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~ APPLE

ID CATALYSIS
A: GENERAL
ELSEVIER Applied Catalysis A: General 142 (1996) 375-386

Dehydrogenation of isopropylic alcohol on a


Cu/SiO 2 catalyst: a study of the activity evolution
and reactivation of the catalyst
A.J. Marchi a J.L.G. Fierro b j. Santamaria c A. Monz6n c.,
a INCAPE, F.I.Q.-U.N.L-CONICET, Santiago del Estero, 2654, 3000-Santa Fe, Argentina
h lnstituto de Cat6lisis y Petroleoqufmica (C.S.L C.), Campus Uniuersidad Autonoma de Madrid, Cantoblanco.
28949 Madrid, Spain
Department of Chemical and Emdronmental Engineering, Unit,ersity of Zaragoza, 50009 Zaragoza, Spain

Received 25 November 1995; revised 13 February 1996; accepted 13 February 1996

Abstract

The activation-deactivation behaviour of a C u / S i O 2 catalyst during isopropyl alcohol (IPA)


dehydrogenation to acetone has been studied. Simultaneous reduction and sintering processes are
responsible for the activation-deactivation behaviour observed, The reducing H 2 atmosphere
impulses the transformation of CuO into Cu ° and at the same time the sintering of the Cu ° phase
formed. The reoxidation treatment in air at 573-673 K is able to regenerate a finely dispersed
CuO phase from the sintered Cu ° phase. As a result, the active phase is redispersed and the
dehydrogenation activity is recovered. The results indicate the existence of two CuO phases on the
catalyst, with different properties. The CuO phase with a low reduction temperature, a small
particle size and a poor crystallinity, is the one responsible for the appearance of the finely
dispersed Cu °, which is the active phase for this reaction.

Keywords: Cu/SiO2; Dehydrogenation; Activation-deactivation; Sintering; Redispersion

1. Introduction

Experimental evidence shows that activation and deactivation processes are


simultaneously present in numerous catalytic processes. This seems evident in
many reaction systems in which the catalytic activity exhibits a maximum with

* Corresponding author. Tel.: ( + 34-76) 761157; fax: ( + 34-76) 761159; e-mail: amonzon@posta.unizar.es.

0926-860X/96/$15.00 Copyright © 1996 Elsevier Science B.V. All rights reserved.


PII S 0 9 2 6 - 8 6 0 X ( 9 6 ) 0 0 0 8 7 - 7
376 A.J. Marchi et al. / Applied Catalysis A: General 142 (1996) 375-386

time on stream. In this situation, activation processes are dominant during the
period of increasing activity, while the decreasing activity period corresponds to
the dominance of deactivation processes [1,2]. In other words, in these systems
the observable evolution of activity is the sum of activation processes which
increase the number of active sites (e.g., reduction of oxides in metal-catalyzed
hydrogenations), and deactivation processes which tend to reduce the number of
available sites (poisoning, coking, sintering, solid phase transformations). Among
the reactions in which activity versus time maxima can be found are Fischer-
Tropsch synthesis [3-6], Kobel-Engelhardt synthesis [7], CO 2 methanation
[8,9], CO oxidation [ 10], hydrodesulfurization processes [ 11,12], alcohol dehy-
drogenation [ 13-15] and polymerization processes [ 16-18], as well as the above
mentioned hydrogenation reactions [19,20].
The period of increasing activity often constitutes a significant fraction of the
operation time of the catalyst between regenerations [1]. This means that the
knowledge of the activation-deactivation kinetics is very useful to appropriately
design and optimize the operation of catalytic reactors where activation and
deactivation processes are present. Also, the investigation of the causes and
mechanisms of activation and deactivation of a given catalyst allows a more
rational approach to its design and preparation. In spite of this, it is often found
that investigations on this type of systems are restricted to the period of net
decreasing activity, i.e., where most of the activation processes are already over
and the deactivation can be studied on its own [1]. In laboratory studies of this
kind, prior to the reaction the catalyst is subjected to an intense activation
process that consumes most of the potentially active sites and essentially
precludes any further activation during reaction. While this method is effective
to simplify the study, it also prevents access to important information concern-
ing the activation process and the behavior of the catalyst in general.
In this work, a study is presented of the activation-deactivation behaviour of
a C u / S i O 2 catalyst during isopropyl alcohol (IPA) dehydrogenation to acetone.
The causes of activation and deactivation are analyzed with the objective of
gaining a better understanding of these processes, and to draw some practical
conclusions regarding appropriate methods for catalyst regeneration on this
system.

