Spent automotive three-way catalysts towards C-C bond forming reactions

Article abstract of DOI:10.1016/j.apcata.2012.02.012

Spent automotive three-way catalysts, containing Rh, Pd and Pt nanoparticles supported on oxide-based ceramic materials, catalyze the Heck cross-coupling of iodobenzene with butyl acrylate and unsaturated alcohols at 140 °C. Under Suzuki reaction conditions, biphenyl was formed with high yield when the same catalysts were applied. Successful hydroformylation of 1-hexene was performed in the presence of PPh₃. The catalytic activity of spent automotive three-way catalysts was compared with that of airborne matter collected in the city of Wroc?aw.

Full text of DOI:10.1016/j.apcata.2012.02.012

Applied Catalysis A: General 421–422 (2012) 148–153
Contents lists available at SciVerse ScienceDirect
Applied Catalysis A: General
journal homepage: www.elsevier.com/locate/apcata
Spent automotive three-way catalysts towards C C bond forming reactions
Ewa Mieczyn´ ska, Andrzej Gniewek, Anna M. Trzeciak∗
Faculty of Chemistry, University of Wrocław, 14 F. Joliot-Curie St., 50-383 Wrocław, Poland
a r t i c l e i n f o
a b s t r a c t
Article history:
Spent automotive three-way catalysts, containing Rh, Pd and Pt nanoparticles supported on oxide-based
ceramic materials, catalyze the Heck cross-coupling of iodobenzene with butyl acrylate and unsaturated
alcohols at 140 ◦C. Under Suzuki reaction conditions, biphenyl was formed with high yield when the
same catalysts were applied. Successful hydroformylation of 1-hexene was performed in the presence of
PPh3. The catalytic activity of spent automotive three-way catalysts was compared with that of airborne
matter collected in the city of Wrocław.
Received 17 December 2011
Received in revised form 8 February 2012
Accepted 9 February 2012
Available online 17 February 2012
Keywords:
Automotive three-way catalysts
Heck reaction
© 2012 Elsevier B.V. All rights reserved.
Suzuki reaction
Hydroformylation
Platinum group metals
Metal nanoparticles
1. Introduction
example, it has been demonstrated that scrap catalytic converters
efficiently catalyze the hydrogenation of various alkenes [20] and
The amount of platinum group metals (PGMs) in atmosphere
and in soil has increased in recent years, mainly as a result of
the worldwide application of catalytic converters in motor vehi-
cles [1–10]. Catalytic converters are widely used today to decrease
the level of pollutants such as CO, NOx, and unburned hydrocarbons
(HCs) emitted with exhaust gases from combustion engines [11,12].
The active components of automotive catalytic converters consist
of PGMs, such as Pd, Pt, and Rh, supported on ceramic material
coated with Al2O3 and other metal oxides (CeO2, ZrO2). Palladium
and platinum are active in the oxidation of CO and HCs to CO2 and
H2O, whereas rhodium catalyzes the reduction of NOx to N2. Besides
a very beneficial effect of automotive catalytic converters on the
environment, especially the atmosphere, some negative aspects
of their application should also be considered. Thus, PGMs in the
form of nanoparticles may be released from the catalytic converter
during car operation and accumulated in dust and subsequently in
water and soil [13–15]. Moreover, spent catalytic three-way con-
verters can be classified as hazardous waste materials, which is why
the development of efficient and cheap methods of PGM recovery
is very important [16–19]. In this context, it is also very important
to recognize the catalytic activity of waste PGMs present in road
dust and to estimate the catalytic activity of spent automotive cat-
alysts which may find application in other catalytic reactions. For
show activity in VOC combustion [21]. Thus, it could also be possi-
ble to use spent catalytic converters not only as a source of PGMs
but also as active catalysts for organic reactions.
The aim of the studies presented in this paper was to estimate
the catalytic ability of (a) airborne particulate matter and (b) spent
automotive three-way catalysts that have been used for a period of
6 years or more for the purification of exhaust gases. We applied
these materials without any special pretreatment as catalysts for
C
C bond forming reactions to test their catalytic potential. Aryl
halides were used as substrates in the model C C bond form-
ing reactions. It is important to point out that the presence of
aryl halides as wastes in water or soil should be seriously consid-
ered today. Consequently, knowledge about the catalytic activity of
waste PGMs towards aryl halides might be useful in anticipation of
possible transformations of aryl halides in the environment.
