solutions were mixed, and
the obtained solution was magnetically stirred for 8 h. The
obtained precipitate was filtered using a 0.20 ¯m membrane
filter, washed with water and then freeze-dried under vacuum.
Here, we refer to the precipitate as the “Au solid sample”.
2.3 Characterization of the Au Solid Sample. XRD
analysis of the Au solid sample was performed using an Ultima
IV (Rigaku, Japan) with a scanning rate of 2°/min and with a
step scan of 0.02° in the 2ª range of 20­80° with Cu Kα radia-
tion. The operating voltage and current were 40 kV and 30 mA,
respectively.
The size and morphology of the Au solid sample were
analyzed using HR TEM (JEOL ARM200F) operated at an
accelerating voltage of 200 kV. The TEM specimens were pre-
pared by dispersing the Au solid sample into water. The sus-
pended solution was put on a perforated carbon mesh supported
by a Cu grid and air-dried.
The 197Au Mössbauer spectra were measured by trans-
mission method at the Research Reactor Institute of Kyoto
University. The Au solid sample was placed in a Teflon sample
holder. The spectra were measured at 9­12 K. The γ-ray source
(197Pt, half-life: 18.6 h, γ-ray energy: 77.4 keV) was prepared
by neutron irradiation to 196Pt. The zero velocity position of
the spectrum is the peak position of pure bulk Au. The spectra
were analyzed using computer software by assuming that each
spectrum consists of a Lorentzian function.
For the XA spectra measurement, the Au solid sample was
diluted with boron nitride (73 mg), and a pellet was made. The
Au L3-edge XA spectra were measured by transmission mode
at the BL14B2 beamline of SPring-8 (8 GeV and 99.5 mA).
This measurement was conducted at room temperature. The
spectra were analyzed using software (Athena and Artemis of
Ifeffit).7 The curve fitting was carried out in R-space using
Artemis with a Fourier transformed range of k = 3­12.5 ¡¹1
and a back-Fourier transform range of R = 1­2 ¡. In the curve
fitting analyses, the backscattering amplitude and the phase
shift were calculated by FEFF 6L, with the following used as
fitting parameters: the number of neighboring atoms, inter-
atomic distances between the absorbed atom and the neighbor-
ing atoms, the Debye­Waller factor and the absorption edge
energy. The intrinsic loss factor was obtained from the curve
fitting analysis of the EXAFS data of the [Au(OH)4]¹ solu-
tion prepared by dissolving H[AuCl4]¢4H2O (500 mg) in a 1.0
mol/dm3 NaOH solution (25 cm3).
The TG/DTA measurement for the Au solid sample was per-
formed by using a TG/DTA7300 (HITACHI, Japan) between
298 and 773 K with a heating rate of 0.5 K/min under air flow
(200 cm3/min). The weight of the Au solid sample was 37 mg
and α-Al2O3 powder was used as a reference material.
2.4 Determination of Solubility of the Au Solid Sample
(Au(OH)3). From the above characterization, the chemical
composition for the Au solid sample was determined to be
Au(OH)3. Finally, the solubility of Au(OH)3 was measured at
298 K. The solid­liquid equilibrium of Au(OH)3 was estab-
lished from both sides of supersaturation (the Au(OH)3 precipi-
tation) and undersaturation (the Au(OH)3 dissolution). In the
supersaturated system, Au(OH)3 (13 mg) was added to water
(100 cm3) in a light shielding bottle to avoid the effects of light,
1386 | Bull. Chem. Soc. Jpn. 2016, 89, 1385–1390 | doi:10.1246/bcsj.20160228
and this suspended solution was heated at 313 K for 4 days to
obtain a supersaturated solution under magnetic stirring. After
cooling, the pH and temperature were continuously monitored
using a glass electrode equipped with a pH meter. At adequate
intervals, the suspension aliquots were taken out and filtrated
with a 0.20 ¯m membrane filter to collect the filtrate. On the
other hand, in the undersaturated system, Au(OH)3 (65 mg) was
added to water (500 cm3) in a light shielding bottle to avoid the
effects of light. The suspended solution was stirred magneti-
cally, and pH and temperature were continuously monitored. At
adequate intervals, the same operations as for the supersatu-
rated system were carried out. Each experiment was repeated
three times under the same conditions. The gold concentration
in these filtrates was determined using atomic absorption spec-
troscopy (AA-6300, Shimadzu, Japan).
3. Results and Discussion
When the H[AuCl4] solution was added to the Na2CO3 solu-
tion, a brown powder was precipitated. Here, the precipitate is
referred to as the “Au solid sample” as described in the exper-
imental section.
3.1 Characterization of the Au Solid Sample. 3.1.1
XRD: The XRD patterns of the Au solid sample and the
standards (Au and Au2O3) are displayed in Figure 1. The XRD
pattern of the Au solid sample showed broad diffraction peaks
at 2ª = 32.5° and 60.0°. No diffraction peaks assigned to
crystalline Au2O3 or bulk Au(0) appeared. The Au solid sample
was X-ray amorphous.
3.1.2 TEM: Figure 2 shows the TEM image (a), the size
distribution (b) and the electron beam diffraction pattern (c)
for the Au solid sample. From the TEM image (a) and the size
distribution (b), the shape of the Au solid sample was deter-
mined to be spherical, and its particle diameter was 8.83 « 3.5
nm. To examine the crystallinity of the Au solid sample, the
electron beam diffraction pattern (c) was measured. The lattice
image was slightly observable. Although the XRD pattern
showed that the Au solid sample was amorphous, the electron
beam diffraction pattern suggested that the Au solid sample
was slightly crystalline. The formation of crystalline Au2O3 by
dehydration under high-vacuum is known empirically. Thus,
the observed lattice image may be due to Au2O3.
3.1.3 197Au Mössbauer Spectroscopy: To examine
the valence state of Au in the Au solid sample, the 197Au
Mössbauer spectra were measured. Figure 3 shows the 197Au
Mössbauer spectra for the Au solid sample and Au foil as a
standard of Au(0). The Au solid sample spectrum only showed
a peak with a positive isomer shift (IS). The 197Au Mössbauer
parameters are tabulated in Table 1. In 197Au Mössbauer spec-
troscopy, different Au chemical states are separately detected
depending on the IS and quadrupole splitting (QS). Figure 4
shows the relationship between the IS and QS as the 197Au
Mössbauer parameters.8 The two shadowed parts in Figure 4
indicate the regions of valence states, which correspond to
linearly coordinated Au(I) compounds and to planar coordi-
nated Au(III) compounds. The IS and QS values for the Au solid
sample were 2.66 and 1.87, which suggests that the Au in the Au
solid sample can be assigned to a planar coordinated Au(III).
3.1.4 XA Spectroscopy: To examine the atoms coordinated
to Au(III) in the Au solid sample and to analyze the structure,
© 2016 The Chemical Society of Japan
 Au solid sample
Au solid sample