2. Experimental

A commercial, shell-type Cu (6 wt.-%)/SiO 2 catalyst with a particle size


between 1000 and 1600 microns was used. Both Cu and the promoter Na were
located in a thin external layer of the catalyst particles. The BET surface area of
the catalyst was 4 m 2 / g , (Micromeritics Pulse Chemisorb 2700), and the pore
volume and the apparent density were respectively 0.61 c m 3 / g and 0.5 g / c m 3
(Micromeritics Autopore II 9215).
A.J. Marchi et al. / Applied Catalysis A: General 142 (1996) 375-386 377

Catalytic activity measurements were carried out in a 15 mm I.D., 200-mm


long fixed-bed reactor operated under differential conditions and in the absence
of diffusional resistances, according to the results obtained in a previous work
[15]. The catalyst bed was diluted (ca. 50% by volume) with inert ceramic
packing of a similar size. Isothermal operation was ensured by immersing the
bed into an external sand fluidized bed, which provided a good heat transfer
coefficient and high thermal inertia. This was necessary in order to minimize
temperature oscillations which, however small, were found to have an important
effect upon the catalytic rates measured in this work. The reaction was carried
out at atmospheric pressure and at temperatures between 433 and 453 K. The
reactor feed contained IPA (with a partial pressure of 0.2 to 0.66 bar), acetone
(0.04 to 0.4 bar), hydrogen (0.10 to 0.24 bar), and nitrogen (balance). A precise
dosifying pump delivered mixtures containing the appropriate proportions of
IPA and acetone to an evaporator. This stream was then mixed with mass flow
controlled streams of H 2 and N 2 and the resulting mixture entered the reactor at
spatial times between 360 and 380 g min/mol.
Prior to the kinetic experiments, the catalyst was activated in situ using a
three stage procedure: (i) purging with nitrogen for 1 h at 573 K; (ii) cooling
down under nitrogen to 453 K; (iii) reduction using 30% H 2 in N 2 for 15 or 30
min. During the kinetic measurements the exit gas stream from the reactor was
passed through a cold trap to remove condensables and then analyzed by on-line
gas chromatography. The only products detected were IPA, acetone and hydro-
gen, indicating that secondary reactions could be neglected under the conditions
employed in this work.
Temperature programmed reduction (TPR) experiments were carried out in a
separate unit using a 5% H 2 - A r mixture with a total flow rate of 20 cm3/min
and a heating ramp of 6 K / m i n . X-ray photoelectron spectroscopy (XPS) data
were obtained in a Fisons Escalab 200 R unit, equipped with a cell for 'in situ'
pretreatments. The measurements were carried out using M g - K a radiation, at a
residual pressure of 2 • 10 - 9 Torr or lower. The C ls line at 284.9 eV was used
as an internal standard. X-ray diffraction (XRD) patterns were obtained in a
R i g a k u / M a x System unit, using Ni-filtered Cu-Kc~ radiation, and a voltage of
40 kV. The patterns were recorded in the range of 3 0 - 7 0 ° using a scanning
velocity of 0.03°/s.

3. Results and discussion

3.1. Evolution of catalytic activity

Under the conditions employed, the same behaviour was observed in all
cases: the activity of the fresh C u / S i O 2 catalyst initially increases with time
until a maximum is reached, and then a rapid deactivation follows. The rate of
378 A.J. Marchi et al. /Applied Catalysis A." General 142 (1996) 375-386

.~ 5
E

o
~3 @

~2,
~t

0
0 40 80 120 160 200

time (min.)
Fig. 1. Evolution of activity with time on stream. The reaction was carried out at T = 433 K, and P1PA = 0.20
bar, and no acetone or hydrogen was added. After 90 rain on stream the reactant feed was interrupted, and the
catalyst was subjected to 30% H 2 in N 2 for 15 min, resuming the initial feed composition thereafter.

both activity increase and loss depends on the experimental conditions employed
(first part of Figs. 1 and 2).
Fig. 1 also shows the effect of a treatment using 30% H 2 in N 2 for 15 rain at
180°C upon the partially deactivated catalyst. It can be seen that this treatment
did not lead to a recovery of catalytic activity, but rather to an additional loss
(Fig. 1). However, the same treatment had a very different effect when
performed after oxidation with air at 300°C. In this case, a strong new activation
period was observed, leading to a maximum activity comparable to that reached
previously (Fig. 2).