Usually, C C cross-coupling reactions are catalyzed by pal-
ladium compounds, both organometallic complexes and Pd(0)
nanoparticles [22–31]. In most cases these catalysts are not only
specially prepared but also stored in an inert atmosphere before
use. In this context, it was interesting to check whether PGM-
containing wastes could compete in catalytic activity with carefully
designed species.
Chemical deactivation or poisoning of the spent three-way
catalysts is an important factor to consider. The properties of
such double-use catalysts, which were first employed as a part
of gasoline-powered vehicle emission control systems, and then
engaged as the catalysts of C C coupling reactions, might be much
∗
Corresponding author. Tel.: +48 713757253; fax: +48 713282348.
E-mail address: anna.trzeciak@chem.uni.wroc.pl (A.M. Trzeciak).
0926-860X/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.apcata.2012.02.012

E. Mieczyn´ska et al. / Applied Catalysis A: General 421–422 (2012) 148–153
149
I
[cat.]
C(O)OBu
+
C(O)OBu
+
NaHCO3, DMF
140oC
C(O)OBu
I
II
Scheme 1.
influenced by contaminants that could have been introduced dur-
ing their operation in car exhaust systems. Sources of three-way
catalysts poisons include: fuel, lubrication oils and wear of engine,
and exhaust tailpipe parts. Pb, S and Si originate from fuel additives,
P, Ca, Zn and Mg from lubricants, while Fe, Cu, Ni, Cr and Cd are
derived from the engine and exhaust pipe construction materials
[32,33].
directly to the Schlenk tube. Next, the Schlenk tube was sealed with
a rubber stopper and introduced into an oil bath preheated to 80 ◦C.
The reaction was carried out at 80 ◦C for period of time between
6 and 24 h and then the reactor was cooled down. The organic
products were separated by extraction with hexane (3 portions
of 10 mL). The combined extracts (25 cm3) were GC-FID analyzed
(Hewlett Packard 5890) with 0.075 mL of dodecane as an internal
standard. The products were identified by GC–MS (Hewlett Packard
5971 A).
2. Experimental
The same procedure was applied for the filters containing air-
borne matter (4.46 g).
2.1. Characterization of PM10 filters
2.5. Heck reaction
Samples of airborne particulate matter were collected on quartz
or glass filters designed for the analysis of particles up to 10 ␮m
(PM10) in diameter. The sampling time was 24 h. The filters were
used in the city of Wrocław in 2005 and 2006 and then stored in
air at ambient temperature.
The Heck reaction was carried out in a Schlenk tube with
magnetic stirring. Reagents: butyl acrylate (0.27 mL, 1.91 mmol),
iodobenzene (0.49 mL, 4.38 mmol), NaHCO3 (0.4 g, 4.76 mmol),
DMF (10 mL), and 1 g of the spent automotive catalyst were intro-
duced directly to the Schlenk tube. Next, the Schlenk tube was
sealed with a rubber stopper and introduced into an oil bath pre-
heated to 140 ◦C. The reaction was carried out at 140 ◦C for period
of time between 4 and 24 h and then the reactor was cooled down.
In order to separate the organic products, 10 mL of diethyl ether
was added to the reaction mixture, which was then stirred for
30 min. Subsequently, 10 mL of water was added and stirring con-
tinued for 10 min. After that time an upper phase was separated,
10 mL of diethyl ether was added to the residue, and stirring contin-
ued for 10 min. The extraction was repeated and all ether fractions
were collected and GC-FID analyzed (Hewlett Packard 5890). The
products were identified by GC–MS (Hewlett Packard 5971A).
The catalytic experiments with the filters containing airborne
matter (0.47 g) were performed according to the same proce-
dure, using the following amounts of reactants: butyl acrylate
(0.13 mL, 0.9 mmol), iodobenzene (0.25 mL, 2.23 mmol), NaHCO3
(0.2 g, 2.38 mmol), DMF (7 mL). The reaction was carried out at
140 ◦C for 48 h.
For analyzes of Pd content, the filters were cut into small pieces
and a sample of ca. 0.3 g was weighed and transferred to a flask.
