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Applied Catalysis A: General 197 (2000) 213219

FriedelCrafts acylation of toluene catalyzed by solid superacids


Kazushi Arata , Hideo Nakamura, Miyuki Shouji
Department of Science, Hokkaido University of Education, Hachiman-cho, Hakodate 040-8567, Japan
Received 17 May 1999; received in revised form 24 September 1999; accepted 4 October 1999

Abstract
Benzoylation of toluene (141 mmol) with 2 mmol of benzoic anhydride or benzoyl chloride was carried out in liq-
uid phase over 0.5 g of solid superacids of sulfated and supported metal oxides at 100 C for 3 h. Yields of o-, m-, and
p-methylbenzophenones in the distribution of 2030% o-, 24% m-, and 7080% p-isomers were 92, 48, 28, 27, 26, and 0%
for the sulfated oxides of SO4 /ZrO2 , SO4 /SnO2 , SO4 /TiO2 , SO4 /Al2 O3 , SO4 /HfO2 , and SO4 /Fe2 O3 with benzoic anhydride as
the acylating reagent. The supported oxides of WO3 /ZrO2 , WO3 /TiO2 , WO3 /SnO2 , and MoO3 /ZrO2 gave yields of 55, 26, 16,
and 15%, respectively; WO3 /Fe2 O3 and B2 O3 /ZrO2 gave no yields. As a whole, yields by the reactions with benzoyl chloride
were lower than those with the anhydride. When benzoyl chloride was the acylating agent, the reactions over SO4 /Fe2 O3 and
WO3 /Fe2 O3 were homogeneously catalyzed by FeCl3 produced during the reaction, though other reactions were heteroge-
neously catalytic. The activity of SO4 /ZrO2 was largely promoted by the addition of Pt and Ru (2 wt.%). Silicaaluminas,
zeolites, and mordenites were almost inactive under the conditions. It was shown from the acid strength and the catalytic
activity for disproportionation of toluene that inactivity of the aluminosilicates for the acylation is based on their catalytic
action by Brnsted acid sites. A rough relationship was obtained between the highest acid strength of the present catalysts and
the acylated yields. The present catalysts were also satisfactorily effective for the acetylation of toluene with acetic anhydride
and acetyl chloride. 2000 Elsevier Science B.V. All rights reserved.
Keywords: Acylation; Benzoylation; Acetylation; Solid superacids; Sulfated metal oxides; Supported metal oxides; Zeolites

1. Introduction Therefore, there is much interest in ways to catalyze


these reactions with solid acids which do not form
The FriedelCrafts reaction (alkylation and acy- such complexes with carbonyl compounds. However,
lation of aromatic compounds) has been studied a high acidic strength is required on the surface to
extensively in the past using various Lewis acid cat- catalyze the acylation; a superacid, with acid strength
alysts (BF3 , AlCl3 , FeCl3 , TiCl4 ) and protonic acids stronger than that of 100% H2 SO4 , is desired.
(HF, H2 SO4 ) [13]. The acylation reactions require Over a wide range of solid acids zeolites and
molar amounts of the Lewis catalyst, which form silicaaluminas hold high acidities on their surface
complexes with both the acylating reagent and the and have received much attention in the petroleum
carbonyl product; thus, work up is needed to decom- industry and in organic syntheses. However, little at-
pose the complexes, and the catalyst is not reusable. tention has been given to those silicoaluminic acids
as catalysts for the FriedelCrafts acylation. Chiche
Corresponding author. Tel.: +81-138444286; and others reported the acylation of toluene and
fax: +81-138444286. p-xylene by various carboxylic acids catalyzed by a
E-mail address: karata@cc.hokkyodai.ac.jp (K. Arata) Y-faujasite-type zeolite exchanged with Ce3+ cation,

