Applied Catalysis A: General 194 195 (2000) 227240

Activity for base-catalyzed reactions and characterization of

alumina-supported KF catalysts
Hajime Kabashima a , Hideto Tsuji a , Shinichi Nakatab,1 ,Yoshinori Tanaka b , Hideshi Hattori a,
a Center for Advanced Research of Energy Technology (CARET), Hokkaido University, Sapporo 060-8628, Japan
b R&D Division, Chiyoda Corporation, Moriya-cho, Kanagawa-ku, Yokohama 221-0022, Japan

Received 6 May 1999; received in revised form 9 July 1999; accepted 2 August 1999

Abstract
Alumina-supported KF (KF/alumina) catalysts containing different amounts of KF were characterized by XRD, XRF, XPS,
and 19 F MAS NMR to elucidate the catalytically active sites, whose appearance varies much with the pretreatment temperature.
The reactions examined are double bond isomerization of 1-butene and 1-pentene, Tishchenko reaction of pivalaldehyde, and
Michael addition of nitromethane to butene-2-one. The pretreatment temperature range in which the catalysts exhibited the
activities depends on the loading of KF. For the double bond isomerization and Tishchenko reaction, the catalysts loaded
with 1.2 and 4.6 mmol KF/g-catalyst exhibited the activities only in the pretreatment temperature range 573873 K, and
the catalyst loaded with 8.2 mmol KF/g-catalyst (Fluka-KF/alumina) exhibited the activities in the range 473773 K. For
the Michael addition, the activity of Fluka-KF/alumina did not vary much with the pretreatment temperature, though the
maximum activity was obtained when the sample was pretreated at 623 K.
Although the main species containing F was K3 AlF6 formed by the reaction of KF with alumina, which was observed by
both XRD and 19 F MAS NMR, it was not related to the formation of active sites. The surface species relevant to the catalytic
activities, in particular for the double bond isomerization and Tishchenko reaction, is the F containing species which gives
a peak at 150 ppm in 19 F MAS NMR. 2000 Elsevier Science B.V. All rights reserved.

Keywords: KF/alumina; Double bond isomerization; Tishchenko reaction; Michael addition; 19 F MAS NMR

1. Introduction may be related to a very hard anion F , the cat-

Since KF/alumina was introduced by Clark and
Ando et al. [1,2] as an effective solid catalyst to
promote base-catalyzed reactions [37], the catalyst
has been applied to a wide variety of organic syn-
theses [812]. Because the basic sites on KF/alumina
Corresponding author. Tel.: +81-11-706-7119;
fax: +81-11-726-0731.
E-mail address: hattori@carbon.caret.hokudai.ac.jp (H. Hattori).
1 Present address: Faculty of Engineering and Resource Science,
Akita University, Akita 010-8502, Japan.
alyst may show the characteristic performances
which differentiate KF/alumina from the oxide-type
solid base catalysts such as alkaline earth oxides
[13].
In contrast to many applications of KF/alumina to
organic syntheses as a base catalyst, mechanisms of
the appearance of the basicity of KF/alumina are not
clarified. Insufficient coordination of KF only with
surface OH groups may result in the formation of the
so-called half-naked and thus active F ions [14].
This possibility was supported by 19 F MAS NMR
[1519].

