683

Studies on the Utilisation of Spent Palladium–Activated Carbon (Pd/AC)

Catalysts
/
L. Dacbek1, A. Swiac tkowski2* and J. Dziaduszek2 ¢
(1) Faculty of Civil Engineering, The Swietokrzyskie
University of Technology, Al. 1000-lecia PP 1, 25-534 Kielce, Poland. (2) Institute of Chemistry, Military Technical Academy,
Kaliski Str. 2, 00-908 Warsaw, Poland.

(Received 28 February 2002; accepted 19 April 2002)

ABSTRACT: The present paper offers an assessment of using wastes such as

palladium–activated carbon (Pd/AC) catalysts through their regeneration or metal
recovery. In order to regenerate a catalyst it has been found necessary to clean up
its surface completely and restore the original form of the metal. Supercritical
fluid extraction can be useful in removing organic substances from the surface of
a spent catalyst whereas microwave mineralisation can be used to recover palladium
from the mass of a spent catalyst.

INTRODUCTION

Owing to their porosity, developed specific surface and capability of modelling both the structure
and chemical constitution of a surface, activated carbons are widely used as sorbents, catalysts and
catalyst supports where metals and metal compounds constitute the active phase (Jüntgen 1986;
Rodriguez-Reinoso 1995, 1998; Erhan Aksoylu 2001).
Of the great number of catalysts prepared on supports such as activated carbon are those whose
active phase consists of palladium scattered over the carbon surface (Pd/AC). According to the
literature (Krishnankutty et al. 1998), Pd/AC catalysts show relatively better catalytic properties
for a series of reactions relative to palladium prepared on SiO2 and, therefore, are used commercially
in numerous processes (Auer et al. 1998), e.g. the following change reactions: monoolefins to
alkanes; diolefins to monoolefins; cyclohexene to cyclohexane; alkynes to alkanes; aromatic ring
hydrogenation; aromatic aldehydes to alcohols; aromatic ketones to alcohols; aliphatic nitro com-
pounds to primary amines; aromatic nitro compounds to anilines; nitrosoaromatic compounds to
anilines; hydrazones to hydrazines; imines to amines; aliphatic nitriles to primary amines; aliphatic
nitriles to secondary amines; aliphatic nitriles to tertiary amines; aromatic nitriles to primary amines;
aromatic nitriles to tertiary amines; reductive alkylation; reductive amination; disproportionation;
hydrodehalogenation; oxidation of alcohols; dehydrohalogenation; the Rosenmund reaction;
debenzylation; carbon–oxygen cleavage; carbon–nitrogen cleavage; hydroxylamine synthesis;
decarbonylation; fat and fatty acid hardening; and carboxylic acid compounds to alcohols.
Catalysts of the palladium–activated carbon type are also used to neutralise Freons (Van de Sand
et al. 1998; Dond Jo Moon et al. 1999), e.g., the commercial reaction between Freon CFC-12
(CCl2F2) and hydrogen in the presence of a Pd/AC catalyst which produces difluoromethane and
hydrogen chloride. The use of activated carbon as a support in the decomposition of Freons is
related to its chemical passivity towards HCl and HF which are products of the hydrogenation of
Freons. It is not advisable to use SiO2 or Al2O3 as supports because SiF4 or AlF3 can be produced in

*Author to whom all correspondence should be addressed. E-mail: mswiatko@elka.pw.edu.pl.

