Applied Catalysis A: General 275 (2004) 149155

www.elsevier.com/locate/apcata

Combined partial oxidation and dry reforming of methane

to synthesis gas over noble metals supported
on MgAl mixed oxide
Andrey I. Tsyganoka,*, Mieko Inabab, Tatsuo Tsunodab, Kunio Suzukib,
Katsuomi Takehirac, Takashi Hayakawab
a

Department of Chemistry, University of Ottawa, DIorio Hall, 10 Marie Curie Street, Ottawa, Ont., Canada K1N 6N5
Institute for Materials and Chemical Process, National Institute of Advanced Industrial Science and Technology (AIST),
Tsukuba Central 5, 1-1-1 Higashi, Tsukuba 305-8565, Japan
c
Department of Applied Chemistry, Faculty of Engineering, Hiroshima University, 1-4-1 Kagamiyama,
Higashi-Hiroshima 739-8527, Japan
Received 18 February 2004; received in revised form 8 July 2004; accepted 22 July 2004
Available online 1 September 2004

Abstract
Combined partial oxidation and dry reforming of methane (PODRM) to synthesis gas at 850 8C over noble metals, supported on MgAl
mixed oxide, has been studied. Ruthenium, rhodium, and platinum catalysts were prepared from layered double hydroxide (LDH) precursors,
synthesized by a reconstruction reaction of MgAl mixed oxide. Due to a memory effect of a calcined hydrotalcite, a layered structure of
catalyst precursors was recreated upon exposure of the mixed oxide to an aqueous solution of noble metals, which were pre-chelated with
ethylenediaminetetraacetate (EDTA) to anionic species. Among the three metals tested, ruthenium revealed the most attractive catalytic
performance toward PODRM reaction. It was shown that amount of metal could be lowered from 2.0 to 0.1% of the weight of support
without any decrease in catalytic activity or in selectivity to syngas product.
# 2004 Elsevier B.V. All rights reserved.
Keywords: Methane oxidation (partial); Dry reforming; Synthesis gas; Noble metal catalysts; Layered double hydroxides

1. Introduction
Production of hydrogen and synthesis gas from natural
gas- or methane as its major component over supported
metal catalysts represents an industrial process of utmost
significance [17]. Although the recent priority has been
given to nickel catalysts due to their low cost, the precious
metals still remain under consideration, as they offer not
only high catalytic performance but also a lower coking
capacity and therefore a longer operation lifetime in

* Corresponding author. Tel.: +1 613 562 5800x6042;

fax: +1 613 562 5170.
E-mail address: andrey_tsyganok@yahoo.com (A.I. Tsyganok),
t.hayakawa@aist.go.jp (T. Hayakawa).
0926-860X/$ see front matter # 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.apcata.2004.07.030

reactions of methane reforming to syngas with steam,

carbon dioxide, and by partial oxidation [819].
The possibility of uniting a slightly exothermic partial
oxidation of methane (reaction 1 in Table 1) with a highly
endothermic reaction of dry reforming (reaction 2) has already
been proposed and experimentally demonstrated in the
literature [20]. Such a combined reaction (for example,
reaction 3 that was studied in this work) needs a considerably
lower amount of external heat to keep a catalytic reactor at a
high temperature. Such information suggests that synthesis
gas from methane feedstock can be produced at a lower cost,
provided that appropriate catalysts are employed.
Among the catalysts reported, those derived from LDH
precursors demonstrated a more pronounced catalytic performance compared to catalysts synthesized by conventional
techniques [2128]. Traditionally, LDHs are prepared by

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Table 1
Enthalpy values for reactions of methane studied in this work
Reaction

(1)
(2)
(3)