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 3 7 0 - 1
228 H. Kabashima et al. / Applied Catalysis A: General 194 195 (2000) 227240
It was proposed on the basis of IR and XRD
studies that the basic sites originate from KOH
and/or aluminate produced by the following reactions
[14,17,18,20].
12KF + Al2 O3 + 3H2 O 2K3 AlF6 + 6KOH (1)
6KF + 2Al2 O3 K3 AlF6 + 3KAlO2 (2)
Ando et al. concluded that there are three basic species
or mechanisms of the appearance of the basicity of
KF/alumina [21]: (1) the presence of active fluoride,
(2) the presence of [AlO ] ion which generates OH
when water is added, and (3) the cooperation of F
and [Al-OH].
In most cases of organic syntheses, KF/alumina has
been used with a drying pretreatment below 473 K.
Since most solid base catalysts become active when
pretreated above 673 K to remove CO2 and H2 O from
the surface [13], it is thus doubtful whether there still
remain CO2 and H2 O in various forms on the surface
of KF/alumina, which would block the active sites
when the material is dried below 473 K.
We have briefly reported that KF/alumina exhibits
the activity for double bond isomerization of 1-pentene
at 273 K when pretreated in vacuo in the temperature
range 573673 K [22]. Recently, Baba and co-workers
also reported that treatment KF/alumina (5 mmol/g)
at 673 K under vacuo resulted in high catalytic ac-
tivities for Tishchenko reaction of benzaldehyde [18]
and metathesis of silylalkynes [19]. It is obvious that
a high temperature treatment reveals active sites on
KF/alumina either by removal of CO2 and H2 O re-
maining on the surface in various forms or by for-
mation of specific surface structure. Baba et al. re-
ported that the F species giving a certain peak in 19 F
MAS NMR spectrum is relevant to the basic sites over
KF/alumina [18,19].
In the present work, we attempted to activate
KF/alumina by thermal treatment at various higher
temperatures, and studied the catalytic activities for
double bond isomerization of 1-butene and 1-pentene,
Tishchenko reaction of pivalaldehyde and Michael
addition of nitromethane to butene-2-one. We also
examined the changes in bulk and surface structures
of KF/alumina catalysts pretreated at different tem-
peratures by XRD, XRF, XPS, and 19 F MAS NMR to
elucidate catalytically active sites formed by thermal
treatment.
2. Experimental
2.1. Catalysts
KF/alumina (Fluka) was purchased from Fluka and
its KF content was determined to be 8.2 mmol g1
by XRF. The detection of -alumina phase in XRD
measurement indicates that the original alumina used
for Fluka-KF/alumina is -alumina.
We also prepared two kinds of KF/alumina by im-
pregnation of -alumina (JRC-AL04, the reference
alumina catalyst supplied from the Catalysis Society
of Japan) with aqueous solutions of KF, followed by
drying at 373 K in air. The amounts of KF were 1.2
and 4.6 mmol g1 .
To compare the activity of KF/alumina with those of
other solid bases, magnesium oxide, calcium oxide and
alkali ion-modified alumina were used. Magnesium
and calcium oxide were prepared by in situ decom-
position of the corresponding hydroxides at elevated
temperatures in vacuo prior to the reaction. The alkali
ion-modified aluminas (without F) were prepared by
impregnation of -alumina (JRC-AL04) with aqueous
solution of KOH, followed by drying at 373 K in air.
The amounts of KOH were 1.2 and 4.5 mmol g1 .
The surface areas of the catalyst were calculated by
applying the BET method to the nitrogen adsorption
at 77 K.
2.2. Gas phase reaction
A closed recirculation reactor connected to a con-
ventional vacuum line and to a gas chromatograph
was used to carry out double bond isomerization of
1-butene at 273 K. Prior to the reaction, the catalyst
was evacuated under ca. 103 Pa at elevated tempera-
tures for 2 h. The products were analyzed by GC with
a VZ-7 column.
2.3. Liquid phase reactions
Double bond isomerization of 1-pentene was car-
ried out in an H-shaped glass batch reactor. The two
branches of the reactor were separated by a break-
able seal. A sample of the catalyst was placed in
one branch, outgassed at an elevated temperature for
2 h, and sealed. The purified 1-pentene was stored