684 L. Dacbek et al./Adsorption Science & Technology Vol. 20 No. 7 2002

the hydrogenation of Freons. SiF4 is volatile and likely to leave the reaction whereas AlF3, which
acts as a Lewis acid in the exchange of chlorine for fluorine, can catalyse side reactions and,
consequently, reduce the selectivity of the reaction. Similarly, zeolites cannot be used as catalyst
supports in the neutralisation of Freons. It should be noted that only microporous activated carbons
of low ash content can be used as catalyst supports in the neutralisation of Freons because they
guarantee high selectivity and no catalysation of side reactions through ash components.
After their use, spent palladium–activated carbon catalysts become waste which, according to
the Council Directive 91/156/EEC of 18 March 1991 amending Directive 75/442/EEC on waste,
belong to group Q6. Their properties are characteristic of ‘ecotoxic’ waste H14 — substances that
are or may be a direct or delay hazard to one or more elements of the environment (Council
Directive 91/689/EEC). Because there is a good chance of recovering the constituents of a catalyst,
they are described as waste R7. Since it can be neutralised, the waste qualifies for groups D9 and
D10 (physical and chemical treatment, and heat conversion).
The use of carbons as catalyst supports, particularly Pd/AC catalysts, is relatively small compared
with the quantities of activated carbons used in water treatment, and sewage and gas purification.
However, the problem of their utilisation still exists after their consumption. Since palladium is
present in the catalysts, it is economically vital to recover the metal.
In considering the possibility of recovering noble metals, including palladium, from spent cata-
lysts, it is necessary to treat the waste as a system where the metal is part of the porous solid matrix.
Because activated carbon is a matrix, it is possible to consider the possibility of burning the catalyst
and recovering metals from its ash (Erhan Aksoylu et al. 2001). However, such metal recovery is
difficult and therefore direct separation from catalysts through extraction is more often used.
The recovery of noble metals from industrial waste (Reksc et al. 1989; Stefanowicz et al. 1989),
/ /

including spent noble metal–activated carbon catalysts, consists in their separation from the matrix
by solubilising in nitric acid (Pd, Ag), in aqua regia (Au, Pt, Pd, Rh) or alkalis (Pt, Ru), and, next,
in the recovery of the metal from the solution obtained. The most advantageous way of separating
a noble metal from solution after its utilisation is to precipitate it as a sparingly soluble compound
or to use electrochemical methods. Among effective precipitating agents are dimethylglyoxime,
2-mercaptanobenzothiazole, sulphides, chlorides, iodides, cyanides, carbonates and hydrazine.
The efficiency of removing impurities from the surface of porous waste depends both on the
selection of solutions for leaching or extraction and from the number of process stages as determined
by the predominant type of pores present, size reduction and the substances themselves (susceptibility
to solubilisation). To improve the efficiency, it is necessary to provide the best extraction conditions,
i.e. to establish the ratio of the volume of regenerating solution to the mass of waste. This ratio
should be as low as possible because it guarantees effective mixing, sedimentation or filtration. On
the other hand, with a porous matrix such as that of carbon, the process of leaching is exceptionally
difficult. This results from the fact that considerable quantities of the leaching solution are arrested
in the waste mass, thereby resulting in the use of a greater number of degrees of leaching and,
consequently, more solution to effect separation. Hence, counter-current leaching would appear to
be the best solution to develop for this process.
The major drawback to the use of extraction methods for recovering metals from porous waste
is that the process produces considerable quantities of after-extraction solutions containing relatively
low concentrations of metals, making their separation from solution difficult. For this reason, new
approaches are being sought. Nowadays, supercritical fluid extraction (SFE) is widely used for
removing toxic metals from different materials, waste and such environmental elements as soil,
bottoms and sewage (Marquez-Alvarez et al. 1996; Grajek 2000). The method is considered an
alternative in those areas where other extraction methods are themselves hazardous to the environ-
Studies on the Utilisation of Spent Palladium–Active Carbon Catalysts 685