Next, 10 mL H2O, 4 mL HNO3, and 3 mL H2O2 were added and left
for 24 h. After that time, the sample was heated for 1 h at 70 ◦C
and again left for 24 h. The resulting mixture was filtered and the
obtained filtrate diluted with water to 25 mL. The palladium con-
tent determined by ICP was found to be in the range from 0.08 ppm
to 8 ppm in five samples analyzed.
2.2. Characterization of spent automotive catalysts
A sample of ca. 0.001 g of the spent catalyst was treated with
3 mL of HCl and 1 mL of HNO3. The resulting mixture was heated
for 10 min at 60 ◦C and left for 48 h. After that time, water was added
to obtain a total volume of 10 mL, and ICP analysis was performed
to determine the PGM content.
2.3. TEM measurements
2.6. Hydroformylation reaction
First, the catalyst was ground to a form of powder. Next, it was
added to several milliliters of methanol and such suspension was
treated for 5 min with ultrasounds. Finally, a droplet of the suspen-
sion was placed on a carbon-coated microscope grid and dried for
40 min. TEM measurements were carried out using a FEI Tecnai G2
20 X-TWIN electron microscope operating at 200 kV.
The kind of noble metal forming nanoparticles observed in the
TEM micrographs was recognized in each case by means of EDX
analysis. Rh was identified using the X-ray K␣ line at 20.167 keV
and L␣ at 2.696 keV, Pd using the K␣ line at 21.123 keV and L␣ at
2.838 keV, Pt using the L␣ line at 2.838 keV and M␣ at 2.051 keV.
Catalytic reactions were carried out in a 55 cm3 steel autoclave,
which was charged with a 1 g sample of the spent automotive cat-
alyst, PPh3 (9.22 × 10−3 g–2.15 × 10−2 g), toluene (7–12 mL), and
1-hexene (1.5 mL, 12 mmol) under N2 atmosphere. Next, the auto-
clave was filled with an equimolar mixture of H2 and CO to a
pressure of 10 atm and heated at 80 ◦C for 24 h. During that time,
the reaction mixture was stirred magnetically. After that, the auto-
clave was cooled down, opened and the organic products were
separated from the catalyst by decantation and analyzed using a
GC-FID (Hewlett Packard 5890).
2.4. Suzuki–Miyaura reaction
3. Results and discussion
The Suzuki–Miyaura reaction was carried out in a Schlenk
tube with magnetic stirring. Reagents: phenylboronic acid (0.183 g,
1.5 mmol), iodobenzene (0.114 mL, 1 mmol), Cs2CO3 (0.652 g,
2 mmol), ethylene glycol (10 mL) or 2-propanol/water (1:1; 10 mL),
and 1 or 2 g of the spent automotive catalyst were introduced
3.1. Airborne matter as catalyst for Heck and Suzuki–Miyaura
reactions
The model Heck reactions with the application of the filters con-
taining airborne matter as the catalysts were carried out according

150
E. Mieczyn´ska et al. / Applied Catalysis A: General 421–422 (2012) 148–153
Table 1
Results of the Heck reaction carried out with different samples of airborne matter.
Sample no.
Product I [%]
Product II [%]
Sample no.
Product I [%]
Product II [%]
1.
2.
3.
4.
5.
6.
7.
26
65
22
27
85
70
8
–
–
–
–
15
30
–
8.
9.
27
28
5
95
98
96
94
–
–
–
5
–
4
6
10.
11.
12.
13.
14.
Reaction conditions: PhI 0.25 mL (2.23 mmol); CH2 CHC(O)OBu 0.13 mL (0.9 mmol); NaHCO3 0.2 g (2.38 mmol); DMF = 7 mL; 140 ◦C; 48 h.
Table 2
Table 3
Results of the Heck reaction carried out with spent automotive catalysts.
Content of PGMs in spent automotive three-way catalysts.
Catalyst
Rh [ppm]
Pd [ppm]
Pt [ppm]
Molar ratio
Catalyst
[PhX]:[Pd]
PhX
Time [h]
Yield [%]
[Rh]:[Pd]:[Pt]
I
II
176 000
75
PhI
PhI
PhI
PhI
PhI
PhI
PhBr
PhI
PhI
PhI
24
24
24
4
4
4
24
24
4
15
100
100
41
100
100
6
0
69
100
I
II
III
IV
V
0.22
100
7.6
100
30
1.9
3200
450
17
1.6
26
65
2.6
–
1:8.4:62
2.9:90:1
5.5:317:1
6.1:1:0
139
144
139
142
156
980
–
19.4:1:0
III
IV
V
25 100
267 000
to Scheme 1 with iodobenzene and butyl acrylate as the substrates.