 H. Kabashima et al. / Applied Catalysis A: General 194 195 (2000) 227240
in the other branch until it was introduced through
the breakable seal by distillation into the branch con-
taining the catalyst thermostated at liquid nitrogen
temperature. The reaction was initiated by melt-
ing the reactant rapidly at a reaction temperature of
273 K, followed by stirring. After a certain reaction
time, the products were filtered out from the catalyst
and then analyzed by GC with an OV-101 capillary
column.
Tishchenko reaction of pivalaldehyde and Michael
addition of nitromethane to butene-2-one were carried
out by the same procedures as in the case of 1-pentene.
The products were analyzed by GC with DEGS
column.
2.4. X-ray analysis
X-ray diffraction (XRD) patterns of the powdered
samples were recorded on a JEOL JDX-3500 system
using Cu K radiation. All the measurements were
performed in the range of 2 = 1090 .
Elemental analysis of KF/alumina by X-ray fluo-
rescence (XRF) spectroscopy was performed on a
RIGAKU RIX-3100 system using Rh K radiation.
X-ray photoelectron spectroscopy (XPS) was per-
formed on a RIGAKU XPS-7000 system with Mg K
radiation. Each binding energy was calibrated to the
binding energy of C1s at 184.5 eV.
2.5. 19 F MAS NMR
High-resolution solid-state NMR spectra were
recorded at room temperature with magic angle spin-
ning (MAS) on a Fourier transform pulsed NMR
spectrometer (JEOL JMN CMX-300) equipped with
a cp/MAS unit. 19 F MAS NMR spectra were taken
at 282.4 MHz with high power decoupling. The cycle
time was 5.0 s and 90 pulse width was 2 s. The
spinning rate of the sample was 15 kHz. 19 F chemical
shifts were referenced to CFCl3 (0.0 ppm).
3. Results and discussion
The reactions examined in the present study are
summarized in Scheme 1.
229
3.1. Double bond isomerization of 1-butene in gas
phase
Fig. 1 shows the variations of the activities of dif-
ferent KF/alumina catalysts for double bond isomer-
ization of 1-butene as a function of pretreatment tem-
perature. The activity of Fluka-KF/alumina appeared
when the sample was pretreated at 473 K, and reached
its maximum at the temperature of 623 K. As the pre-
treatment temperature was raised higher than 623 K,
the activity decreased sharply and finally disappeared
at the temperature of 823 K. After being pretreated at
823 K, the Fluka-KF/alumina did not exhibit any ac-
tivity even when the reaction temperature was elevated
to 423 K.
Similar relations between the pretreatment tem-
perature and the activity were observed for 1.2 and
4.6 mmol g1 -KF/alumina, but the temperatures of
appearance of the activity and the maximum activity
shifted to higher temperature. The activities of 1.2
and 4.6 mmol g1 -KF/alumina appeared when they
were pretreated at 573 K, and reached maxima at the
temperature of 723 K. Such activities were eliminated
by pretreatment at 873 K.
When TPD was measured with untreated KF/alumina
catalysts of all types, evolution of H2 O and CO2
was observed in the temperature range 523873 K.
Therefore, it is suggested that the appearance and
the increase of the activity observed as the pretreat-
ment temperature was increased are caused mainly
by removal of H2 O and/or CO2 from the surface. The
active sites are covered with H2 O and/or CO2 when
pretreated below 523 K.
Calcination of KF/alumina at 773 K in air prior to
the pretreatment by evacuation resulted in a marked
decrease in the activity. The variation of the activity
of 1.2 mmol g1 -KF/alumina as a function of the pre-
treatment temperature is also shown in Fig. 1. The
activity of the calcined catalyst was two-orders of
magnitude lower than that of uncalcined catalyst.
Fig. 2 shows the initial cis/trans ratios of 2-butene
as a function of the pretreatment temperature over
different KF/alumsina catalysts. Generally, the initial
cis/trans ratio in 2-butene produced in double bond
isomerization of 1-butene is high for base-catalyzed
reaction. The initial cis/trans ratios obtained for
KF/alumina catalysts were at least 8, though the
ratios varied with the pretreatment temperature, indi-
230 H. Kabashima et al. / Applied Catalysis A: General 194 195 (2000) 227240