ment. The advantage of SFE is that the supercritical solvent retains the density and solvency
characteristics of a fluid as well as the diffusion rate and penetrating power typical of a gas. A
decrease in pressure leads to the removal of the solvent and the extracted substance remains pure.
Carbon dioxide is the most popular solvent in SFE because of its low critical temperature, low
critical pressure, non-flammability, non-toxicity and passivity. In the supercritical state, it acts as a
Lewis base with proton–acceptor properties and polarity comparable to that of n-hexane.
However, most literature data (Wilson 1996; Wang et al. 1995; Zacharia et al. 1999; Ondrejovicv
and Sirota 1999; Wenclawiak et al. 1997) indicate that since CO2 is itself a non-polar substance in
both the liquid and supercritical states it is poor for the extraction of positive metal ions. The
removal of metal ions with liquid and supercritical CO2 must be accompanied by the presence of a
ligand soluble in CO2 and capable of forming a complex with the metal which is soluble in the
extraction medium. More and more information is available on the supercritical extraction of metals
from solid materials through the use of CO2 and a chelation system consisting of fluoro derivatives
of macrocyclic organic compounds, crown ethers and porphyrins. The use of such chelation systems
for the supercritical extraction of metals results from the fact that metal complexes with compounds
such as fluoro derivatives of macrocyclic organic compounds are two or three times as soluble in
supercritical CO2 as those free from fluorine, which makes this method more efficient.
For the separation of metals such as Rh and Pd from old porous matrices by SFE, it was found
effective to initially complex the metals with chelating agents such as 2,2,6,6-3,5-heptanedione,
acetylacetone or benzylacetone and then to remove them with supercritical CO2 (Wenclawiak et al.
1997).
The present paper is aimed at an assessment of the possibility of managing wastes such as spent
Pd/AC catalysts through their regeneration and the recovery of the metal. The present studies
concentrate upon the variety of Pd/AC catalysts used in the hydrogen reduction of systems such as:
1. hexanoylbenzene ® hexylbenzene
2. 4-hexanoylbiphenyl ® 4-hexylbiphenyl
3. 4-hexyl-4’-octanoylbiphenyl ® 4-hexyl-4’-octylbiphenyl
4. 4-propylnitrobenzene ® 4-propylaniline
5. 4-pentylnitrobenzene ® 4-pentylaniline
6. 4-[(4-trans-propylcyclohexyl)-1-phenyl]-1-cyclohexene ® 4-[(4-trans-propylcyclohexyl)-
1-phenyl]cis,trans-cyclohexane
7. 2-[(4-trans-pentylcyclohexyl)-1-(4-benzyl-oxyphenyl)]-1-ethanol ® 2-(4-trans-
pentylcyclohexyl)-1-(4-hydroxyphenyl)ethane
The system studied was defined as one representing real waste as obtained industrially.

EXPERIMENTAL

The following Pd/AC catalyst samples were investigated: (i) a commercial Aldrich 10 wt% Pd
catalyst, indicated as K below; (ii) a variety of spent catalysts, indicated as K1 below; and (iii) a
spent catalyst subjected to supercritical extraction, indicated as K2 below. Experimental samples
of catalysts were taken according to the rules for taking solid samples (Brands 1983).

Determination of the porous structure of the commercial catalyst K

The porous structure of the commercial Pd/AC catalyst (K) was determined by low-temperature
nitrogen adsorption studies at 77 K. For this purpose, a Sorptiomatic 1900 apparatus was used to
686 L. Dacbek et al./Adsorption Science & Technology Vol. 20 No. 7 2002

Figure 1. Adsorption/desorption isotherm of nitrogen at 77 K on a commercial Pd/AC catalyst (K). Data points: F , adsorption;
u , desorption.

TABLE 1. Parameters of the Porous Structure of Commercial Pd/AC Catalyst K

Micropore volume, W0 (cm3/g) 0.357

Characteristic adsorption energy, E0 (kJ/mol) 19.8
Specific surface area, SBET (m2/g) 865
Mesopore surface area, Smeso (m2/g) 221
Studies on the Utilisation of Spent Palladium–Active Carbon Catalysts 687

Figure 2. Micropore size distribution of commercial Pd/AC catalyst (K).

determine the adsorption and desorption isotherms via a volumetric method. A typical adsorption/
desorption isotherm obtained is depicted in Figure 1.
The data obtained allowed the determination of parameters describing the microporosity
(micropore volume, W 0, and the characteristic energy of adsorption, E0) through application of the
Dubinin–Radushkevich equation (Dubinin 1991). The results obtained are listed in Table 1.
Using the Horvath and Kawazoe method (Horvath and Kawazoe 1983) and employing the nitrogen
adsorption isotherm, the micropore size distribution shown in Figure 2 was also obtained.
The surface area of the mesopores, Smeso, was determined by the method of Dollimore and Heal
(1964) whereas the specific surface area, SBET, was determined via the BET equation (Brunauer et
al. 1938). The corresponding data are included in Table 1.
688 L. Dacbek et al./Adsorption Science & Technology Vol. 20 No. 7 2002

Figure 3. Micrograph of surface of fresh Pd/AC catalyst (K) (×500 magnification).