CH4 + 1/2O2 = 2H2 + CO

CH4 + CO2 = 2H2 + 2CO
11CH4 + 5O2 + CO2 = 22H2 + 12CO

DH0 (kJ per mole of

CH4) at temperature
25 8C

850 8C

35.65
247.34
9.92

21.79
260.35
3.86

coprecipitation of Mg(II) and Al(III) cations at basic pH

[2932]. An additional (guest M) metal is introduced as a
cationic species, which results in a partial substitution of Mg
or Al in brucite-like layers and therefore a formation of a solid
with lamellar structure similar to that of a hydrotalcite
[Mg6Al2(OH)16]CO3
4H2O (MgAlCO3; HT) [3336] or a
meixnerite [Mg6Al2(OH)16](OH)2
4H2O (MgAlOH) [3740].
An alternative technique of introducing metals into LDH
structure has also been reported [41,42]. It was based on a
well-known capacity of metal cations to form highly stable
EDTA chelates that are negatively charged (MY ) [43,44];
these were further introduced into LDH via coprecipitation,
anion-exchange, and reconstruction reactions [45]. Versatility of a novel approach was then demonstrated by
synthesizing meixnerite-like LDHs bearing chelates of
precious metals [46]. For the test reaction of dry reforming
of methane, a ruthenium (2.0 wt.%) catalyst was found the
most suitable among all the noble metals tested.
In this work, we present details of preparing ruthenium,
rhodium, and platinum catalysts, supported on MgAl
mixed oxide. The method of synthesis was based on a

Fig. 1. Powder XRD patterns of MgAl double hydroxides bearing noble

metal EDTA-chelates (pattern of a reference meixnerite is shown for
comparison).

memory effect of calcined HT, i.e. on the ability of

Mg(Al)Ox mixed oxide to re-create (or reconstruct) a
layered structure upon rehydration with aqueous solutions
[4749]. Results of catalytic activity tests and characterization of catalysts and catalyst precursors by X-ray powder
diffraction (XRD), thermogravimetry and differential
thermal analysis (TG-DTA), and transmission electron
microscopy (TEM) techniques will be presented and
discussed. It will be shown that the amount of a supported
noble metal can be substantially lowered without viewable
reduction in the activity/selectivity of a catalyst.

2. Experimental
2.1. Reagents and solutions
Chemicals from Wako Pure Chemical Industries, Ltd.
included the nitrates of Mg(II) and Al(III); sodium
hydroxide, carbonate, and edetate; and platinum(IV)

Fig. 2. Thermal behavior under oxidative conditions of MgAl LDHs

having EDTA-chelated noble metals: MgAlRuY (A), MgAlRhY (B),
MgAlPtY (C), and a reference meixnerite (D). LDH loading: 0.040.05 g;
air flow: 20 cm3 min 1; rate of temperature increase: 5.0 8C min1.

A.I. Tsyganok et al. / Applied Catalysis A: General 275 (2004) 149155

chloride dissolved in a hydrochloric acid. The nitrate of

ruthenium(III) nitrosyl was purchased from Sigma-Aldrich
Co., the nitrate of rhodium(III) was purchased from Strem
Chemicals Inc. All the reagents had 9899% purity and were
used without additional purification. Distilled and deionized
water was used throughout the work.
Amounts of precious metals corresponded to 2 wt.% to
the weight of Mg(Al)Ox support unless indicated otherwise.
Equimolar amounts of sodium edetate were taken for
preparing metal complexes. Chelation of noble metals with
EDTA was carried out in an aqueous solution at room
temperature.
Methane and carbon dioxide were from Tokyo Gas
Chemical Co. and Showa Tansan Co., respectively. Oxygen
as well as nitrogen to dilute a feeding gas mixture was
from a pipeline supply. All gases employed were of purity
higher than 99.99%.
2.2. Synthesis of LDHs

151

ground up to a fine powder, which was further calcined in air

at 500 8C for 16 h to produce Mg(Al)Ox mixed oxide.
Preparation of a reference material of meixnerite
involved rehydration of HT-derived MgAl mixed oxide
with degassed and deionized water. The oxide powder (2 g)
was placed into a 100 cm3 conical flask with a Tefloncoated stirring magnet bar. Then the flask was filled with
water to almost no headspace volume and tightly capped
in order to minimize contamination of the synthesized
solid with carbonate that would come from CO2 of air.
The suspension was kept under vigorous stirring for 4 h at
room temperature. Then followed the steps of filtering a
solid out, rinsing it with water, and drying in air as for HT
synthesis.
Incorporation of noble metals into MgAl LDHs was
done by reconstruction reactions using aqueous solutions of
pre-chelated metals. Each metal salt and sodium edetate,
taken in equimolar amounts, were first placed into a conical
flask (100 cm3 capacity) and dissolved in 80 cm3 of water.
Then pH of the solution was adjusted to 10.5 by dropwise