0926-860X/00/$ see front matter 2000 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 6 - 8 6 0 X ( 9 9 ) 0 0 4 8 4 - 6
214 K. Arata et al. / Applied Catalysis A: General 197 (2000) 213219

but the conditions were quite severe: operating in an temperature of 6070 C; aqueous ammonia so-
autoclave heated at 150 C for 2 days [4]. Olah and lution (28%) was added dropwise with stirring
co-workers investigated the heterogeneous catalysis into 100 g of ZrOCl2 8H2 O dissolved in 2 l of
by a perfluorinated resinsulfonic acid (Nafion-H) for distilled hot water; then, the precipitated solution
the acylation of substituted benzenes [5]. The reac- was kept at 6070 C for 3 h; the precipitate was
tions were conducted by heating a stirred mixture washed several times with hot water, and finally
of acid chloride, aromatics, and the solid Nafion-H dried.
catalyst under reflux. Satisfactory results were ob- 2. Sn(OH)4 : aqueous ammonia was added into a so-
tained, though the catalyst was not a usual solid acid lution of SnCl4 xH2 O (10 g) in water (2 l) with
consisting of metal oxides. stirring at 60 C, the final pH of the solution be-
Solid superacids, sulfated zirconia and alumina ing 8. The precipitates were washed by decanta-
(SO4 /ZrO2 and SO4 /Al2 O3 ) showed activities for tion five times, using 1 l of hot water for each, and
the benzoylation of toluene with benzoyl chloride dried.
and benzoic anhydride at temperatures below reflux 3. H4 TiO4 : a 290 ml volume of Ti[OCH(CH3 )2 ]4
of the mixture [6,7]. Tungsten oxide supported on was added to 2 l of distilled water in a 5 l beaker
zirconia (WO3 /ZrO2 ), a superacid by the system of with stirring; the white precipitates which formed
metal oxides, was also active for the acylation [8]. were dissolved by adding 250 cm3 of conc. HNO3 .
We have reported that, on the oxide surfaces of Fe, Ammonium hydroxide was added into the aque-
Ti, Hf, Sn, and Si, superacids with an acidity stronger ous solution with stirring until the pH of the
than that of 100% H2 SO4 are generated by addition solution reached 8, followed by washing the pre-
of the sulfate species [9]. Superacids by metal oxides cipitates by decantation of the 5 l beaker twice and
were also synthesized in the same manner as those of drying.
the sulfate superacids by supporting SnO2 , TiO2 , and 4. Hf(OH)4 : the hydroxide was obtained by hydolyz-
Fe2 O3 with WO3 and ZrO2 with MoO3 and B2 O3 ing HfCl4 with ammonia water to pH 8, washing
[10]. Metal-promoted superacids, which were highly the precipitates, and drying.
active for the reaction of butane to isobutane, were 5. Fe(OH)3 : to a solution of Fe(NO3 )3 9H2 O (500 g)
prepared recently: PtSO4 /ZrO2 , RuSO4 /ZrO2 , and dissolved in 2 l of water in a 5 l beaker was added
Fe2 O3 /ZrO2 [1113]. aqueous ammonia with stirring to precipitate
Most of the above-mentioned superacids have not Fe(OH)3 . The aqueous portion was decanted from
been examined as to the acylation. The present pa- the precipitate after allowing the solution to stand.
per is concerned with a comparative study of those Then, the precipitates were washed by decantation
superacids in company with several zeolites and seven to eight times, and dried.
silicaaluminas for the benzoylation of toluene with All of the precipitated hydrogels were dried at
benzoic anhydride and benzoyl chloride at mild tem- 100 C for 24 h and powdered to below 100 mesh.
peratures below reflux operating in a batch mode.
Several catalysts were also examined in a less reac-
tive acylation: the acetylation of toluene with acetic 2.1.2. Sulfate treatment of metal hydroxides
anhydride or acetyl chloride. Materials prepared as above were treated with sul-
fate ions by exposing 2 g of dried and powdered metal
hydroxide in 30 ml of aqueous sulfuric acid on a glass
filter for 1 h, followed by filtering, drying in a desic-
2. Experimental cator at room temperature, and finally calcining. The
concentration of H2 SO4 was 1 N for the hydoxides of
2.1. Catalyst preparation Ti and Zr, 0.5 N for Fe, 2 N for Hf, and 6 N for Sn;
the calcination temperature was 500 C for Fe, 525 C
2.1.1. Preparation of metal hydroxides for Ti, 550 C for Sn, 600 C for Zr, and 700 C for Hf.
1. Zr(OH)4 : the hydroxide was obtained by hydrolyz- The catalysts prepared are indicated as SO4 /ZrO2 ,
ing ZrOCl2 with aqueous ammonia to pH 8 at a SO4 /Fe2 O3 , SO4 /TiO2 , SO4 /HfO2 , and SO4 /SnO2 .
K. Arata et al. / Applied Catalysis A: General 197 (2000) 213219 215