Supercritical fluid extraction (SFE)

The spent catalyst K1 was subjected to supercritical extraction. Initially, it was dried at 333 K in an
atmosphere of CO2 at 1.2 bar for 18 h. Supercritical extraction of the dried catalyst was carried out
at two pressures and two extraction times (I and II) under the following conditions: temperature,
333 K; pressure I, 16 MPa; CO2 flow rate, 30 dm3/h; extraction time I, 150 min; pressure II, 20
MPa; CO2 flow rate, 30 dm3/h; extraction time II, 690 min. The extract was separated from CO2 in
a receiver at 268 K.

Scanning electron microscope studies

Micrographs of the catalyst surface (×500 magnification) were obtained using a JEOL EME JSM 5400
scanning electron microscope. Examples of the resulting micrographs are given in Figures 3 and 4.
Studies on the Utilisation of Spent Palladium–Active Carbon Catalysts 689

Figure 4. Micrograph of surface of spent Pd/AC catalyst (K2) after treatment by SFE (×500 magnification).

XPS investigations

Two Pd/AC catalysts (K and K2) were subjected to XPS investigations employing a VG Scientific
ESCALAB-210 photoelectron spectrometer using Al Ka X-rays at 15 kV and 20 mA, respec-
tively. Spectral regions corresponding to Pd and C were scanned using a constant CAE value of 30
eV. In addition, the spectrum was also measured at CAE = 50 eV. The number of sweeps of the
range under investigation was determined by the signal-to-noise ratio. The spectra measured were
subjected to the standard treatment using the ECLIPSE programme which removed any ‘satellites’
and detached the non-linear background via Shirley’s method (Shirley 1972). Next, the spectra in
the individual regions were processed by adjusting the possible forms of a given element using the
different characteristic values of the bond energy BE associated with a given sample. Quantitative
analysis was based upon the sensitivity coefficients for individual electron levels and elements
according to Scofield (1976). The results obtained are given in Tables 2 and 3.
690 L. Dacbek et al./Adsorption Science & Technology Vol. 20 No. 7 2002

TABLE 2. XPS Spectrum of Commercial Catalyst K

Peak Bond energy (eV) Area (%) FWHM

C 1s
284.50 68.71 1.56
286.08 11.91 1.65
287.26 5.83 1.66
288.45 4.92 1.72
289.90 3.31 1.71
291.46 5.32 2.96
Pd 3d
5/2 335.78 80.16 1.93
5/2 338.06 19.84 2.10
3/2 341.03 1.94
3/2 343.31 2.21

TABLE 3. XPS Spectrum of Catalyst K2 (Spent and

Subject to SFE)

Peak Bond energy (eV) Area (%) FWHM

C 1s
284.50 70.97 1.57
286.29 13.01 1.65
288.04 7.13 1.65
289.84 5.24 1.65
291.61 3.64 1.65
Pd 3d
5/2 335.31 31.65 1.58
5/2 336.83 57.86 1.82
5/2 338.63 10.49 2.03
3/2 340.56 1.58
3/2 342.08 2.03
3/2 343.88 2.00

Microwave mineralisation
A weighed sample of the catalyst (up to 3 g) was flooded with 4 cm3 of concentrated HNO3 and
subjected to microwave mineralisation. Mineralisation of all samples was carried out in a UniClever
high-pressure (110 atm) and high-temperature (525 K) mineraliser using a constant microwave
energy of 150–300 W. Such mineralisation was undertaken in three stages: 5 min heating/60%
power, 10 min heating/80% power, 10 min heating/100% power. The cooling time between each
stage was 5 min. The solutions obtained after mineralisation were transferred into 25 cm3 measur-
ing flasks and made up to the mark with distilled water.
Studies on the Utilisation of Spent Palladium–Active Carbon Catalysts 691