Normalized Relative Transmission

Au foil

Au 2O3
Intensity ( a. u. )

-6 -3 0 3 6 9
Velocity / mm s-1
Au(0) Figure 3. 197Au Mössbauer spectra for the Au solid sample
and Au foil.
Table 1. 197Au Mössbauer parameters for Au foil and the Au
solid sample

Parameters
Sample
IS/mm s¹1 QS/mm s¹1
Au foil 0.00 « 0.02 ®
20 30 40 50 60 70 80 Au solid sample 2.66 « 0.05 1.87 « 0.05
2θ ( Cu Kα ) / o

Figure 1. XRD patterns of the Au solid sample, Au2O3

(ICDD: 00-043-1039) and Au(0) (ICDD: 00-001-1172).
The diffractograms for Au2O3 and Au(0) are obtained from
a data base (ICDD).

(a)

8
(b)
Number of Particles

(c) 2 Figure 4. The relationship between the IS and QS as 197Au

Mössbauer parameters.8 The blue region and red region
0
indicates the corresponding to linearly coordinated Au(I)
0 3 6 9 12 15 compounds and planar coordinated Au(III) compounds,
Diameter of the Au solid sample / nm respectively.

XA spectra for the Au solid sample and standard materials were

measured. Figure 5 shows the Au L3-edge XANES spectra for
K[AuCl4] as a standard of Au(III) that Cl¹ is coordinated with,
Figure 2. TEM image (a), size distribution (b), and electron [Au(OH)4]¹ solution as a standard of Au(III) that OH¹ is coor-
beam diffraction pattern (c) for the Au solid sample. dinated with, the Au solid sample and Au foil as a standard of