SO4 /Al2 O3 was prepared by powdering -Al2 O3 B2 O3 /ZrO2 -3 was prepared by impregnating
(Japan Chromato, AE-11), followed by treating with Zr(OH)4 (XZO 632/03) with aqueous boric acid
5 N H2 SO4 and calcining at 650 C. (H3 BO3 ), followed by evaporating water and calcin-
Two more SO4 /ZrO2 catalysts were prepared. One ing in air at 550 C for 3 h (5 wt.% B).
was prepared by calcining sulfated zirconia of Wako Fe2 O3 /ZrO2 -3 was obtained by impregnating
Pure Chemical Industries at 550 C. The other was Zr(OH)4 (XZO 632/03) with an aqueous solution of
prepared by powdering zirconium hydroxide, XZO Fe(NO3 )3 , followed by evaporating residual water,
632/03, of MEL Chemicals (dried at 100 C for 24 h), drying at 300 C for 3 h, treating with 1 N H2 SO4 , dry-
followed by treating with 1 N H2 SO4 and calcin- ing, and calcining in air at 700 C for 26 h (2 wt.% Fe).
ing at 600 C. The former catalyst was denoted as The calcination temperature of the present materials
SO4 /ZrO2 -1 and the latter as SO4 /ZrO2 -3; thus, the is high, above the melting point of Pyrex glass. Thus,
sulfated zirconia prepared from ZrOCl2 was denoted the calcination at temperatures above 700 C was per-
as SO4 /ZrO2 -2. formed in a ceramic crucible, followed by calcining
All the catalysts were calcined in Pyrex glass tubes in Pyrex glass tubes at 500 C for 1 h and sealing in
in air for 3 h and sealed in ampoules while hot, to ampoules until use.
avoid humidity until use.
2.1.5. Preparation of aluminosilicates
2.1.3. Preparation of Pt- and Ru-added sulfated Silicaaluminas and acidic zeolites and mordenites
zirconias were supplied from the Catalysis Society of Japan
PtSO4 /ZrO2 -3 was obtained by treating Zr(OH)4 as reference catalysts and calcined at 500 C for 3 h:
(XZO 632/03 MEL Chemicals) with 1 N H2 SO4 , JRC-SAH-1 and JRC-SAL-2 with SiO2 /Al2 O3 ratios
followed by drying, impregnating with aqueous of 2.5 and 6 for silicaaluminas; JRC-Z5-70H and
H2 PtCl6 6H2 O (to obtain 2 wt.% Pt in the final cat- JRC-Z-HY5.6 with the ratios of 70 and 5.6 for zeo-
alyst after calcination), evaporating residual water, lites: JRC-Z-HM20 and JRC-Z-HM15 with the ratios
drying, and calcining in air at 600 C for 3 h. of 20 and 15 for mordenites; respectively. These were
RuSO4 /ZrO2 -3 was obtained by impregnating denoted as SiO2 Al2 O3 -1 and -2, zeolite-1 and -2, and
Zr(OH)4 (XZO 632/03) with an aqueous solution of mordenite-1 and -2, respectively.
RuCl3 nH2 O, followed by evaporating residual water,
drying at 300 C for 3 h, treating with 1 N H2 SO4 ,
2.2. Reaction procedure
drying, and finally calcining in air at 550 C for 3 h,
the concentration being 2 wt.% Ru based on the
2.2.1. Acylation of toluene
hydroxide.
The acylation was carried out with a mixture of
15 ml (141 mmol) of toluene, 2 mmol of acylating
2.1.4. Preparation of superacids by metal oxides reagent (0.281 g for benzoyl chloride, 0.452 g for ben-
The catalysts of WO3 /ZrO2 -3, WO3 /TiO2 , WO3 / zoic anhydride, 0.157 g for acetyl chloride, 0.204 g
SnO2 , WO3 /Fe2 O3 , and MoO3 /ZrO2 -3 were ob- for acetic anhydride), 0.5 g of catalyst, and 0.185 g
tained by drying the hydroxides of Zr, Ti, Sn, (1 mmol) of tridecane as an internal standard with
and Fe (prepared in Section 2.1.1) at 300 C, fol- stirring under nitrogen atmosphere. A small amount
lowed by impregnating with aqueous ammonium of the sample was withdrawn periodically with a 1 ml
metatungstate (NH4 )6 (H2 W12 O40 ) or ammonium syringe, diluted with ethyl acetate, separated from
molybdate (NH4 )6 Mo7 O24 4H2 O), evaporating water the catalyst by filtration, and analyzed by gasliquid
at room temperature, drying, and calcining in air. The chromatography with an FID detector using a 25 m
concentration was 15 wt.% W or 5 wt.% Mo metal column of OV-1701 BONDED (180 C for benzoyla-
based on the hydroxides. The calcination temperature tion, 150180 C for acetylation). The product isomers
was 700 C for WO3 /TiO2 and WO3 /Fe2 O3 , 800 C were identified by the spectral comparison with au-
for WO3 /ZrO2 -3 and MoO3 /ZrO2 -3, and 1000 C for thentic samples. Since toluene was in excess, yields
WO3 /SnO2 . were based on the acylating reagents.
216 K. Arata et al. / Applied Catalysis A: General 197 (2000) 213219