XRF analysis

An XRF analysis of solutions of the present catalysts after mineralisation was undertaken using a
Canberra Packard-ND-Data apparatus. The results of such analysis of the palladium content in the
after-mineralised solution relative to the catalyst mass were as follows: (a) Pd content in commer-
cial catalyst K = 9.95 wt%; (b) Pd content in catalyst K2 = 9.20 wt%.

Catalytic efficiency of a Pd/AC catalyst

Catalysts K1 and K2 were tested in the following reduction with hydrogen: octanoylbenzene ®
octylbenzene. Thus, 40.8 g (0.2 mol) ketone and 1.3 g Pd/AC catalyst were employed passing
hydrogen of 99% purity as the reducer through the system. The activity of the catalyst was assessed
by measuring the amount of hydrogen used relative to the theoretical value necessary for the reaction.

RESULTS AND DISCUSSION

Investigations of the possibility of regenerating a Pd/AC catalyst and its decomposition to recover
palladium were made. Initially, the porous structure of the catalyst which is vital to the regeneration
and the method of utilization chosen was defined. The isotherm given in Figure 1 shows a Langmuir
course with increasing adsorption at low pressures, the presence of quite a wide hysteresis loop
suggesting a developed mesoporous structure. The specific surface of the Pd/AC catalyst, SBET, was
equal to 865 m2/g while the mesopore surface area, Smeso, was 221 m2/g. Micropores of radii 0.5–
1.0 nm were predominant in the microporous structure. Such a porous structure suggests that the
active phase of the catalyst, i.e. dispersed Pd, was mostly present in the mesopores.
In view of the use of Pd/AC catalysts, their regeneration and subsequent re-use were considered
the most efficient method of proceeding. Since the basic aim of regeneration was to remove only
organic substances produced as by-products in the reduction processes, supercritical extraction
was chosen as a possible method. This was related to the fact that the method is relatively simple,
efficient as regards organic substances and relatively cheap, and also that the catalyst obtained
would not need to be purified additionally or dried. Non-modified CO2 was mostly used as the
extraction solvent for economic reasons.
The spent Pd/AC catalyst subjected to supercritical extraction was re-used in the hydrogen
reduction of octonoylbenzene.Under the circumstances employed, the activity of catalyst K2 proved
to be much lower than that of the commercial catalyst K, with the efficiency being less than 40%.
Such results indicate that the spent Pd/AC catalyst subject to supercritical extraction was not
regenerated satisfactorily.
However, it would seem that obstruction of the catalytic surface with reaction by-products was
not the only reason for the loss of the catalytic capability of the system. To find reasons for the
virtually complete loss of the catalytic powers of K2, micrographs of the surface of both K and K2
were taken. The views of the surface depicted in Figures 3 and 4 show no differences sufficiently
significant to account for the lack of catalytic activity with K2. Hence, XPS investigations were
undertaken at a further stage in the experiments. As shown by the data recorded in Tables 2 and 3,
the palladium present in the fresh catalyst K occurs in two states, i.e. as ionic palladium Pd2+ (peak,
338.06 eV) and as metallic clusters (peak, 335.78 eV). Normally palladium exhibits a bond energy
in the range 335.1–335.3 eV whereas the peak observed for the present catalyst was situated slightly
beyond this zone, although it should be noted that such an effect is frequently observed for reduced
and highly dispersed palladium on supports. However, in the spent catalyst subjected to supercritical
692 L. Dacbek et al./Adsorption Science & Technology Vol. 20 No. 7 2002

