PERGAMON Carbon 38 (2000) 1241–1255

Palladium catalysts on activated carbon supports

Influence of reduction temperature, origin of the support and
pretreatments of the carbon surface
a a a, b b
M. Gurrath , T. Kuretzky , H.P. Boehm *, L.B. Okhlopkova , A.S. Lisitsyn ,
V.A. Likholobov b
a
¨ Anorganische Chemie, Universitat
Institut f ur ¨ Munchen
¨ ¨
, Butenandtstr. 5 -13 ( Haus D), D-81377 Munchen , Germany
b
Boreskov Institute of Catalysis, Novosibirsk 630090, Russia
Received 25 February 1997; accepted 21 January 2000

Abstract

A number of activated carbons produced from peat, coconut shell, and by pyrolysis of hydrocarbons have been subjected
to treatment with oxygen, chlorine, hydrogen or ammonia at elevated temperatures to get a representative series of catalyst
supports differing in porous structure and surface chemistry (characterized by nitrogen adsorption and selective titrations).
Palladium was deposited from anionic (H 2 PdCl 4 ), neutral (Pd(OAc) 2 , in acetone), and cationic ([Pd(NH 3 ) 4 ](NO 3 ) 2 )
complexes. Temperature-programmed reduction, CO chemisorption, and testing in olefin hydrogenation were used to study
the possible effects of preparation variables. The origin of the carbon support and the temperature of the catalyst reduction
with hydrogen proved to have a profound influence on the properties of the catalysts. In contrast, no unambiguous correlation
has been found between catalyst properties and the pretreatments of the carbons. It is concluded that the effect of the support
comes mainly from the differences in the porous structure of the carbons, and occurrence of steric hindrance for organic
substrates in contacting the metal particles on the microporous supports is suggested.  2000 Elsevier Science Ltd. All
rights reserved.

Keywords: A. Activated carbon, Catalyst support; D. Catalytic properties, Microporosity, Surface properties

1. Introduction preparation are concerned. Even in the case of oxide-

Activated carbons have some advantages as catalyst
supports. They are relatively inexpensive, possess a high
surface area, allow easy recovery of supported metal by
simple combustion of the support, show chemical inertness
both in acidic and basic media, and at the same time do not
contain very strongly acidic centers on their surface, which
could provoke undesirable side reactions during the cata-
lytic run. All that makes them attractive or even indispens-
able as supports in many cases, in particular in small-scale
organic syntheses catalyzed by platinum group metals
(PGM) [1].
Although PGM / carbon catalysts were, in all likelihood,
the first supported PGM catalysts made, as described more
than a century ago, catalysts on carbon supports remained
rather little studied for a long time as far as the aspects of
*Corresponding author.
supported systems there is still not much scientific litera-
ture on the chemical processes taking place during catalyst
generation and on the factors governing the course of the
processes. However, catalysts on activated carbons are
more difficult to investigate, firstly, because of a more
complex porous structure, and, secondly, because of the
possible variation in the surface chemistry of the supports.
There is also the well-known difficulty of the application
of traditional physical investigation methods, e.g. spectro-
scopic ones, in this case due to the non-transparency of
carbon materials to IR, visible and UV radiation. There-
fore, despite a great demand for new catalysts, with the
characteristics of the carbon support and the state of the
active phase adjusted to specific conditions of the catalyst
application, the preparation methods continue to be pre-
dominantly empirical in nature. Only recently the number
of scientific publications on the subject started to show an
increasing tendency [1–4].