30

,,..., 25
do
.~ 20
E k
o 15 ~,.
E
10 ~"
••m

0 . . . . i, , . , L . . . . i . . . . i .. J , l , a . . i . . . . i.

0 40 80 120 160 200 240 28q

time (min.)
Fig. 2. Evolution of activity with time on stream. The reaction was carried out at T = 453 K, PleA = 0.60 bar,
PAc = 0.035 bar and PH2 = 0.23 bar. After 110 min on stream the reactant feed was interrupted, and the
catalyst was subjected to oxidation in air for 1 h, then to 30% H 2 in N 2 for 15 min, resuming the initial feed
composition thereafter.
A.J. Marchi et a l . / Applied Catalysis A: General 142 (1996) 375-386 379

The evolution of catalytic activity, both for the fresh catalyst (Figs. 1 and 2)
and for the catalyst after the treatment in air and hydrogen (Fig. 2) strongly
suggests the presence of simultaneous activation and deactivation processes. The
initial activation period is a consequence of the mild reduction conditions
employed during the pretreatment of the catalyst before reaction. It seems likely
that only part of the CuO capable of reduction at 453 K was converted during
this pretreatment. Thus, the hydrogen released in the reaction would continue
the reduction of CuO thereby increasing the number of active sites and
consequently the observed reaction rate. However, Figs. 1 and 2 show that, after
a certain time on stream, the deactivation of the catalyst causes a net decrease in
the observed reaction rate.
Given the characteristics of the system studied, three possible causes of
deactivation were considered: (i) sintering of metallic Cu particles; (ii) deposi-
tion of carbonaceous residues on the catalyst surface; (iii) poisoning of the
active surface by sulphur a n d / o r chlorine. The last possibility was rejected in
view of the purity of the reactants used, which was specifically verified
regarding these compounds. Also, temperature programmed oxidation (TPO)
experiments did not detect carbonaceous compounds on the deactivated catalyst
surface. Supplementary evidence was provided by XPS analysis, in which the
intensity of the C 1s peak relative to the Si 2p peak was very similar in samples
before and after reaction. Therefore, the sintering of Cu ° particles seems to be
the most likely cause of the observed deactivation in agreement with the
explanation given by Pepe et al. [21-23], for this type of catalysts.
On the other hand, the reactivation of the catalyst after treatment in air and
hydrogen can be explained as a result of: (i) recovery of the original CuO phase
by oxidation of the sintered Cu °, and (ii) regeneration of the Cu ° phase by
reduction with the hydrogen-containing mixture. The treatment in air and
hydrogen would therefore redisperse the sintered Cu ° phase, leading to a
recovery of the initial catalytic activity. There is ample information in the
literature on catalytic systems with a behaviour similar to the one shown in this
case [24-26].

3.2. Characterization of fresh and used catalysts

In order to further substantiate the above suggested explanations, the catalyst


at different reaction stages was characterized using XPS, TPR and XRD. In
general, three different types of samples were used: fresh catalyst, used catalyst
with some degree of remaining activity and completely deactivated catalyst.
The TPR analysis of the fresh catalyst revealed the presence of two overlap-
ping wide bands (Fig. 3a). The corresponding hydrogen consumption maxima
were found at 543 and 593 K. The first peak accounted for a hydrogen
consumption of 0.44 mmol of H z / g catalyst, and the second for 0.92 m m o l / g ,
i.e., a total hydrogen consumption of 1.36 mmol H z / g of catalyst. These results
380 A.J. Marchi et al. /Applied Catalysis A: General 142 (1996) 375-386

,-.2,.

.o (a)

(c)
. . . . I . . . . I . . . . I . . . . . . . , I , , , , I . . . . I . . . .