To prepare synthetic hydrotalcite, we first dissolved

Mg(II) and Al(III) nitrates (150 and 50 mmol) in distilled
and deionized water (100 cm3). Then this solution was
dropwisely added to a 200 cm3 aqueous solution of sodium
carbonate (200 mmol), which was poured into a 3-neck
round-bottom reaction flask and pre-heated to 6063 8C.
During coprecipitation, the slurry was vigorously stirred
with a Teflon-coated magnet bar and kept at pH 10 by
dropwise addition of 1 M solution of NaOH. After complete
addition of the metal nitrates solution, the suspension was
stirred at 6063 8C for an hour, followed by ageing for 18 h
without stirring at the same temperature. Thus synthesized
colorless solid was filtered out, rinsed with a large volume of
water, and dried in air at 80 8C for 16 h. The dried solid was

Fig. 3. Powder XRD patterns of ruthenium-containing MgAl mixed

oxides, obtained from LDHs by calcination in air at 1000 8C: Ru2.0%/
Mg(Al)Ox (A), Ru0.5%/Mg(Al)Ox (B), and Mg(Al)Ox from a reference
meixnerite (C).

Fig. 4. Combined partial oxidation and dry reforming of methane over

noble metal catalysts: reaction temperature, 850 8C; catalyst loading,
0.03 g; gas feed, CH4/O2/CO2/N2 = 35.2:16.2:3.18:45.8 (vol%); F/W space
velocity, 226666 cm3 g 1 h 1; pressure, 1 atm.

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Table 2
Surface areas of the mixed oxides derived from MgAl LDHs

(1)
(2)
(3)
a

Starting LDH material

Treatment

Specific surface area (m2 g 1)a

MgAlRuY (i.e. precursor of Ru2.0%/Mg(Al)Ox catalyst)

MgAlOH
MgAlCO3

Calcination in air at 1000 8C for 5 h

Calcination in air at 1000 8C for 6 h
Calcination in air at 1000 8C for 6 h

70
80
82

Measured by BET method.

addition of 1 M NaOH solution. After that, a fine powder of

Mg(Al)Ox mixed oxide (2 g) was put into the solution, and
the slurry was vigorously stirred by Teflon-coated magnet
bar at room temperature. After stirring for 4 h, the solid was
filtered out, rinsed with 1000 cm3 of water, and dried in air at
80 8C for 16 h.
2.3. Characterization techniques
XRD patterns of powdered samples were recorded at
room temperature under air using a MacScience MXP18

diffractometer with a Cu Ka irradiation source (l =

) at voltage 40 kV and current 50 mA.
1.54056 A
TG-DTA studies of solids were carried out under a flow of
air (20 cm3 min 1) with TGA-50 and DTA-50 analyzers
(both from Shimadzu Co.) using 0.04 to 0.05 g of a sample
and a 5 8C min 1 temperature increase rate.
Specific surface area of solids calcined was measured by
N2 adsorption at liquid nitrogen temperature using a
Quantachrome Automated Gas Sorption System and
powdered samples (0.120.13 g), which were outgassed at
320 8C for 3 h.

Fig. 5. High-resolution TEM micrograph image of a spent Ru2.0%/Mg(Al)Ox catalyst after PODRM reaction at 850 8C for 5 h: reaction conditions are the same
as in Fig. 4.