0008-6223 / 00 / $ – see front matter  2000 Elsevier Science Ltd. All rights reserved.
PII: S0008-6223( 00 )00026-9
1242 M. Gurrath et al. / Carbon 38 (2000) 1241 – 1255
The two metals which are most widely used in catalysis
by PGM / carbon are platinum and palladium. From the
economics standpoint, they should be provided with the
highest dispersion (the fraction of atoms on the surface
relative to their total number, both on the surface and in
the bulk of the metal particles). Factors affecting the
obtained metal dispersion may be the pore structure of the
carbon, i.e. the pore width and the surface area, and the
chemical state of the surface, e.g. its coverage with oxygen
complexes. The obtained dispersions tend to be relatively
low in microporous carbons [5,6] while higher dispersions
can be obtained when mesopores are present [6].
The possibility of easy surface cleaning by oxidative
calcination is often perceived as an advantage of using
metal oxides as supports for catalytically active metals.
However, this leaves no room for variation of the nature
and concentration of specific surface sites, in contrast to
the situation with carbons. It is assumed that functional
groups on the support surface can act as anchoring sites for
metal complexes. The role of oxygen complexes on carbon
surfaces on the metal dispersion has been the subject of
´
numerous studies (see references cited by Roman-Martınez ´
et al. [7] and Refs. [6,8–10]). Many of these aspects are
described in detail in a recent review [2]. However, most
of these studies were concerned with platinum catalysts,
whereas fewer publications dealt with Pd / C catalysts
[8,9,11–18], and the supports used often were non-porous
carbon blacks but not activated carbons. As a rule, the
previous studies concerned the effect of preparation vari-
ables either on the state of the resulting metal or on its
catalytic properties only. In addition, relatively high tem-
peratures were usually applied in the reduction of the
supported phase, which is rare in real practice.
This paper describes a part of our study carried out with
carbon-supported Pd and Pt catalysts (see also Refs.
[19,20]). The focus of our attention was in the possible
influence of the chemical state of carbon surface and of the
palladium precursor compounds on the genesis of such
catalysts, in view of the discrepancies on the subject in the
existing literature. To be sure that the effect of surface
functional coverage, if found, is not an accidental one,
several activated carbons from different sources have been
used. They have been subjected to pretreatments in oxi-
dizing or reducing surroundings, and the corresponding
catalysts were produced with variation of the preparation
conditions. Also, activated carbons are included in this
study that had undergone reaction with chlorine or am-
monia at elevated temperatures. It has been shown that on
chlorination of carbon blacks chlorine is bound to sp 2 and
sp 3 carbon atoms [21], and nitrogen functions similar to
pyrrole and pyridine are produced on the carbon surface
after the treatment with ammonia [22]. Particular care has
been taken to avoid side factors in the catalyst preparation,
such as the presence of adsorbed admixtures on the surface
of the supports or the detrimental influence of water, HCl
and other reduction products (by means of high flow-rates
of the reducing gas).
Somewhat surprisingly, the effect of the carbon pretreat-
ment proved rather small, in particular with Pd acetate as
the precursor. Not all supports and catalysts were studied
to the same extent but it was found that, in general, the
origin of the carbon used and the temperature of the
reductive treatment of the catalysts clearly prevailed in
terms of their influence on the catalyst properties.
2. Experimental
2.1. Reagents
Reagent grade chemicals were used in all cases. Nitro-
gen (99.999%), hydrogen (99.999%), oxygen (99.995%)
and carbon monoxide (99.97%) were obtained from Linde