400 450 500 550 600 650 700 750 800

Temperature (K)
Fig. 3. Temperature programmed reduction of: (a) fresh catalyst, (b) partially deactivated catalyst, (c)
completely deactivated catalyst.

suggest the existence of two different Cu species on the catalyst. One possibility
would be that both species are CuO, with a different particle size. In this case,
the largest crystallites would appear in the TPR as species reducible at a higher
temperature because of the diffusion hindrance on the reduction process. Also,
Fig. 3a shows only a very small consumption of hydrogen at temperatures of
473 K and lower. Therefore, only a small fraction of the CuO would be
expected to undergo reduction during the activation pretreatment (15 min under
30% H 2, at 453 K). The hydrogen generated during the reaction would then be
responsible for the observed activation process.
When partially deactivated catalysts were subjected to temperature pro-
grammed reduction the result was a single peak, with a maximum at 588 K. This
peak was markedly asymmetric, suggesting that part of the CuO that can be
reduced at low temperature still remains as such in the used catalyst. The total
hydrogen consumption in this case was 0.76 mmol H z / g catalyst, i.e., only 55%
of the total consumption measured for the fresh catalyst. Finally, the TPR
analysis of the completely deactivated catalyst revealed a single peak with a
maximum at 583 K (Fig. 3c). The total hydrogen consumption was 0.65 mmol
H 2 / g catalyst, i.e. 48% of the total consumption for the fresh catalyst. Besides,
the peak was much more symmetric, suggesting that essentially all the CuO
species that could be reduced at the reaction temperature had been converted to
Cu °.
The results of the temperature programmed reduction experiments therefore
confirm the reduction of CuO species during reaction and, in view of the activity
maximum reached with time on stream, they also seem to indicate that beyond a
certain degree of reduction the activity of the catalyst decreases. This is
consistent with the above described scenario in which the hydrogen species in
the reaction atmosphere would favour the transition of Cu 2+ to Cu °, thus
producing new active sites, and at the same time accelerating the sintering
A.J. Marchi et al. / Applied Catalysis A: General 142 (1996) 375-386 381

i • Cu° I
1/ I "cuo I

o,.~

.g

30 35 40 45 50 55 60
20 (o)
Fig. 4. X-ray diffraction pattern of: (a) fresh catalyst after pretreatment in nitrogen for 120 min at 573 K, (b)
fresh catalyst after a reduction treatment under 30% H 2 in N 2 for 120 min at 453 K, (c) completely
deactivated catalyst after a reduction treatment under 30% H 2 in N 2 for 120 min at 453 K.

processes and the associated elimination of active sites, which becomes predom-
inant beyond a certain degree of reduction.
Fig. 4a shows the XRD patterns obtained for the fresh catalyst after pretreat-
ment in N 2 for 2 h at 573 K. The only identifiable phase is CuO, with a poorly
organized crystalline structure and a small particle size. The fresh catalyst was
then reduced, and subjected again to XRD analysis. After the standard reduction
treatment in 30% H 2 at 453 K for 30 rain (Fig. 4b), two different phases are
present: CuO and Cu °. The XRD pattern of this sample shows two additional
interesting features: only one peak corresponding to CuO is present, slightly
displaced with respect to the highest intensity peak in Fig. 4a. This would be
consistent with the presence of two CuO phases on the catalyst surface. On the
other hand, regarding Cu °, only one wide peak is observed, corresponding to the
highest intensity peak normally associated with Cu °. This indicates that the Cu °
generated in this stage is finely dispersed on the silica support. Finally, when a
sample of the catalyst deactivated during reaction is subjected to the reduction
treatment using 30% H 2 a t 453 K for 30 min (Fig. 4c), the XRD data show a
considerable increase of the crystallite size and concentration of Cu °, with
respect to that observed on the fresh catalyst sample after the same reduction
treatment. Simultaneous with the increase in the Cu ° peaks, the CuO peak
decreases, thus indicating a greater degree of reduction.
Finally, additional evidence concerning this point was provided by XPS
measurements. The Cu 2p3/2 core level spectra of two representative samples
are displayed in Fig. 5a. They show the principal peak at ca. 933.0 eV with a
shoulder at ca. 935.4 eV, which correspond to reduced (Cu ° and Cu +) and
unreduced Cu 2+ copper species, respectively. Since Cu ° and Cu t + species show
essentially the same binding energy, XPS alone cannot discriminate among these
species. A shake-up satellite above 943.0 eV, whose intensity depends on the
reduction of copper, is also observed. As only Cu 2+ ions show this satellite, but
A.J. Marchi et al. / Applied Catalysis A: General 142 (1996) 375-386
382