2.2.2. Disproportionation of toluene the homogeneous FriedelCrafts acylation, the reac-


Disproportionation of toluene was carried out in a tion is generally performed with an acid chloride as the
microcatalytic pulse reactor with a fixed-bed catalyst acylating agent and with metal halides such as FeCl3
(He carrier gas 20 ml/min, catalyst 0.05 g, pulse size or AlCl3 as catalysts. In the reactions with SO4 /Fe2 O3
1 l); effluent products were directly introduced into and WO3 /Fe2 O3 , a question arises whether the ac-
a g.c. column for analysis (SE-30, 2 m, 90 C). The tive species are on the solid surface or in the liq-
catalyst was again heated at 300 C for 1 h in the He uid as FeCl3 derived from the reaction of Fe2 O3 and
flow before reaction. Activities were compared with HCl produced or Cl , caused by the formation of the
the first pulse value. acyl cation (PhCO+ ) from benzoyl chloride. When
the catalysts were removed from the reaction mix-
ture by filtration, the mixture was found to be col-
3. Results and discussion ored brown. This color was brought about by Fe3+ ,
though the mixture over most of the catalysts was
The benzoylation of toluene with benzoic anhy- clear. In fact, Cl was detected in the mixture, and the
dride or benzoyl chloride, a typical example of the mixture turned clear when washed with water. That
FriedelCrafts acylations, was carried out in liquid the reaction over SO4 /Fe2 O3 and WO3 /Fe2 O3 is ho-
phase over various solid superacids of sulfated and mogeneous can be obvious from the results that the
supported metal oxides along with silicoaluminic SO4 /Fe2 O3 and WO3 /Fe2 O3 catalysts were not active
acids at 100 C; the results for 3 h are shown in when the reaction was performed with benzoic anhy-
Table 1 for sulfated metal oxides and in Table 2 for dride, though the yields were 38 and 74% in the reac-
supported metal oxides, silicaaluminas, zeolites, and tion with benzoyl chloride. The inactivity with the an-
mordenites. hydride is based on their weak acidity on the surface,
Most of the reactions showed a continual increase as will be described later. The reaction mixture over
of yield with time, and were thus judged to be hetero- MoO3 /ZrO2 with benzoyl chloride was also slightly
geneously catalytic, but the materials of SO4 /Fe2 O3 bluish, but the reaction progressed continuously.
and WO3 /Fe2 O3 failed to react further after 3060 min The reactivity with acylating reagents is generally
when benzoyl chloride was the acylating reagent. In PhCOCl > (PhCO)2 O > PhCO2 H; strong acid sites are
needed for the formation of acyl cation (PhCO+ ) from
Table 1 the anhydride. However, the present results are not
Benzoylation of toluene with benzoic anhydride or benzoyl chlo- coincident with the reactivity, in particular, with the
ride over sulfated metal oxides at 100 C for 3 h case of SO4 /ZrO2 -1. A supplementary examination
Catalyst Benzoic anhydride Beyzoyl chloride with the SO4 /ZrO2 -1 catalyst gave the same results as
Yield Isomers Yield Isomers those in Table 1. The reason is not clear at the present
(%) (%) (%) (%) stage: probably, strong interaction between oxygens
o- m- p- o- m- p-
of the anhydride and acid sites on the surface; this
should be a strong point of the present catalysts for the
SO4 /ZrO2 -1 92 27 0 73 22 31 0 69 acylation. Benzoylation by the benzoic acid produced
SO4 /ZrO2 -2 52 30 2 68 60 30 2 68
SO4 /SnO2 48 25 4 72 52 24 3 73
was not caused under the conditions when the reaction
SO4 /TiO2 28 23 4 73 17 24 3 73 was performed with (PhCO)2 O; the reaction occurred
SO4 /Al2 O3 27 24 4 72 18 23 4 74 at temperatures above reflux of the mixture [6].
SO4 /HfO2 26 25 3 72 Among the solid superacids synthesized so far, the
SO4 /Fe2 O3 0 38 27 0 73 SO4 /ZrO2 catalyst showed the highest acid strength
SO4 /ZrO2 -3 25 30 0 70
PtSO4 /ZrO2 -3 79 28 3 69
(Ho < 16) [10] and gave the highest yield in the
RuSO4 /ZrO2 -3 40 25 2 73 benzoylation as shown in Tables 13. Table 1, how-
SO4 /ZrO2 -3a 19 26 2 71 ever, shows how the preparation method controls the
PtSO4 /ZrO2 -3a 71 28 2 70 catalytic activity; SO4 /ZrO2 -1 is especially the most
RuSO4 /ZrO2 -3a 35 25 2 73 effective when carried out with the anhydride, in com-
a Reaction at 90 C. parison with SO4 /ZrO2 -2 and -3. The SO4 /ZrO2 -1
K. Arata et al. / Applied Catalysis A: General 197 (2000) 213219 217