A.I. Tsyganok et al. / Applied Catalysis A: General 275 (2004) 149155

TEM was done with a JEOL JEM-2010F machine

equipped with a Gatan slow-scan camera for high-resolution
observation. The accelerating voltage applied was 200 kV.
Specimens for TEM were prepared by standard techniques.
Element composition of TEM specimens was measured by
registering an emission of X-rays from specimen with an
attached Link ISIS energy dispersive X-ray spectrometer
(EDS) from Oxford Instruments plc.
2.4. Catalytic activity tests
Prior to catalytic tests, every LDH was pressed into a
tablet and ground up to sieve a 212425 mm fraction of
particles. These were calcined in air at 1000 8C for 5 h. A
resultant mixed oxide (0.03 or 0.15 g in loading) was diluted
with Wakogel silica G (0.15 g; 300600 mm), and the
mixture was placed into a quartz tube reactor (8 mm i.d.). No
reductive activation pretreatment was applied. A reaction
gas mixture CH4/O2/CO2/N2 (35.2:16.2:3.18:45.8 vol%)
was introduced with a 6800 cm3 h 1 total flow rate at
1 atm pressure. Then the reactor was heated from room
temperature to 850 8C within an hour. When the temperature
approached the value, the sampling of post-reactor gas phase
was started. Analysis of reaction products was carried out by
gas chromatography (GC) using columns packed with
Porapak Q and molecular sieve 5A. After 5 h time on stream
at 850 8C, admission of CH4, O2, and CO2 was stopped, and
reactor was cooled to room temperature under flow of
nitrogen. Spent catalysts were removed from the reactor and
some of them were characterized with XRD and TEM
techniques.

153

average cationcation distance in the brucite-like layers

remained unchanged regardless of the kind of anionic
complex introduced.
As (i) the amount of metal complexes introduced was
considerably lower than that allowable by stoichiometry, (ii)
the time of LDH syntheses was shortened to 4 h, and (iii) due
to a high rate of LDH reconstruction from MgAl mixed
oxide [50], the synthesized LDHs were most probably
similar to a meixnerite, with introduced species being
located on the outer surface of the reconstructed LDH
crystallites.
Similar thermal behavior of reconstructed LDHs and of a
reference MgAl-OH was observed as well. As TG analysis
revealed, all the synthesized solids experienced a 2-step
reduction in weight, with a final weight loss of 43.0 to
44.6%. In turn, the reference MgAl-OH revealed a 36.8%
reduction in weight. Two endothermic peaks appeared in
DTA profiles of all the synthesized solids and a reference
meixnerite, which was typical of MgAl LDHs (Fig. 2). The
first peak at 220230 8C was due to the release of structural

3. Results and discussion

3.1. Incorporation of noble metals into the structure of
MgAl double hydroxide
Solutions of all three noble metal chelates were
intensively colored. This made it simple to control the
efficiency of chelates incorporation into reconstructed
LDH. In fact, after 4 h stirring at room temperature, the
synthesized solids acquired the color of chelates, while an
aqueous solution, employed for rehydration, was colorless
after filtration. Both findings indicated the complete
involvement of noble metal chelates into a solid matrix of
the synthesized materials.
Formation of a layered structure of the rehydrated solids
was confirmed by the results of XRD studies. Diffraction
patterns very similar to that of a meixnerite MgAl-OH were
recorded for all the prepared solids (Fig. 1). The presence of
a set of three reflection peaks at 2Q 11.08, 22.78, and 34.58
indicated that the solids had a regular layered structure with
a 3R symmetry for layers stacking as in MgAl-OH and HT.
No shift was observed in the peak position at 2Q 60.48
attributed to reflection from (1 1 0) plane indicating that the

Fig. 6. Combined partial oxidation and dry reforming of methane, catalyzed by supported ruthenium: reaction temperature, 850 8C; catalyst
loading, 0.15 g; gas feed, CH4/O2/CO2/N2 = 35.2:16.2:3.18:45.8 (vol%);
F/W space velocity, 45333 cm3 g 1 h 1; pressure, 1 atm.