Bull. Chem. Soc. Jpn. 2016, 89, 1385–1390 | doi:10.1246/bcsj.20160228 © 2016 The Chemical Society of Japan | 1387
 Normalized Absorption K[AuCl 4]
-
[Au(OH) 4] solution
Au solid sample
Au foil
11.90 11.95 12.00 12.05
Photon Energy / keV
Figure 5. Normalized Au L3-edge XANES spectra for
K[AuCl4], [Au(OH)4]¹ solution, the Au solid sample and
Au foil.
Table 2. EXAFS fitting parameters for the Au solid sample (k3: ¦k = 3­12.5 ¡¹1 and ¦r = 1.0­2.0 ¡)
Sample Shells CN a)
[Au(OH)4]¹ solution Au­O 4.0e)
Au solid sample Au­O 3.63 « 0.37
a) First shell coordination number. b) Bond length. c) Debye­Waller factor. d) Goodness of fit index. e) Coordination
number was fixed as that of a square plane.
Au(0). The Au L3-edge XANES spectrum for the Au solid
sample showed a white line at 11.922 keV, which indicates an
ionic character. The XANES spectrum for the Au solid sample
was different from that for K[AuCl4]. The peak at 11.938 keV
of K[AuCl4] is considered to be due to Au­Cl interaction.9
However, no peak appeared at 11.938 keV in the spectrum of
the Au solid sample, which suggests that no Au­Cl interaction
was present. Because the XANES spectrum for the Au solid
sample resembled the [Au(OH)4]¹ solution spectrum, the Au
oxidation state in the Au solid sample was demonstrated to be
Au(III) that OH¹ is coordinated with. This conclusion is sup-
ported by the 197Au Mössbauer measurement result. Figure 6
shows the Fourier transform of the EXAFS oscillation extract-
ed from Au L3-edge XA spectra for K[AuCl4], [Au(OH)4]¹
solution, the Au solid sample and Au foil (their k3-weighted
EXAFS oscillation extracted from Au L3-edge XA spectra are
shown in the Supporting Information; Figure S1). In Figure 6,
the peaks at 1.8, 1.6, and 2.5 ¡ are assigned to the Au­Cl, Au­
O and Au­Au interactions, respectively. Thus, the peak at 1.6 ¡
of the Au solid sample is assigned to the Au­O interaction. The
EXAFS fitting parameters are shown in Table 2. The theoret-
ical radial structure functions fit well with the experimental
ones, as evidenced by the R-factor of 0.372. From the fitting
model, the Au­O coordination number was calculated to be
1388 | Bull. Chem. Soc. Jpn. 2016, 89, 1385–1390 | doi:10.1246/bcsj.20160228
K[AuCl 4]
FT Magnitude
[Au(OH) 4]- solution
Au solid sample
Au foil
0 1 2 3 4 5
R/ύ
Figure 6. Fourier transform of the EXAFS oscillation
extracted from Au L3-edge XA spectra for K[AuCl4],
[Au(OH)4]¹ solution, the Au solid sample and Au foil.
R/¡b) ΔE0 · 2/¡2 c) Rfactord)
1.98 « 0.007 3.96 « 1.87 0.00227 « 0.0008 0.621
2.00 « 0.006 4.93 « 1.32 0.00353 « 0.0008 0.372
3.63 « 0.37. From the EXAFS curve fitting analysis of the Au
solid sample, the Au(III) coordination number in the Au solid
sample is considered to be four, which is the same as in
[Au(OH)4]¹. Because the Debye­Waller factor (· 2) is small,
the Au solid sample can be considered to consist of a single
phase. However, from only the results of 197Au Mössbauer
spectroscopy and XA spectroscopy, it is difficult to distinguish
whether the Au solid sample is Au(OH)3 or Au2O3¢nH2O.
3.1.5 TG/DTA: The Au solid sample was formed when the
H[AuCl4] solution was added to the Na2CO3 solution, and no
Au­Cl interaction was included, as described above. Therefore,
the Au solid sample is considered to be Au(OH)3 or Au2O3¢
nH2O. To determine the chemical composition, the TG/DTA
was applied. The TG/DTA curves for the Au solid sample at
298­773 K are presented in Figure 7. From the TG curve, the
Au solid sample weight decreased independently in 2 steps and
the total weight loss was 18% until 773 K. For the DTA curve,
two sharp endothermic peaks were observed at approximately
310 K and 570 K. The weight loss in the first and second steps
was 8.4% and 9.6%, respectively. If the Au solid sample is
Au(OH)3, the first step reaction is dehydration from Au(OH)3
and the formation of Au2O3, and the second step reaction is
the thermal decomposition of Au2O3 to Au. These reactions are
represented as eqs (1) and (2).
© 2016 The Chemical Society of Japan
 0 0.0024
TG (% of weight loss)
-5
DTA (a. u.)
-10
-15
-20
300 400 500 600 700
Temperature / K
Figure 7. The TG/DTA curves for the Au solid sample.
HO OH OH
Au O Au O Au
H H
HO OH OH
Figure 8. A proposal structure of Au(OH)3.
AuðOHÞ3 ! 1=2 Au2 O3 þ 3=2 H2 O ð1st stepÞ
1=2 Au2 O3 ! Au þ 3=4 O2 ð2nd stepÞ
If the Au solid sample is Au(OH)3, the theoretical thermal