extraction, palladium occurred in three states, i.e. ca. 30% as a metal (large crystallites) (peak,
335.31 eV), ca. 60% as PdO (peak, 336.83 eV) and the remainder of ca. 10% as Pd2+ ions (peak,
338.63 eV) (Moulder et al. 1992).
The results of such XPS investigations indicate that a change occurred in the form of the palla-
dium present on the catalyst surface. Hence, the reasons for the loss in catalytic ability of the
system under investigation could be associated both with obstruction of the catalytic surface by
by-products as well as in a change in the chemical form of the active metal. With the sample of
spent catalyst subjected to supercritical extraction (K2), it may be assumed that its activity was
proportional to its effective surface area accessible to reactants and hence indispensable to the
effectiveness of the elementary catalytic act.
Since the complete regeneration of a Pd/AC catalyst by SFE with CO2 was practically impossible,
recovery of palladium was found to be the most efficient method of proceeding. Such recovery
could be effected either by burning the spent catalyst and separating the metal from its ash or by
direct extraction from the waste. Both methods are closely related to the transfer of palladium to a
solution and, hence, to its separation. When the above-mentioned disadvantages of extraction are
considered, especially the considerable dilution of the after-extraction solutions and thus the difficult
separation of the metal (plus significant volumes of solutions), the use of microwave mineralisation
was suggested in the present case. The decomposition of the carbon matrix is effected in one stage
during microwave mineralisation with the simultaneous transfer of the palladium to an oxidising
solution such as nitric acid. In contrast to extraction methods, this avoids the problem of separating
a solution from the solid residue and the necessity of its management (neutralisation), uses minimal
volumes of solution and hence contributes to attaining higher concentrations of the metal.
According to the results of XRF analysis, all the palladium present in the catalyst was transferred
to solution as a result of microwave mineralisation in an HNO3 medium. The difference shown
between the palladium content of a commercial catalyst (9.95 wt%) and the spent catalyst subjected
to supercritical extraction (9.20 wt%) may be accounted for by the partial removal of palladium
together with the extraction of organic impurities in the extraction process. The presence of minute
quantities of palladium collected as liquid products after SFE supports this view.
This suggests that removed organic substances change the polarity of supercritical carbon dioxide
and also favour the removal of the metal. A similar effect was observed when SFE was used to
remove organic impurities from the spent catalyst arising from vinyl acetate synthesis where zinc,
i.e. the active phase of the catalyst, was separated alongside organic substances (Dac bek 2002). The
loss of palladium from the spent Pd/AC catalyst during supercritical extraction was confirmed by
the results of XPS investigations (i.e. the palladium content in K2 and K2 as determined by XPS
methods). However, since the investigations were undertaken on real wastes and not on model
systems, it was not possible to calculate the palladium balance achieved.

CONCLUSIONS

The reported data and their analysis lead to the following conclusions:
1. In view of the widespread use of Pd/AC catalysts in different commercial syntheses and the
high mass content of the precious metal, it is considered advisable to regenerate the spent
catalyst and to effect the removal of palladium using relatively cheap and simple methods.
2. Regeneration of a spent Pd/AC catalyst, irrespective of the reaction in which it has been used,
should be based on the complete removal of by-products and cleaning the catalyst surface as
well as on restoring the original form of the palladium.
Studies on the Utilisation of Spent Palladium–Active Carbon Catalysts 693

3. SFE may be used to remove organic substances deposited on the surface of a spent Pd/AC
catalyst, but this issue needs further extensive and detailed study (e.g. modification of the CO2
used in SFE).
4. Palladium may be recovered from a spent Pd/AC catalyst by the use of microwave mineralisa-
tion, where decomposition of the carbon matrix and organic substances deposited in the catalyst
is accompanied by the transfer of palladium to solution. The volume of solution obtained in
this process is relatively low whereas the concentration of the metal is quite high, thereby
making its recovery easier.

ACKNOWLEDGEMENTS

This work was partly supported by the Polish Committee for Scientific Research, Project No.
3 T09C 046 17. We thank Dr. J. Sobczak from the Institute of Physical Chemistry (PAN), Warsaw
(Poland) for the XPS measurements.

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