Cu 2p312 Cu o (a}
CB~+

Curve1 /~

Curve2 \

948 943 938 933 928


BE (eV)
2,2 (b)
2,0
1,8
1,6
1,4
1,2
1,0 •
0,8 _m m ~ _
0,6 •
O~ 4 ~ t i I . . . . I i 1,1 ¢ I I I I i | I I I ' I ~

40 50 60 70 80 90
%Cu red.
Fig. 5. (a) XPS spectra of two representative samples: after partial activation (curve l), and after reaction
(completely deactivated, curve 2). These samples yielded Icu/Isi ratios of 1.61 and 0.80 respectively, with
percentages of reduction of 42 and 64% respectively. (b) lc~ / lsi ratios versus percentage of reduction of Cu
on the catalyst, obtained from XPS analysis.

in no case Cu ~+ or Cu t), the observation of this line in partially reduced catalysts


can be taken as conclusive that certain proportion of copper still remains as
Cu 2+ ions. In order to evaluate the Cu reduction degree, curve synthesis
procedures have been applied. The formula used to quantify the proportion of
reduced copper is: 1933/]Total, where 1933 is the area of the peak centered at 933
eV (reduced copper) and 1Tota~is the total area of the Cu 2p3/2 peak, including
satellite line. Thus, from XPS measurements, the amount of reduced Cu and the
total Icu/lsi ratio can be calculated, i.e., the reduction and the sintering
processes taking place on the catalyst surface can be followed and quantified.
XPS measurements on the fresh catalyst yielded a Icu/lsi ratio of 17.0,
A.J. Marchi et al. / Applied Catalysis A: General 142 (1996) 375-386 383

,'->.

8
cq

400 500 600 700 800


Temperature (K)
Fig. 6. Temperature programmed reduction experiments carried out after a regeneration treatment with air at
673 K. (a) Partially deactivated catalyst, (b) completely deactivated catalyst.

indicating a high degree of dispersion, in agreement with XRD data. XPS


spectra of used catalyst samples (Fig. 5a), also indicated an increase of the
degree of reduction with time on stream, evidenced by a decrease in the
intensity of the 2p3/2 band and its satellite corresponding to Cu 2+, with respect
to Cu °. The Icu/Isi ratio calculated for used samples is plotted in Fig. 5b versus
the degree of reduction of the copper species on the catalyst. It can be seen that,
as the catalyst is progressively reduced, the degree of sintering increases. Thus,
when the degree of reduction increases from 40 to 55%, the C u / S i atomic ratio
decreases from 2 to about 0.75 (it must also be remembered that the value
corresponding to the fresh catalyst, not included in Fig. 5b, yielded a Icu/Isi
ratio of 17). Beyond 50% reduction, the degree of sintering is already high, and
further reduction treatments do not seem to decrease the dispersion of copper.

3.3. Catalyst regeneration

It has been shown (Fig. 2), that the original activity of deactivated catalyst
samples can be substantially recovered by an oxidation-reduction treatment. To
further investigate this aspect, partially deactivated and completely deactivated
catalyst samples were subjected to a treatment in air at 673 K, and then to
temperature programmed reduction experiments. The results are shown in Fig. 6.
In both cases the TPR profiles showed some similarities with respect to those of
the fresh catalyst (comparison of Figs. 3 and 6). For the partly deactivated
catalyst the two peaks were observed at 543 and 628 K (Fig. 6a), with hydrogen
consumption values of 0.51 and 0.84 mmol H 2 / g of catalyst, respectively, i.e.,
the total consumption was 1.35 mmol H z / g of catalyst, approximately the same
as that of the fresh catalyst. For the completely deactivated catalyst (Fig. 6b), the
TPR peaks were situated at 546 and 623 K, with hydrogen consumption values
of 0.65 and 0.69 mmol H 2 / g catalyst, again giving a total consumption of 1.35
mmol H 2 / g catalyst. These results indicate that in both cases the CuO phase has
384 A.J. Marchi et al./Applied Catalysis A: General 142 (1996) 375 386

Cu o
"~" • CuO

"~ • • (c

....... ().