Scheme 1. Various reactions over KF/alumina catalyst.

cating that the isomerization proceeds via an anionic
intermediate.
Fig. 3 shows the influence of pretreatment temper-
ature on the surface area of KF/alumina catalysts and
KOH/alumina. The surface areas of Fluka-, 1.2 and
4.6 mmol g1 -KF/alumina did not decrease much with
the pretreatment temperature. It is concluded that the
rapid decrease in the activity above 673 and 773 K of
the pretreatment temperature is not caused by the de-
crease of surface area. The surface chemical state of
the KF/alumina seems to change with thermal treat-
ment above 673 K or 773 K.
The catalytic activities of KF/CaF2 and KF alone
were measured after pretreatment at 623 K for com-
 H. Kabashima et al. / Applied Catalysis A: General 194 195 (2000) 227240 231

Fig. 1. Variation of the activity of KF/alumina for double bond isomerization of 1-butene at 273 K as a function of pretreatment temperature.
: Fluka-KF/alumina, 4: 4.6 mmol g1 -KF/alumina, : 1.2 mmol g1 -KF/alumina, : calcined 1.2 mmol g1 -KF/alumina.

Fig. 2. Initial cis/trans ratio of 2-butene for double bond isomerization of 1-butene at 273 K over KF/alumina as a function of pretreatment
temperature. : Fluka-KF/alumina, 4: 4.6 mmol g1 -KF/alumina, : 1.2 mmol g1 -KF/alumina.
232 H. Kabashima et al. / Applied Catalysis A: General 194 195 (2000) 227240

Fig. 3. Influence of pretreatment temperature on the surface area of KF/alumina and KOH/alumina. : Fluka-KF/alumina, 4:
4.6 mmol g1 -KF/alumina, : 1.2 mmol g1 -KF/alumina, : 1.2 mmol g1 -KOH/alumina.

parison with those of KF/alumina catalysts, but they
did not show appreciable activity under the same re-
action condition.
Fig. 4 shows the variation of the activities of
1.2 mmol g1 -KOH/alumina as a function of the pre-
treatment temperature both for calcined and uncal-
cined samples. In contrast to KF/alumina, the activity
of 1.2 mmol g1 -KOH/alumina kept increasing as the
pretreatment temperature increased. No doubt the de-
activation caused by the pretreatment under a vacuum
at high temperature is the characteristic feature only
for KF/alumina catalyst.
3.2. Double bond isomerization of 1-pentene in
liquid phase
We have briefly reported that the variations of
the activities for 1-pentene and Michael addition
of nitromethane to butene-2-one are different [22].
Fig. 5 shows the variations of the activities of the
Fluka-KF/alumina for these two reactions as a func-
tion of the pretreatment temperature together with
Tishchenko reaction of pivalaldehyde. The varia-
tion of the activity of Fluka-KF/alumina for double
bond isomerization of 1-pentene is similar to that of
1-butene. With an increase in the pretreatment tem-
perature, the activity for double bond isomerization
of 1-pentene appeared at 523 K, reached a maximum
at 623 K and disappeared at 723 K. No activities were
observed for KF and -alumina at a reaction temper-
ature of 273 K. This suggests that the active sites of
Fluka-KF/alumina are not the same as those on the
surface of KF, but are generated by interaction of KF
with the surface of alumina.
3.3. Tishchenko reaction of pivalaldehyde in liquid
phase
Because of the similarity of the reaction mecha-
nism, Tishchenko reaction has been considered to
be closely related with Cannizzaro reaction, which
is a typical base-catalyzed reaction. Fluka- and
4.6 mmol g1 -KF/alumina exhibited the activity for
Tishchenko type esterification of pivalaldehyde, and
the selectivity for the neopentyl pivalate was more
than 98%.
As already shown in Fig. 5, the variations of the
activity of Fluka-KF/alumina for the Tishchenko
 H. Kabashima et al. / Applied Catalysis A: General 194 195 (2000) 227240 233

Fig. 4. Activities of uncalcined KOH/alumina and KOH/alumina calcined at 773 K in air for double bond isomerization of 1-butene at
273 K. : uncalcined 1.2 mmol g1 -KOH/alumina, : calcined 1.2 mmol g1 -KOH/alumina.