AG, and ammonia (99.98%) from BASF. They were used
without further purification.
2.2. Carbons and their treatment
The starting activated carbons were selected from
commercially available samples. The main part of the
work was carried out with Anthralur STA, abbreviated as
Ant, produced from peat by Lurgi (Frankfurt / M) and AR,
made from coconut shells (Sutcliffe Speakman Carbon,
Ashton-in-Makerfield, UK). In some cases, Norit SGM
(Nor, from peat, by Norit, Amersfoort, The Netherlands)
and Sibunit (Sib, mesoporous carbon, produced industrially
in Russia by hydrocarbon pyrolysis, followed by gas
activation [23,24]) were used for comparison.
Following grinding (if necessary), fractions,100 mm
were isolated by sieving. To remove ash constituents from
the activated carbons, especially transition metal oxides,
they were treated for 3 days with boiling concentrated
hydrochloric acid, then washed with hot water in a Soxhlet
extractor for 3–4 weeks, and finally outgassed at 570 K in
vacuo (the extended washing and outgassing were neces-
sary to remove all chlorine from the activated carbons).
After such purification the ash residue did not exceed 2.6%
for Ant, 2.1% for Nor, and 0.1–0.2% in the other cases.
Gas treatments were performed in a vertical reactor
made from quartz glass. The pre-heated gas passed from
the bottom through a bed of the carbon (usually 6 g)
resting on a porous silica frit of ca. 25-mm diameter.
To remove surface complexes, the carbons were heated
to 1270 K in an N 2 stream for 6 h. They were exposed to
the ambient atmosphere only after cooling to room tem-
perature under N 2 . Surface cleansing with saturation of
reactive surface sites by hydrogen was achieved using an
analogous treatment under H 2 at 1170 K.
Surface oxides were produced by heating the carbons
first to 650 K under N 2 ; after 15 min the gas was switched
to O 2 (50 ml min 21 , the temperature in the carbon bed
rose to ca. 770 K) and after 30 min the oxidized carbons
were cooled under N 2 to room temperature. Using this
procedure, the burn-off could be kept below 10%. The
 M. Gurrath et al. / Carbon 38 (2000) 1241 – 1255
samples were homogenized by mechanical agitation over
several hours, this was also done when several batches
were oxidized to have a larger quantity of a sample.
In order to fix nitrogen functions on the surface, carbons
were treated at 1170 K with N 2 (1 h), then with NH 3 (4 h),
and cooled under N 2 . During NH 3 treatment, a substantial
fraction of the carbon is gasified as CH 4 , HCN and (CN) 2
[25] and nitrogen is bound to the surface in the form of
various functions that can be identified using XPS
[22,26,27]. Chemisorption of chlorine was effected by
passing a Cl 2 stream (20 ml min 21 , 2 h) through the
carbons which had been pretreated under N 2 (15 min) to
473 or 723 K. The nitrogen content of the prepared
samples was determined using the Kjeldahl method as
described earlier [22,25], and chlorine by fusion of the
carbons with Na 2 O 2 1Na 2 CO 3 in a Parr bomb, followed
by potentiometric titration of Cl 2 with a standard AgNO 3
solution.
The gas-treatment performed with a carbon will be
indicated in the code for the carbon by adding -H, -ox, -Cl
or -am, respectively. Carbons which underwent no treat-
ment, other than the previous HCl extraction and evacua-
tion, are designated by the symbol -u and those heat-
treated under N 2 at 1170 K by -HT.
The conditions of both the treatments and the storage of
the samples (in tightly closed vessels) prevented contami-
nation of the carbon surface by side-products and volatile
contaminants in the air. Additionally, all the carbons were
outgassed at 570 K at 10 22 Pa immediately prior to their
use as supports or performing titration and nitrogen
adsorption measurements. In particular, such a final treat-
ment can be considered adequate for getting correct
titration data on the nature and concentration of surface
oxides (especially CO 2 and strongly retained HCl from the