Typical reaction conditions, 140 ◦C and DMF as the solvent, were
applied.
4
Reaction conditions: catalyst 1 g; PhI 0.49 mL (4.38 mmol) or PhBr 0.46 mL
(4.38 mmol); CH2 CHC(O)OBu 0.27 mL (1.91 mmol); NaHCO3 0.4 g (4.76 mmol);
DMF 10 mL; 140 ◦C.
To estimate the reproducibility of the Heck reaction, ten exper-
iments were performed with different filters from 2005 to 2006. In
each series of reactions, three were unsuccessful; however, in seven
cases the mono-arylated cross-coupling product, butyl cinnamate,
was found after 48 h reaction. The yield of butyl cinnamate varied
from 8% to 85% for the samples from 2005 and from 5% to 98% for
samples collected in 2006 (Table 1). In addition, in four reactions
the product of a second arylation, ␤-phenyl cinnamate, was also
formed with yields of up to 30%.
Attempts to use bromobenzene as a substrate for the Heck cross-
coupling with methyl acrylate failed and in five experiments the
product was not found.
In contrast to the relatively high activity in the Heck coupling,
the product of the Suzuki–Miyaura coupling, biphenyl, was formed
only in one experiment in the reaction of iodobenzene with phenyl-
boronic acid, with a yield of 38% (Scheme 2).
and only some of them exhibited a rather spherical shape (30%).
Particle size distributions of each of the noble metals (Rh, Pd, Pt) in
the selected catalyst (II, IV, or V) were narrow (standard deviation
ꢀ = 5) with well-defined average crystal diameters (Fig. 1).
3.2.2. Heck reaction
The results illustrating the catalytic activity of the spent auto-
motive catalysts in the Heck reaction are collected in Table 3.
The model reaction was carried out according to Scheme 1 with
iodobenzene and butyl acrylate as the substrates. Subsequently,
other substrates were also used for comparison.
Remarkably good activity was noted for catalyst V, which
formed a coupling product with 100% yield already after 4 h despite
a high excess of iodobenzene in respect to palladium. Very good
results were also obtained with catalyst II, which contained the
highest amount of palladium. Interestingly, catalyst II also showed
some activity in the coupling of bromobenzene with butyl acrylate.
When catalyst IV was used, the best result obtained was 69% of butyl
cinnamate after 4 h. From the data presented in Table 3, it can also
be concluded that there is no clear correlation between palladium
content and conversion. The activity of the spent automotive three-
way catalysts in the Heck process depends also on other important
factors. For instance, catalyst II showed 41 and 100% in identical
experiments (Table 3). Most likely, in spite of the high Pd con-
tent, the fragment of the catalyst used in the experiment with a
lower yield was partially poisoned. Contaminants introduced dur-
ing operation of the catalyst in a vehicle exhaust system may cause
deactivation of the metal sites or modify electronic properties of
palladium [32,33].
3.2. Spent automotive three-way catalysts in cross-coupling
reactions
3.2.1. Characterization of spent automotive catalysts
In the next step of our studies, five different spent automotive
three-way catalysts were tested in the Suzuki–Miyaura and Heck
reactions. All the catalysts had been previously used for a period
of 6 years or more for the original purpose of purifying exhaust
gases in different cars. The content of PGMs, determined by the ICP
method, was from 1.6 to 3200 ppm of Pd, from 2.6 to 65 ppm of Pt,
and from 0.22 to 100 ppm of Rh (Table 2).
The results of TEM studies of the spent catalytic converters
revealed that noble metals (Rh, Pd and Pt) were present in the form
of nanoparticles supported on oxide-based ceramic materials. In
the catalytic converters investigated, the nanoparticles were well
dispersed on the support without forming aggregates. Usually they
were characterized by typical crystal outlines (approximately 70%)
With catalyst II, very good results, 97% and 57% of the product,
were also obtained for the coupling of iodobenzene with 2-methyl-
2-propen-1-ol and with its isomer, but-2-en-1-ol (crotyl alcohol)
[cat.]
+
I
B(OH)2
Cs2CO3, ethylene glycol
80oC
Scheme 2.