Fig. 5. Variation of activity of Fluka-KF/alumina for double bond isomerization of 1-pentene, Tishchenko reaction of pivalaldehyde and
Michael addition of nitromethane to butene-2-one as a function of pretreatment temperature. : double bond isomerization of 1-pentene;
Catalyst, 200 mg; 1-Pentene, 4 mmol; Reaction temperature, 273 K; Reaction time, 0.5 h. : Tishchenko reaction of pivalaldehyde; Catalyst,
50 mg; Pivalaldehyde, 5 mmol; Reaction temperature, 323 K; Reaction time, 5 h. 4: Michael addition of nitromethane to butene-2-one:
Catalyst, 10 mg; Nitromethane, 12 mmol; Butene-2-one, 4 mmol; Reaction temperature, 273 K; Reaction time, 0.5 h.
234 H. Kabashima et al. / Applied Catalysis A: General 194 195 (2000) 227240
Table 1
Activity for Tishchenko reaction of pivalaldehyde at 323 Ka
Catalyst Pretreatment temperature (K)
Fluka-KF/alumina 623
4.6 mmol g1 -KF/alumina 623
KF 623
-alumina (JRC-ALO4) 773
MgO 873
CaO 873
Mg(OH)2 373
Ca(OH)2 373
4.5 mmol g1 -KOH/alumina 623
1.2 mmol g1 -KOH/alumina 623
1.2 mmol g1 -RbOH/alumina 623
a Pivalaldehyde, 5 mmol; Catalyst weight, 50 mg; Reaction time, 5 h.
reaction of pivalaldehyde and 1-pentene isomeriza-
tion as a function of the pretreatment temperature are
similar to each other. The active basic sites on the
Fluka-KF/alumina for the Tishchenko reaction of pi-
valaldehyde are suggested to be the same as those for
double bond isomerization of 1-butene and 1-pentene.
The activities of catalysts other than Fluka-KF/
alumina for Tishchenko reaction of pivalalde-
hyde are given in Table 1 together with that
of Fluka-KF/alumina pretreated at 623 K. Only
KF/alumina catalysts, CaO and MgO exhibited the
activity; non-supported KF and KOH/alumina cat-
alysts with different amounts of KOH showed no
activity. Such high activity of KF/alumina suggests
that active sites of KF/alumina are generated by inter-
actions of KF with the surface of alumina. It should
be noted that the activity of the KOH/alumina for
the Tishchenko reaction of pivalaldehyde was much
lower than that of KF/alumina. A low activity of
KOH/alumina for the Tishchenko reaction as com-
pared to that of KF/alumina was also pointed out in
the studies of the reactions of n-butyraldehyde [23]
and benzaldehyde [24].
3.4. Michael addition of nitromethane to
butene-2-one in liquid phase
Michael addition of nitromethane to butene-2-one
proceeds on Fluka-KF/alumina to produce 5-nitropen-
tane-2-one. The activities of Fluka-KF/alumina for
the Michael addition are plotted against pretreatment
temperatures and are included in Fig. 5. The maxi-
Surface area (m2 g1 ) Conversion (%)
39 41
39 23
0.5 0
171 1
172 55
59 88
74 0
6 0
110 0
157 0
132 0
mum activity was obtained by the pretreatment of
Fluka-KF/alumina at 623 K, which is the same temper-
ature for the maximum activity for double bond iso-
merization of 1-pentene and for Tishchenko reaction of
pivalaldehyde. Although the Fluka-KF/alumina exhib-
ited activity for neither isomerization of 1-pentene nor
the Tishchenko reaction of pivalaldehyde when treated
at 823 K, it exhibited activity for the Michael addition
to a considerable extent. The conversion was 56% rela-
tive to that of the catalyst pretreated at 623 K under the
same reaction conditions. The fact that the activity for
Michael addition of nitromethane to butene-2-one did
not change much with the pretreatment temperature in
contrast to a large change in the activities for double
bond isomerization of 1-butene and 1-pentene and for
Tishchenko reaction of pivalaldehyde, indicates that
the active sites for Michael addition are different from
those for the other reactions. Consequently, at least two
types of basic sites are suggested to be generated on
KF/alumina. Their generation depends strongly upon
the pretreatment condition.
The activities of the other catalysts for the Michael
addition are summarized in Table 2 together with those
of Fluka- and 4.6 mmol g1 -KF/alumina. The activi-