initial cleaning procedure affect the results of the acid–
base titrations.)
2.3. Titration measurements
Acidic groups on the carbon surface were determined
from adsorption neutralization with NaHCO 3 , Na 2 CO 3 ,
NaOH or NaOEt solutions. Three-hundred milligram sam-
ples were equilibrated overnight with 25 ml of 0.05 N
NaHCO 3 , Na 2 CO 3 or NaOH solutions; then 10 ml 0.05 N
HCl were added to 10 ml aliquots and back-titrated with
0.05 N NaOH after boiling off the CO 2 . This has been
described in detail elsewhere [28,29]. Adsorption from 0.1
N sodium ethoxide in ethanol was determined analogously.
Basic surface sites were determined similarly by adsorp-
tion from 0.05 N HCl solution.
2.4. Catalyst preparation
PdCl 2 (in 1 M HCl), Pd acetate (in acetone) and
[Pd(NH 3 ) 4 ](NO 3 ) 2 (aqueous solution) have been used as
metal precursors (all Pd compounds from Degussa). Typi-
cally, they were introduced into the pores of the supports
by incipient-wetness impregnation, with the Pd concen-
1243
tration in the solutions being adjusted to get a metal
loading of 100 mmol per gram of support, in some cases
also 50 and 200 mmol g 21 . Samples with supported Pd
complexes were dried in an oven at |380 K, followed by
final outgassing in a high vacuum at the same temperature
(420 K in some cases). A small amount of the resulting
sample (not more than 100 mg) was then taken for
reduction. With the exception of TPR experiments, the
reduction was performed in pure hydrogen, with a flow-
rate of 20 ml min 21 and heating to the final temperature at
a heating rate of 20 K min 21 .
2.5. BET surface areas and metal dispersion
The N 2 adsorption isotherms for the determination of
the BET surface areas were measured volumetrically at 77
K, using an apparatus built from stainless-steel tubing and
Swagelok connections. Only the sample bulb was made
from glass. Pressures were measured using Baratron gages.
Micropore volumes, Vmicro , were determined in the usual
way from Dubinin–Radushkevich (DR) plots of the N 2
adsorption isotherms. The widths of the micropores, Lmicro ,
were estimated from the DR characteristic energy, E0 ,
following Stoeckli et al. [30]: Lmicro 510.8 /(E0 211.4)
with E0 in kJ mol 21 and L in nm. For the surface area of
ideal, slit-shaped pores it follows from geometrical consid-
erations that Smicro 52Vmicro /Lmicro . Mesopore volumes and
surface areas were determined from the desorption branch-
es of the isotherms with the assumption of slit-shaped
pores, following the procedure outlined by Orr and Dalla
Valle [31].
Metal dispersions were measured using dynamic CO
chemisorption. A Pulse Microsorb 2700 instrument (Mi-
cromeritics) was used with hydrogen as the carrier gas
[12,32,33]. A freshly reduced surface was prepared by in
situ heating of the sample (ca. 10 mmol metal) to 323 K
under hydrogen for 1 h. These reduction conditions were
identical to those in the preparation of the catalysts. After
cooling to room temperature and stabilization of the heat-
conductivity cell, several 70-ml pulses of CO were injected
into the H 2 stream (20 ml min 21 ). Since CO is slowly
desorbed under flowing H 2 , consecutive pulses were
injected immediately after the curve had returned to the
base line (0.5–1 min). It was ascertained that the loss of
adsorbed CO was negligible under these conditions (the
results with a few test samples agreed well with those
obtained under static adsorption measurements).
2.6. Temperature-programmed reduction
The carbon samples loaded with the metal salts (40–50
mg) were outgassed at 383 K for ca. 16 h and placed into a
tubular flow reactor equipped with temperature-pro-
grammed heating. The samples remained in a stream of the
reducing gas (H 2 / N 2 1:19 v / v) overnight to stabilize the
base line of a heat conductivity cell before the heating up
to 600 K was turned on, typically with a heating rate of 10
1244 M. Gurrath et al. / Carbon 38 (2000) 1241 – 1255