E. Mieczyn´ska et al. / Applied Catalysis A: General 421–422 (2012) 148–153
151
Fig. 1. Typical forms and most common diameters of transition metal nanoparticles observed in spent catalytic converters.
(Table 4). It was also possible to couple iodobenzene with cinnamyl
Table 4
aldehyde (34% after 4 h) and with ethyl cinnamate (77% after 24 h).
Catalyst V was active in reaction of iodobenzene with crotyl alcohol
(45% after 24 h). With cinnamyl aldehyde and 2-methylpropen-
2-ol, 19% of the cross-coupling product was formed. Again, it is
important to point out that the [PhI]:[Pd] ratio for catalyst V was in
the range from 200 000 to 300 000.
According to the literature, palladium is considered the most
active catalyst for C C cross-coupling reactions and it is most prob-
ably also responsible for the catalytic results observed in these
studies [22–31]. However, some activity originating from platinum
or rhodium cannot be fully excluded in the Heck reaction or in the
Suzuki–Miyaura reaction. Therefore, other metals or components
of the spent automotive catalysts might influence the activity of
palladium and result in a lack of correlation between palladium
content and the observed activity.
Results of the Heck reaction of iodobenzene with different olefins carried out with
spent automotive catalysts.
Catalyst
II
[PhI]:[Pd]
Olefin
Time [h]
Yield [%]
137
142
140
70
137
PhCH CHC(O)H
4
24
34
77
57
64
97
1
PhCH CHCOOEt
MeCH CHCH2OH
MeCH CHCH2OH
CH2 C(Me) CH2OH
PhCH CHCOOEt
PhCH CHC(O)H
MeCH CHCH2OH
MeCH CHCH2OH
CH2 C(Me) CH2OH
PhCH CHCOOEt
PhCH CHC(O)H
IV
V
25 900
25 900
27 000
13 600
25 000
243 000
243 000
302 100
146 000
300 500
24
24
3
17
46
3
5
19
49
45
19
MeCH CHCH2OH
MeCH CHCH2OH
CH2 C(Me) CH2OH
The post-reaction mixture obtained after the Heck reaction with
catalyst II was analyzed to estimate the amount of PGMs leached
from the support. According to ICP, 12 ppm of Pd, 0.3 ppm of Rh and
Reaction conditions: catalyst 1 g; PhI 0.49 mL (4.38 mmol); olefin 1.91 mmol; NaHCO3
0.4 g (4.76 mmol); DMF 10 mL; 140 ◦C.

152
E. Mieczyn´ska et al. / Applied Catalysis A: General 421–422 (2012) 148–153
[cat.]
O
+ CO + H2
+
O
toluene
10 atm, 80oC
n
iso
Scheme 3.
Table 5
Results of the Suzuki–Miyaura reaction carried out with spent automotive catalysts.
Catalyst
II
[PhI]:[Pd]
Solvent
Time [h]
Yield [%]
15
29
32
30
30
Ethylene glycol
Ethylene glycol
2-Propanol/water
2-Propanol/water
Ethylene glycol
Ethylene glycol
2-Propanol/water
2-Propanol/water
Ethylene glycol
2-Propanol/water
24
24
24
24
24
6
6
6
24
24
100
100
100
100
100
39
97
35
0
4
32
33
IV
V
8300
40 600
44 500
Reaction conditions: catalyst 1 or 2 g; PhI 0.114 mL (1 mmol) or PhBr 0.106 mL (1 mmol); PhB(OH)2 0.183 g (1.5 mmol); Cs2CO3 0.652 g (2 mmol); ethylene glycol 10 mL or
2-propanol/water (1:1) 10 mL; 80 ◦C.
Table 6
Results of 1-hexene hydroformylation carried out with spent automotive catalysts.
Catalyst
IV
[1-hexene]:[Rh]
[PPh3]:[Rh]
n/iso
Conversion [%]
2-hexene [%]
Aldehydes [%]
4000
4000
4000
5100
5100
5100
18
9
29
15
12
24
2.1
–
41
–
31
–
11
–
–
4
6
V
0.9
1.0
1.9
61
79
66
57
73
8
58
Reaction conditions: catalyst 1 g; 1-hexene 1.5 mL (12 mmol); CO + H2 10 atm; PPh3 9.22 × 10−3 g–2.15 × 10−2 g (3.52 × 10−5–8.2 × 10−5 mol); toluene 7–12 mL; 80 ◦C; 24 h.