weight loss is 10.9% for the first step reaction and 9.7% for
the second step reaction. The experimental weight loss can be
considered to be almost correspondent to the theoretical weight
loss. Therefore, the endothermic peaks on the DTA curve can
be assigned to the two reactions of eqs (1) and (2), which indi-
cates that the Au solid sample is Au(OH)3. On the other hand, if
the Au solid sample is Au2O3¢nH2O, the first step reaction is
the dehydration reaction of lattice water from Au2O3¢nH2O to
Au2O3. The broad endothermic peak on the DTA curve should
be observed at the first reaction, because the lattice water
evaporates gradually at various temperatures. However, a sharp
endothermic peak was observed at the first step reaction.
Therefore, the Au solid sample is considered to be Au(OH)3.
Based on the 197Au Mössbauer spectroscopy, XA spectros-
copy and TG/DTA results, the basic structure of Au(OH)3 is
thought to be a linear polymer bridged by OH¹ groups between
Au(III) as shown in Figure 8. In addition, there is a possibility
that the linear polymer may combine together randomly like a
graft bridged structure.
3.2 Solubility Measurement of Au(OH)3. The solubility
of metal hydroxide (g/100 g of H2O) is one of the basic
properties in chemistry. The solid­liquid equilibrium of metal
hydroxide is generally attained in two ways: (1) dissolution
of metal hydroxide in water and (2) precipitation of metal
hydroxide from a supersaturated solution. Here, the solu-
bility of Au(OH)3 was measured in two ways. First, an excess
amount of Au(OH)3 was added to water, and the variation of
Bull. Chem. Soc. Jpn. 2016, 89, 1385–1390 | doi:10.1246/bcsj.20160228
-1
Supersaturated system
Solubility / g (100 g of H2O)
Undersaturated system
0.0016
0.0008
0
0 200 400 600 800
Time / h
Figure 9. Solubility measurement of Au(OH)3 from both
sides of the supersaturation and undersaturation.
Au concentration in water with time was measured at 298 K.
At the same time, the pH and temperature of water were
monitored. Second, a supersaturated solution with respect to
Au(OH)3 was prepared by dissolving Au(OH)3 in hot water.
After cooling to 298 K, the same measurements were carried
out. Figure 9 shows the variations of Au concentration in water
with time. The result included those from the undersaturated
n condition (1) and the supersaturated condition (2). In the case
of (1), the Au concentration increased with time. On the other
hand, in the case of (2), the Au concentration decreased with
time. Finally, these Au concentrations approached a constant
ð1Þ value (0.00109 « 0.00005 g/100 g of H2O in case of (1) and
0.00132 « 0.00005 g/100 g of H2O in case of (2)). These
ð2Þ experimental results are shown in Table 3. After 440 h, the Au
concentration in each experiment approached to almost the
same value, which suggests that the solid­liquid equilibrium
was attained. From the two experiments, a mean Au concen-
tration after 440 h was calculated to be 0.00120 « 0.00007 g/
100 g of H2O. This value is considered to be the solubility of
Au(OH)3 at 298 K. Johnston and Leland measured the solu-
bility of Au(OH)3.5 The reported solubility of Au(OH)3 in pure
water was 0.00769 g/100 g of H2O using an electrochemical
method. In their method, they used the standard potential of
[AuCl4]¹ to determine the Au concentration in water. In fact,
the dissolved Au species is not [AuCl4]¹, as described later.
Thus, the solubility of Au(OH)3 in the previous paper is higher
compared with the value found in this investigation.
The pH value was approximately constant during the two
solubility measurements. The pH values are also given in
Table 3. The lack of change in pH suggests that neither the
H+ nor OH¹ ions participate in the dissolution reaction of
Au(OH)3. In addition, the Au3+ ion has a square planar struc-
ture due to its electronic structure, and its coordination num-
ber is four. Therefore, the dissolution reaction of Au(OH)3 is
represented as eq (3).
AuðOHÞ3 þ H2 O ! ½AuðOHÞ3 ðH2 OÞ0 ð3Þ
4. Conclusion
When the H[AuCl4] solution was added to the Na2CO3
solution, a brown powder was precipitated. The precipitate
was identified to be Au(OH)3, which is X-ray amorphous. The
© 2016 The Chemical Society of Japan | 1389
 Table 3. Results of the Au(OH)3 solubility measurements from the supersaturated and under-
saturated systems