Table 2
Benzoylation of toluene with benzoic anhydride or benzoyl chloride over supported metal oxides and silicoaluminic acids at 100 C for 3 h
Catalyst Benzoic anhydride Beyzoyl chloride

Yield (%) Isomers (%) Yield (%) Isomers (%)

o- m- p- o- m- p-
WO3 /ZrO2 -3 55 31 0 69 19 31 0 69
WO3 /TiO2 26 19 3 78 20 31 0 69
WO3 /SnO2 16 18 0 82 14 18 0 82
WO3 /Fe2 O3 0 74 16 0 82
MoO3 /ZrO2 -3 15 23 2 75 18 23 3 74
B2 O3 /ZrO2 -3 0
Fe2 O3 /ZrO2 -3 49 26 1 73
SiO2 A12 O3 -1 0 0
SiO2 A12 O3 -2 0 0
Zeolite-1 0 0
Zeolite-2 0 0
Mordenite-1 1 0 0 100 1 0 0 100
Mordenite-2 2 12 0 88 3 10 0 90

Table 3
the dehydrogenation of butane to butene, followed by
Acetylation of toluene with acetic anhydride at 100 C for 3 h
dimerization and cracking to isobutane [14,15]. Acid-
Catalyst Yield (%) Isomers (%) ity of metal-promoted sulfated zirconias is not char-
o- m- p- acterized in detail, and such study is desired. As per
this point of view, Fe2 O3 /ZrO2 -3 prepared in the same
SO4 /ZrO2 -1 7 2 0 98
PtSO4 /ZrO2 -3 7 2 0 98 manner as RuSO4 /ZrO2 -3 is also a noteworthy cata-
WO3 /ZrO2 -3 3 2 0 98 lyst, judging from its yield (49%), which was higher
than that of SO4 /ZrO2 -3 (25%).
The products were o-, m-, and p-methylbenzo-
matter is exceptionally prepared as a catalyst suitable phenones, and the distribution was not varied much:
for the organic synthesis 1 . 2030% o-, 24% m-, and 7080% p-isomers. The
It is reported that impregnation of SO4 /ZrO2 with predominant p-substitution is similar to that by the
Fe and Mn as well as with noble metals such as Pt and usual homogeneous reaction. An experimental homo-
Ru leads to pronounced activity for the reaction of bu- geneous reaction using benzyl chloride and AlCl3
tane to isobutane [10]; in particular, impregnation with gave the isomeric composition of 13% o-, 3% m-, and
a large quantity of Pt and Ru is exceedingly effective 84% p-methylbenzophenones, the o-substitution over
[11,12]. Thus, SO4 /ZrO2 -3 was modified by the addi- the present catalysts being close to double.
tion of Pt and Ru (2 wt.%) and examined in the benzoy- Silicaaluminas, zeolites, and mordenites were
lation with the anhydride. The activities were largely almost inactive for the reaction, even a famous ze-
promoted by the addition of the metals, as shown in olite, ZSM-5 (JRC-Z5-70H), being not active at
Table 1. A supplementary examination was tried at the all. These materials hold acidities enough to cause
lower temperature, 90 C; the enhancement by the ad- the FriedelCrafts reactions, and their acidities are
dition of Pt and Ru was 3.5 and two times, respectively. known to be in the range of superacidity [16]. The
It was assumed from the case of butane that the ac- acid strength was examined by the visual color
tivity enhancement would be uncertain because it was change method of the Hammett indicators; the indi-
reported that the promotion by the addition of metals cators were adsorbed on the solid surface in dried
was not based on acidity but on the metallic effect for cyclohexane at room temperature [7,9]. Zeolite-1
changed the basic forms (colorless) of p-nitrotoluene
1 A private communication from the company. (pKa = 11.35), p-nitrochlorobenzene (12.70), and
218 K. Arata et al. / Applied Catalysis A: General 197 (2000) 213219