0.6 ppm of Pt were found, indicating a very low, but measurable,
dissolution of PGMs in the presence of Heck reactants. Redeposition
of the leached noble metal species on the support was not observed.
which confirms the positive effect of the phosphine. All the dis-
cussed hydroformylation reactions were carried out with addition
of PPh3. It is known that in the first reaction stage the phosphorous
ligand labilizes the coordination sphere of rhodium, facilitating
formation of [HRh(CO)(PPh3)3], the most active hydroformylation
reaction catalyst precursor [35]. Moreover when phosphorus-free
rhodium systems were applied in hydroformylation, typically n/iso
close to 1 was noted [36–38] or sometimes only the isomerization
product was formed [35].
Rhodium is known as the most active catalyst for hydroformy-
lation [31,34–40]; therefore, the observed catalytic effect should
be related to the presence of rhodium. However, as in the case of
palladium, an additional influence of other components present in
spent automotive three-way catalysts is possible.
3.2.3. Suzuki–Miyaura reaction
Results obtained in the Suzuki–Miyaura reaction (Scheme 2)
carried out in the presence of five spent automotive catalysts are
presented in Table 5. In these experiments the amount of a cat-
alyst ranged from 1 to 2 g regardless of the PGM content. As a
consequence, the [PhI]:[Pd] ratio varies remarkably for the sys-
tems studied. If the amount of palladium is considered, the best
results were noted for catalyst IV, which produced biphenyl with
35% yield in 6 h at a high excess of PhI in respect to palladium
([PhI]:[Pd] = 8300).
Catalyst II, containing the highest amounts of PGMs, formed
39% of the coupling product in 6 h in ethylene glycol and 97% in
2-propanol-water mixture. When the less reactive bromobenzene
was used instead of iodobenzene, 43% of biphenyl was formed
in 6 h. With catalysts IV, 35% of biphenyl was obtained after 6 h,
whereas with catalyst V only 4% of biphenyl was obtained and
catalysts I and III were practically inactive in the Suzuki–Miyaura
coupling.
4. Conclusions
It was shown that the spent automotive three-way catalytic con-
verters contain PGMs (Rh, Pt, Pd) in the form of nanoparticles well
dispersed on oxide-based ceramic materials. They exhibit catalytic
activity when used without any pretreatment in C C bond form-
ing reactions, such as the Heck or Suzuki–Miyaura cross-coupling.
Similarly, airborne matter collected on filters is catalytically active
in these reactions. Although the observed catalytic activity cannot
be directly correlated with PGM content, the obtained results con-
firmed a very high catalytic potential of the waste materials. In
some cases the molar ratio of converted substrate to catalyst (Turn
Over Number; TON) up to 200 000 was noted, which should be con-
sidered high even for specially designed organometallic catalysts.
Interestingly, the same waste materials showed reactivity towards
olefins, forming isomerization or hydroformylation reaction
products.
3.2.4. Hydroformylation reaction
Two catalysts, IV and V, exhibited activity in catalytic transfor-
mation of 1-hexene under hydroformylation reaction conditions
(Table 6). This activity most probably originated from the presence
of rhodium nanoparticles, similarly as reported by Dupont [34].
In three cases, 2-hexene was the major product, formed with
yields of up to 73%. The highest yield of aldehydes (Scheme 3), 58%,
was obtained when catalyst V was used with a 24-fold excess of
PPh3 in respect to rhodium. In this reaction, the n/iso ratio was 1.9,

E. Mieczyn´ska et al. / Applied Catalysis A: General 421–422 (2012) 148–153
153
The only disadvantage of the studied systems is the poor repro-
ducibility of catalytic results. However, it can probably be improved
by a special pretreatment or activation step before the main reac-
tion.
The observed activity of the spent automotive three-way cata-
lysts opens up the possibility of considering their application not
only as a source of PGMs but also as active components of catalytic
systems applied in organic synthesis.
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Acknowledgements
The authors are grateful to Ms Agata Szumska, Ms Joanna Tylip-
ska, Ms Anna Popiel and Ms Anna Kuleta for testing of the catalysts
and to Mr Marek Hojniak (Faculty of Chemistry, University of
Wrocław) for GC and GC–MS analyzes.
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