ties of non-supported KF, -alumina, MgO and CaO
were small.
3.5. Structural analysis of KF/alumina by XRD
Structural changes caused by pretreatment at
different temperatures were studied by XRD for
Fluka-KF/alumina and 4.6 mmol g1 -KF/alumina.
 H. Kabashima et al. / Applied Catalysis A: General 194 195 (2000) 227240
Table 2
Activity for Michael addition of nitromethane to butene-2-one at 273 Ka
Catalyst Pretreatment temperature (K)
4.6 mmol g1 -KF/alumina 373
4.6 mmol g1 -KF/alumina 673
4.6 mmol g1 -KF/alumina 823
KF 623
-alumina (JRC-ALO4) 823
1.2 mmol g1 -KOH/alumina 873
MgOc 873
CaOd 873
a Nitromethane 12 mmol; Butene-2-one, 4 mmol; Catalyst weight, 50 mg; Reaction time, 0.5 h.
b Conversion was calculated by the decrease in butene-2-one percentage.
c MgO (10 mg) was prepared by in situ decomposition of Mg(OH) .
2
d CaO (10 mg) was prepared by in situ decomposition of Ca(OH) .
2
XRD patterns are shown in Fig. 6. With 4.6 mmol g1 -
KF/alumina, only diffraction peaks ascribed to
K3 AlF6 and -alumina were observed, regardless of
the pretreatment temperature. With Fluka-KF/alumina
which contained 8.2 mmol g1 KF, diffraction peaks
ascribed to KF and K2 CO3 were observed in addition
to the peaks for K3 AlF6 and -alumina. Appearance
of the peaks ascribed to KF and K2 CO3 depended
upon the pretreatment temperature, but the peaks
ascribed to K3 AlF6 and -alumina were observed,
regardless of the pretreatment temperature. When
the pretreatment temperature was raised from 623 to
873 K, the peaks ascribed to K2 CO3 appeared, with a
concomitant decrease of the peaks ascribed to KF.
Duke et al. reported the formation of K2 CO3
(carbonate will form when K2 O, which is produced
as the alumina lattice is destroyed, absorbs atmo-
spheric CO2 ) by IR spectroscopy [17]. They proposed
that K2 CO3 is formed by the following successive
reactions (Eqs. (3) and (4)), and postulated that con-
sumption of K2 O by the formation of K2 CO3 caused
deactivation of KF/alumina when the pretreatment
temperature was increased.
12KF + Al2 O3 2K3 AlF6 + 3K2 O (3)
+3CO2 3K2 CO3
3K2 O+ (4)
The possibility that the formation of K3 AlF6 is rel-
evant to the catalytic activity of KF/alumina is quite
low, because the diffraction peaks ascribed to K3 AlF6
were still present after the pretreatment at 873 K, due
to which the activities for isomerization of 1-butene
235
Surface area (m2 g1 ) Conversionb (%)
11
110 51
100 39
0.5 3
170 1
160 27
235 2
132 1
and 1-pentene as well as those for Tishchenko re-
action disappeared. Baba et al. also reported that
K3 AlF6 is not the catalytically active species for
self-condensation of benzaldehyde [18] and methathe-
sis of trimethylsilylethylene [19]. They found no ac-
tivity of neat K3 AlF6 and alumina-supported K3 AlF6 .
However, the possibility that K3 AlF6 is active species
for Michael addition of nitromethane to butene-2-one
can not be excluded, because the KF/alumina pre-
treated at 873 K still exhibited the activity for this
reaction.
3.6. Elemental analysis of KF/alumina by XRF
Changes in bulk composition of two kinds of
KF/alumina with the pretreatment temperature were
measured by XRF; the results are summarized in
Table 3. It is evident that both K and F were lost
from the catalysts during pretreatment at high tem-
peratures. From the original content of K and F,
Fluka-KF/alumina lost 17.1% K and 36.6% F, and
4.6 mmol g1 -KF/alumina lost 15.2% K and 23.9% F
by heating from 373 to 873 K. The percentages lost
from the catalyst were different for K and F, indicating
that K and F escaped independently from the catalyst.
The change in bulk composition can not explain the
change in the catalytic activities for double bond iso-
merization of 1-butene and 1-pentene, and Tishchenko
reaction of pivalaldehyde. There still remained large
fractions of K and F, but the activities were completely
diminished after pretreatment at 873 K.
236 H. Kabashima et al. / Applied Catalysis A: General 194 195 (2000) 227240