K min 21 and a controlled gas flow of 20 cm 3 min 21 . lytic runs were carried out upon adding a new portion of
Volatile reduction products were frozen out at 77 K in a cyclohexene into the reaction mixture after completion of
trap between the reactor and the catharometer. the previous run.

2.7. Catalytic activity

Cyclohexene hydrogenation was performed at 303 K
and 1 bar of total pressure. A static reactor approximately
50 cm 3 in volume was used, and intensive stirring of the
reaction mixture was provided. Cyclohexene was prepared
by dehydration of cyclohexanol (Fluka) with hot concen-
trated phosphoric acid and distilled twice before use.
Special experiments were carried out varying the catalyst
amount added (2–30 mg), the stirring rate, or using a
shaker-type reactor. The results showed an absence of
strong poisons in the reaction mixture and a negligible
influence of external diffusion limitations under the stan-
dard conditions applied. To minimize internal diffusion
limitations, all catalysts were thoroughly ground in a
mortar to an average particle size of approximately 5 mm
prior to the catalytic runs.
The ground catalyst was placed into the reactor and
outgassed for 5 min. The reactor was filled with hydrogen,
and after 5 min methanol was added (8 ml) and the stirring
turned on. After another 5 min the reaction was started by
injecting 0.4 ml of cyclohexene. Charging the reactor
under such conditions ensured good reproducibility of the
catalytic measurements. The consumption of H 2 was
followed gas-volumetrically. In some cases, several cata-
3. Results
3.1. Selective titrations and nitrogen adsorption
Data on structural characteristics of the carbons after
different treatments and on the concentration of acidic and
basic sites on their surface are presented in Table 1. As
shown earlier [29], relatively strongly acidic groups such
as carboxylic acids are neutralized by NaHCO 3 , whilst
carboxyl groups condensed to lactone or lactol functions
require Na 2 CO 3 for neutralization. NaOH neutralizes, in
addition, weakly acidic groups such as phenolic OH
groups. Sodium ethoxide, NaOEt, reacts also with reactive
carbonyl groups, leading to salts of hemiacetals.
In full agreement with what might be expected from
previous work in the field [29], treatment with oxygen
gave supports with a significantly larger number of acidic
groups, especially those capable of being titrated by the
weak bases (carbonates). A simultaneous decrease in
consumption of HCl (see Table 1) is also in agreement
with earlier observations [29]. It is very probable that some
of these new groups were created at the expense of former
basic sites. As expected, the reductive treatment in nitro-
gen, hydrogen, or ammonia led to the opposite trends, that

Table 1
Characteristics of the carbon supports after various treatments
DR
Carbon SBET S micro V DR
micro Lmicro Smeso Vmeso Titration using
(m 2 g 21 ) (m 2 g 21 ) (cm 3 g 21 ) (nm) (m 2 g 21 ) (cm 3 g 21 )
NaOEt NaOH Na 2 CO 3 NaHCO 3 HCl
(meq g 21 ) (meq g 21 ) (meq g 21 ) (meq g 21 ) (meq g 21 )
Ant-u 630 640 0.246 0.77 28 0.083 890 355 155 80 400
Ant-ox 650 600 0.253 0.84 28 0.078 1430 940 560 200 300
Ant-HT 660 585 0.248 0.85 – – 360 100 65 7 450
Ant-H 710 680 0.266 0.78 31 0.072 – – – – –
Ant-am a 1000 730 0.366 1.00 – – 340 160 20 0 740
Ant-Cl b 440 410 0.170 0.86 24 0.059 880 335 65 75 –
AR-u 1310 1010 0.490 0.97 10 0.051 677 315 108 8 260
AR-ox 1390 900 0.550 1.23 16 0.070 – 400 – – 180
AR-H 1370 – – – – – 148 19 0 0 350
AR-am a 1350 850 0.520 1.24 10 0.043 – 103 – – 530
AR-Cl b 1210 920 0.490 1.06 – – – 302 – – –
Nor-u 1250 |750 0.450 |1.2 40 0.130 360 135 75 35 450
Nor-ox 1220 |720 0.430 |1.2 40 0.110 860 390 225 50 390
Nor-HT 1180 |700 0.420 |1.2 40 0.120 380 100 20 4 490
Sib-u 410 – 0.170 c 4.9 d .300 0.700 – 40 10 0 350
1.28 and 0.84 mmol N g 21 in Ant-am and AR-am, respectively.
a

All values based on carbon content to take account of mass increase by chlorination; 3.18 and 1.52 mmol Cl g 21 in Ant-Cl and AR-Cl,
b

respectively.
c
Formal value obtained by application of the DR equation, without accounting for the large surface area of the mesopores.
d
Formal calculation using the Stoeckli equation applicable at 0.4,L ,2.0.
 M. Gurrath et al. / Carbon 38 (2000) 1241 – 1255 1245

Table 2
Changes in BET surface area and micropore characteristics of Anthralur after loading with palladium complexes or treatment with the
solvents (all samples were outgassed at 570 K prior to the nitrogen adsorption measurements)
Treatment SBET Smicro Vmicro Lmicro
(m 2 g 21 ) (m 2 g 21 ) (cm 3 g 21 ) (nm)
No treatment 618 613 0.237 (0.241)c 0.77
H2O 609 600 0.235 0.77
Acetone 566 540 0.215 (0.232)c 0.80
Pd(OAc) 2 a / acetone 578 559 0.220 0.79
Pd(OAc) 2 b / acetone 574 561 0.219 (0.239)c 0.78
Aqueous HCl 562 489 0.219 (0.232)c 0.90
H 2 PdCl b4 / H 2 O 557 474 0.217 (0.235)c 0.91
Pd loading 100 mmol g 21 .
a