m-nitrochlorobenzene (13.16) to the conjugate acid


forms (yellow), but did not change the color of
2,4-dinitrotoluene (13.75). Thus, the acid strength
is estimated to be 13.75 < Ho 13.16. Similarly,
the strength of moldenite-1 was determined to be
16.04 < Ho 14.52, that of silicaalumina-1 be-
ing 12.7 < Ho 11.35. Since acids stronger than
Ho = 12 are superacids, these solids are superacids.
However, zeolites are composed of Brnsted acid
sites, and this is the point of their inactivity.
In order to know whether Brnsted acid is inac-
tive for the acylation or not, several catalysts given
in Tables 13 were examined in the cracking of
cumene into benzene and propylene, a well known
reaction catalyzed by Brnsted sites. The reactivity
was, however, too high to compare the conversions,
and the decomposition of ethylbenzene into benzene
and ethylene was also too reactive. Thus, the dis-
proportionation of toluene into benzene and xylenes
was taken. Determination of the catalytic strengths
was tried by temperature/conversion comparisons
of silicaalumina-1, zeolite-1, and mordenite-1 with
WO3 /ZrO2 -3 and SO4 /ZrO2 -3; the results are shown
in Fig. 1. The temperature difference to show 5% con-
version among the catalysts is coincident with the acid
strength determined by the color change method of
the Hammett indicators: Ho < 16.04 for SO4 /ZrO2
and 16.04 < Ho 14.52 for WO3 /ZrO2 [9].

Fig. 2. Relation between the yields in the benzoylation and


the highest acid strength (Ho) of sulfated and supported metal
oxides. () SO4 /SnO2 , () SO4 /ZrO2 -2, ( ) SO4 /HfO2 , ()
WO3 /ZrO2 -3, (4) SO4 /TiO2 , (5) SO4 /Al2 O3 , () WO3 /TiO2 ,
() MoO3 /ZrO2 -3, () SO4 /Fe2 O3 , () B2 O3 /ZrO2 -3.

Fig. 1 as well as the results in the benzoylation indi-


cate that the inactivity of aluminosilicates for the acy-
lation is based on their catalytic action by Brnsted
acid sites. SO4 /ZrO2 is characterized to hold both
Lewis and Brnsted sites [1724]. SO4 /Al2 O3 was
recently reported to have both sites [25].
Although the Lewis acid strength as well as its vol-
ume of the present catalysts were not determined, a
relation between the acid strength and the yield in the
benzoylation was examined. The highest acid strength
Fig. 1. Comparison of the activities of SiO2 Al2 O3 -1 (),
(Ho) of sulfated and supported metal oxides was de-
zeolite-1 (), and mordenite-1 () with those of SO4 /ZrO2 -3 termined by TPD using pyridine as well as by the
() and WO3 /ZrO2 -3 () for the reaction of toluene. color change method using the Hammett indicators
K. Arata et al. / Applied Catalysis A: General 197 (2000) 213219 219

Acknowledgements

The authors thank Professor Makoto Hino, Hako-


date Technical College, for kindly providing us with
samples of PtSO4 /ZrO2 -3 and RuSO4 /ZrO2 -3.

References

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[24] R.C. Comelli, S.A. Canavese, S.R. Vaudagna, N.S. Figoli,
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