Fig. 6. XRD pattern of KF/alumina. (a) 373 K pretreated Fluka-KF/alumina, (b) 623 K pretreated Fluka-KF/alumina, (c) 873 K pretreated
Fluka-KF/alumina, (d) 373 K pretreated 4.6 mmol g1 -KF/alumina, (e) 723 K pretreated 4.6 mmol g1 -KF/alumina, (f) 873 K pretreated
4.6 mmol g1 -KF/alumina. : KF, : K3 A1F6 , 4: A12 O3 , : K2 CO3 .
 H. Kabashima et al. / Applied Catalysis A: General 194 195 (2000) 227240 237

Table 3
XRF analysis on KF/alumina pretreated at different temperaturesa
Sample Pretreatment temperature (K) K (mmol g1 ) F (mmol g1 ) Al (mmol g1 )

Fluka-KF/alumina 373 8.2 8.2 10.3

623 7.5 7.0 11.2
873 6.8 5.2 12.4
4.6 mmol-KF/alumina 373 4.6 4.6 14.4
723 4.3 3.9 14.8
873 3.9 3.5 15.4
a Rh K, 30 kV130 mA; K, LiF; F, TAP; Al, PET.

3.7. Surface analysis of KF/alumina by XPS
Changes in surface composition of two kinds
of KF/alumina with the pretreatment temperature
were measured by XPS; the results are summarized
in Table 4. The surfaces of Fluka-KF/alumina and
4.6 mmol g1 -KF/alumina were covered with K and
F by 40% and 15%, respectively. With increasing the
pretreatment temperature, the contents of K and F
increased to a small extent by pretreatment at 623 K
or 723 K, and decreased by pretreatment at 873 K for
both KF/alumina samples. Percent decreases in K and
F by pretreatment at 873 K were close to 10% of the
original content for both samples.
The changes in surface composition can not explain
the changes in the catalytic activities with the pretreat-
ment temperature. It is obvious that all the K and/or
F present on the surface are not necessarily associated
with the formation of catalytically active sites.
3.8. Chemical state analysis of KF/alumina by 19 F
MAS NMR
The state of F and its change with the pretreat-
ment temperature were studied by 19 F MAS NMR
for two kinds of KF/alumina: Fluka-KF/alumina and
1.2 mmol g1 -KF/alumina. 19 F MAS NMR spectra are
shown in Figs. 7 and 8 for Fluka-KF/alumina and
1.2 mmol g1 -KF/alumina, respectively.
With Fluka-KF/alumina, four peaks appeared: at
123, 132, 157 and 166 ppm. These four peaks
are ascribed to KF associated with water, KF, K3 AlF6 ,
and AlF3 , respectively [1419]. The strongest peak
appeared at 157 ppm, regardless of the pretreat-
ment temperature. The peak at 123 ppm decreased
with an increase in the pretreatment temperature, and
disappeared when pretreated at 873 K. The peak at
132 ppm, which is ascribed to KF, increased on an
increase in the pretreatment temperature from 373
to 623 K, and then disappeared when pretreated at
873 K. The peak at 166 ppm was small and remained
almost constant for any pretreatment temperatures.
Besides these four peaks, a broad shoulder peak seems
to exist around 150 ppm for the samples pretreated
at 373 and 623 K. The peak appears to decrease after
pretreatment at 873 K.
As the NMR spectra are compared with the cat-
alytic activities, the change in the peak intensity at
132 ppm with the pretreatment temperature runs
almost parallel to the activities for isomerization