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A.I. Tsyganok et al. / Applied Catalysis A: General 275 (2004) 149155

water, while the second peak (around 400 8C) was attributed
to the dehydroxylation of Mg and Al hydroxides and
decomposition of the acquired metal complexes. A small
exothermic peak was registered at 361 8C for LDH bearing
RhY species (Fig. 2(B)); this was ascribed to the combustion
of EDTA ligand itself [42].
Calcination of LDHs in air at 1000 8C caused drastic
changes in phase composition of the resultant mixed oxides.
Very similar XRD patterns were recorded for the mixed
oxides obtained from catalyst precursors and for those from
reference LDHs. Due to a low content, no phases involving
noble metals were detected by XRD. The patterns recorded
for two Ru-containing mixed oxides and a calcined
meixnerite are shown in Fig. 3. Additionally to a periclase
MgO, a spinel structure of MgAl2O4 was clearly detected.
One should here mention that, despite the high temperature
for LDH calcination in air, the produced mixed oxides
retained sufficiently high surface areas (Table 2).
3.2. Combined partial oxidation and dry reforming of
methane over noble metal catalysts
Results of activity tests for catalysts containing 2 wt.% of
noble metals in PODRM at 850 8C are shown in Fig. 4.
Ru- and Rh-catalysts revealed activity values markedly higher
than that of platinum, as well as higher yields of syngas
components. It should be mentioned that the mixed metal
catalysts were not reductively pretreated and thus the

formation of catalytically active metallic phase occurred in

situ under the reaction conditions. It is seen that the Ru- and
Rh-catalysts approached their maximal activity, which
appeared to be limited by equilibrium, since the beginning
of the test runs. One can here propose that reduction of noble
metal oxides to metallic phase could occur at a lower
temperature or in the very beginning of test reaction at 850 8C.
However, the formation of noble metal particles could not be
detected with either XRD or high-resolution TEM (Fig. 5).
Also, TEM observation revealed the absence of any
carbonaceous deposits on catalyst and the presence of a
crystalline material of support without any spots potentially
attributable to supported noble metal clusters. At the same
time, EDS analysis confirmed the presence of noble metals in
specimens. One can here assume that noble metal clusters
were not observed with TEM due to their very small size.
Another reason could be a complete conversion of metallic
clusters back into a supported oxide due to contact with
oxygen of air, as the samples of spent catalysts were removed
from the reactor and kept under air after reaction.
Among the noble metals tested, the supported ruthenium
revealed the highest yield of syngas and H2-to-CO ratio. It
was therefore selected for the next step of studies aimed
at determining the minimal amount of supported metal
required for high catalytic performance. Additionally to
Ru2.0%/MgAlOx catalyst, four more samples with various
Ru-contents were prepared from LDH precursors and tested
in PODRM reaction at 850 8C. Results obtained are shown

Fig. 7. Synthetic strategy of preparing noble metal catalysts, supported on MgAl mixed oxide (explanation for steps 14 is given in text).

A.I. Tsyganok et al. / Applied Catalysis A: General 275 (2004) 149155

in Fig. 6. It is seen that the amount of introduced ruthenium

could be lowered to 0.1 wt.% without a marked decrease in
CH4 conversion, hydrogen yield, and H2-to-CO ratio.

4. Conclusion
Finally, the synthetic strategy applied for preparing noble
metal catalysts, supported on MgAl mixed oxide support, is
summarized in Fig. 7. By calcining synthetic hydrotalcite in
air at 500 8C, a Mg(Al)Ox mixed oxide was produced (step
1). Due to a memory effect, a layered structure was then
reconstructed, and negatively charged chelates of noble
metals (MY ) were thus introduced into the LDH matrix
(step 2). Calcination in air at 1000 8C converted LDH to a
mixed metal oxide, mainly composed of a periclase-like
Mg(Al)Ox structure and of MgAl2O4 spinel (step 3). The
metal introduced was supposed to be present in the form of
fine oxide clusters (MOx) bound to the surface of the support.
Such surface-bound metal oxide clusters turned into metallic
species (M0) under the PODRM reaction conditions (step
4) thus producing highly active and selective catalysts
having a low coking capacity.
The method reported in this work represents a novel
and sufficiently general concept for fabricating mono- and
multi-component heterogeneous catalysts for various reactions catalyzed by metals and/or metal oxides supported on
MgAl mixed oxide.

Acknowledgements
The support of this work by The Japan Society for the
Promotion of Science (JSPS) organization and The Japan
Research and Development Center for Metals (JRCM) is
gratefully acknowledged.

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