30 40 50 60 70

2e (o)
Fig. 7. X-ray diffraction pattern of: (a) fresh catalyst after pretreatment in air for 120 min at 673 K, (b) fresh
catalyst after a reduction treatment under 30% H 2 in N 2 for 120 min at 493 K, (c) partly deactivated catalyst
after a oxidation-reduction treatment under air for 120 min at 673 K and then under 30% H 2 in N 2 for 120
min at 493 K, (d) completely deactivated catalyst after an oxidation-reduction treatment in air for 120 rain at
473 K and then under 30% H 2 in N 2 for 120 min at 493 K.

been completely regenerated, since the total consumption equals that of the fresh
catalyst. However, the hydrogen consumption for the CuO phase which is
reducible at lower temperatures increases from the fresh to the completely
deactivated catalyst, i.e., increases with the degree of reduction. This would
suggest that the reoxidation treatment favours the formation of the low reduction
temperature CuO phase from the Cu ° generated during the course of the
reaction. With respect to the high reduction temperature CuO, the effect seems
to be the opposite since the displacement of the high temperature peak towards
higher temperatures would indicate a higher degree of sintering.
The partly and completely deactivated catalyst samples were also subjected to
XRD analysis after treatment in air at 673 K. The fresh catalyst yielded similar
XRD patterns whether treated with nitrogen or with air (Figs. 4 and 7a). After
reduction with 30% H 2 in N 2 at 493 K (Fig. 7b), the catalyst displayed patterns
corresponding to two phases: Cu ° and a CuO phase which was not reduced
under the conditions employed. When a sample of partly deactivated catalyst
was subjected to the same treatment in air, the CuO phase was regenerated (Fig.
7c). However, there are several significant features in this curve: (i) the shoulder
in the peak at 20 = 35.7 degrees becomes visible after the regeneration treat-
ment indicating the presence of two phases, (ii) the width of this peak is lower
than the corresponding peak of the fresh catalyst indicating an increase of the
crystallite size, and (iii) the appearance of a clearly visible shoulder at around
35 °, which cannot be easily observed in the fresh catalyst, might be due to an
increase of the concentration of the CuO phase reducible at lower temperature.
These results are in agreement with those observed in the TPR experiments. The
lower width of the peak at 35.7 ° and the appearance of the new peaks at 42.4 °
and 61.3 ° seem to be related with the sintering of the CuO phase reducible at
A.J. Marehi et al. /Applied Catalysis A: General 142 (1996) 375-386 385

higher temperatures. This sintering was also detected in the TPR experiments, as
mentioned above. Finally, when the reoxidated catalyst was treated with 30%
H 2 in N 2 at 493 K (Fig. 7d), a metallic copper phase was obtained, with similar
characteristics to that obtained from the fresh catalyst (Fig. 7b and d). The
shoulder of the peak at 35.7 and the peak at 38.7 ° disappear, which confirms that
they are part of the phase with the lower reduction temperature. On the other
hand, the persistence of the peaks at 35.7 °, 42.4 ° and 61.3 ° show that these
belong to the phase which is not reducible at the temperatures employed.

4. Conclusions

The results of this work indicate that simultaneous reduction and sintering
processes are responsible for the activation-deactivation behaviour observed for
a C u / S i O 2 shell catalyst during the dehydrogenation of isopropyl alcohol to
acetone. The reducing H 2 atmosphere impulses the transformation of CuO into
Cu ° and at the same time the sintering of the Cu ° phase formed. This growth of
the Cu ° crystallites and the associated loss of metal surface area is favored by
the low interaction between the Cu ° crystallites and the silica support. When the
degree of reduction reaches a certain value, the rate of loss of active area due to
sintering is higher than the rate of creation of new active sites associated to the
reduction process, and the net deactivation period starts.
The reoxidation treatment in air at 573-673 K is able to regenerate a finely
dispersed CuO phase from the sintered Cu ° phase. The result is the redispersion
of the active phase and the recovery of the catalytic activity for the reaction. It
must be noted that the redispersion process affects the CuO phase with a lower
reduction temperature. This confirms the existence on the catalyst of two CuO
phases with different properties. In agreement with the TPR and XRD results, it
can be said that it is the CuO phase with a low reduction temperature, a small
particle size and a poor crystallinity, the one responsible for the appearance of
the finely dispersed Cu ° phase, which is the active phase for this reaction.

Acknowledgements

The authors wish to acknowledge the financial support of DGICYT (Spain),


for this work (Project PB94-0568).

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