Table 4
Calculated results of at.% KF/alumina by XPS analysis dataa
Catalyst Pretreatment temperature (K) K (at.%) F (at.%) Al (at.%) O (at.%)
Fluka-KF/alumina 373 20.8 19.6 12.7 46.9
623 22.1 20.8 12.9 44.2
873 18.8 17.7 17.2 46.3
4.6 mmol-KF/alumina 373 8.1 6.0 27.1 58.8
723 8.4 6.3 27.1 58.2
873 7.2 5.4 28.7 58.9
a Mg K 1254 eV, 12 kV-20 mA. At.% was calculated by using the atomic cross-sections presented by reference [25] and the peak

areas of F 1s, K 2p, Al 2p and O 1s.

238 H. Kabashima et al. / Applied Catalysis A: General 194 195 (2000) 227240

Fig. 7. 19 F MAS NMR spectra of Fluka-KF/alumina pretreated at different temperatures. (a) Only KF, (b) 373 K, (c) 623 K, (d) 873 K. :
123 ppm KFwater, : 132 ppm KF, : 157 ppm K3 AlF6 , : 166 ppm AlF3 .

of 1-butene and 1-pentene, and Tishchenko reac- self-condensation of benzaldehyde and methathesis
tion. Baba et al. also found the similarity in the of trimethylsilylethyne for the KF/alumina catalyst
change with pretreatment temperature between the possessing 5 mmol KF [19]. They concluded that F
peak intensity at 135 ppm and the activities for the ion species giving a peak at 135 ppm are related to
 H. Kabashima et al. / Applied Catalysis A: General 194 195 (2000) 227240
Fig. 8. 19 FMAS NMR spectra of 1.2 mmol g1 -KF/alumina at dif-
ferent temperatures; (a) 373 K, (b) 723 K, (c) 873 K. : 121 ppm
KFwater, : 150 ppm This peak is directly related to the cat-
alytic activity, : 157 ppm K3 AlF6 , : 171 ppm AIF3 .
the active sites, though the peak was not assigned to
a specific species but only to F ion species. How-
ever, the possibility that the species giving a peak at
132 ppm (or 135 ppm in their paper) are relevant
to the active sites has to be excluded when 19 F MAS
NMR of 1.2 mmol g1 -KF/alumina was measured.
Fig. 8 shows 19 F MAS NMR spectra of 1.2
mmol g1 -KF/alumina pretreated at different tem-
peratures. Since the amount of KF is smaller for
1.2 mmol g1 -KF/alumina than Fluka-KF/alumina,
the peak at 157 ppm is smaller for 1.2 mmol g1 -KF/
alumina, which enables the broad peak at about
150 ppm to appear clearly. Four peaks appear at 171,
239
157, 121 and 150 ppm. The former three peaks are
ascribed to AlF3 , K3 AlF6 and KF associated with wa-
ter, respectively [1419]. The peak ascribed to KF was
hardly visible after pretreatment at any temperatures.
The absence of the peak at 132 ppm after pretreat-
ment at 723 K demonstrates that the species of the
peak at 132 ppm are not relevant to the active sites.
The broad peak at about 150 ppm varied its inten-
sity parallel to the catalytic activities for double bond
isomerization of the olefins and Tishchenko reaction.
The peak at about 150 ppm appeared clearly only
when the material was pretreated at 723 K. Therefore,
it is suggested that the species giving a peak at about
150 ppm are relevant to the catalytic activities.
The structure of the species giving a peak at about
150 ppm is not certain at present. However, it is pos-
tulated that (1) the compound is formed by the reac-
tion of KF and alumina and (2) this F ion species is
more electron-poor than F ion species of AlF3 and
K3 AlF6 .
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