Solubility
System pH Temperature/K
/g (100 g of H2O)¹1
supersaturated system #1 0.00137 6.06 « 0.07 297.0 « 0.19
supersaturated system #2 0.00121 5.94 « 0.06 296.9 « 0.11
supersaturated system #3 0.00137 6.06 « 0.03 297.0 « 0.09
undersaturated system #1 0.00124 6.06 « 0.06 297.6 « 0.16
undersaturated system #2 0.00120 6.56 « 0.08 299.3 « 0.18
undersaturated system #3 0.000826 6.25 « 0.1 298.3 « 0.14

average solubility 0.00120 « 0.00007

Au(III) in Au(OH)3 coordinates with four oxygen atoms. The
morphology and size of Au(OH)3 were spherical and 8.83 « 3.5
nm (particle diameter), respectively. The Au(OH)3 structure is a
linear polymer bridged by OH groups between Au(III).
The solubility of Au(OH)3 at 298 K was determined to be
0.00120 « 0.00007 g/100 g of H2O. However, the solubility
of Au(OH)3 determined in this investigation was smaller com-
pared with the value found in previous work.5 The difference is
attributed to differences in the experimental methods.
This study was financially supported by a Grant-in-Aid for
Young Scientists (B) (25790017) from the Ministry of Educa-
tion, Culture, Science, Sports and Technology of Japan. The
XA spectra measurement was conducted at BL14B2 in SPring-
8 as a selected joint work (Project numbers: 2013A1820,
2013B1598). The 197Au Mössbauer spectra measurement was
conducted at the Research Reactor Institute of Kyoto Univer-
sity as a selected joint work (Project number: 25P-8).
Supporting Information
The k3-weighted EXAFS oscillation extracted from Au L3-
edge XA spectra for K[AuCl4] as a standard of Au(III) that
Cl¹ is coordinated with, [Au(OH)4]¹ solution as a standard of
Au(III) that OH¹ is coordinated with, the Au solid sample and
Au foil as a standard of Au(0) are shown in the Supporting
Information; Figure S1. This material is available on http://
dx.doi.org/10.1246/bcsj.20160228.
References
1 M. Haruta, N. Yamada, T. Kobayashi, S. Iijima, J. Catal.
1989, 115, 301.
2 H. Nishikawa, D. Kawamoto, Y. Yamamoto, T. Ishida, H.
Ohashi, T. Akita, T. Honma, H. Oji, Y. Kobayashi, A. Hamasaki, T.
Yokoyama, M. Tokunaga, J. Catal. 2013, 307, 254.
3 S. Tsubota, D. A. H. Cunningham, Y. Bando, M. Haruta,
Stud. Surf. Sci. Catal. 1995, 91, 227.
4 K. Okumura, K. Yoshino, K. Kato, M. Niwa, J. Phys.
Chem. B 2005, 109, 12380.
5 H. L. Johnston, H. L. Leland, J. Am. Chem. Soc. 1938, 60,
1439.
6 H. Schütza, I. Schütza, Z. Anorg. Allg. Chem. 1940, 245,
59.
7 B. Ravel, M. Newville, J. Synchrotron Radiat. 2005, 12,
537.
8 G. J. Long, Mössbauer Spectroscopy Applied to Inorganic
Chemistry, Plenum Press, New York, 1984, Vol. 1. doi:10.1007/
978-1-4899-0462-1.
9 X. Chen, W. Chu, D. Chen, Z. Wu, A. Marcelli, Z. Wu,
Chem. Geol. 2009, 268, 74.

1390 | Bull. Chem. Soc. Jpn. 2016, 89, 1385–1390 | doi:10.1246/bcsj.20160228 © 2016 The Chemical Society of Japan