Pd loading 200 mmol g 21 .

b

c
Data in parentheses for the same samples treated in hydrogen at 673 K for 4 h.

is the number of basic sites increased but the concentration
of acidic ones decreased. In the case of ammonia, since the
reagent used for the treatment is itself a base, the increase
in surface concentration of the basic groups appeared
especially pronounced. As has been shown earlier,
pyridine- and pyrrole-like functions are created at the
edges of the graphene layers by such treatment [22,26].
Treatment with chlorine resulted in a small decrease of the
oxygen-containing acidic sites as well. The relatively high
consumption of basic reagents in this case can be assigned,
in part, to a hydrolysis of chemisorbed chlorine, since
substantial quantities of chloride ions were found in the
solutions [34,35]. Some chloride is already found in
solution after washing with water.
In contrast to the remarkable changes in the nature and
concentration of surface functionalities, the conditions
used for the treatments allowed for relatively small
changes in the porous structure of the carbons. An
appreciable increase of apparent surface area and pore
volume can be noticed only for Anthralur treated with
ammonia. Substantial quantities of carbon were gasified in
this case and additional micropores were created [25,36].
A considerable decrease of the micropore volume of
Anthralur after chlorination is caused by blocking of the
entrances to the micropores by chemisorbed chlorine
atoms. They can be removed by treatment in hydrogen at
670 K, after which the micropores become accessible again
[34,35].
The changes in the porosity after deposition of the metal
precursors was measured with the Anthralur carbon.
Samples with supported metal complexes showed a some-
what lower surface area and a decreased pore volume, as
compared to the original Anthralur (Table 2). The same
was observed, however, for the carbon treated with HCl
only, or with acetone. Acetone may undergo condensation
reactions under the influence of basic or acidic surface
sites producing oligomeric or polymeric products, analo-
gously to the reactions known to occur on alumina [37,38]
or titania surfaces [39]. As for H 2 PdCl 4 and / or HCl,
obviously, they are adsorbed predominantly in micropores
or at the entrances to such pores, thus preventing nitrogen
adsorption in part of the pores. The data in the last column
of Table 2 show an appreciable increase in the apparent
average size of the micropores for the samples treated with
HCl or HCl1H 2 PdCl 4 , which is very likely caused by
blocking of the smallest pores by the acidic species. One
can see in Table 2 that the micropore volumes were largely
restored after subsequent heating to 673 K in hydrogen.
Under these conditions, hydrogen chloride introduced into
the sample in the treatments with H 2 PdCl 4 and / or HCl
was eliminated and the chlorine content became the same
as that in the initial carbon (Table 3).

Table 3
Changes of chlorine content of Anthralur-based samples after treatment in hydrogen at increasing temperature
Sample Sample Cl content (mmol g 21 )
no.a code a
Without Reduction Reduction
reduction at 523 K (2 h) at 673 K (4 h)
1 Ant 190 155 150
2 PdCl x /Ant 710 305 –
3 HCl /Ant 365 285 165
a
1, Initial carbon; 2, sample with supported palladium chloride (incipient wetness impregnation with solution in 1 N HCl, Pd loading 100
mmol g 21 ), evacuated at 423 K; 3, Anthralur treated with 1 N HCl under the same conditions as for sample 2.
1246 M. Gurrath et al. / Carbon 38 (2000) 1241 – 1255
3.2. Temperature-programmed reduction
TPR studies have been carried out with palladium
complexes deposited on Ant and AR carbons. All samples
showed intense TPR signals at higher temperatures, with
the maxima being typically in the 400–500 K range, whilst
barely any hydrogen was consumed by the parent carbons.
The position, width and intensity of the peaks depend
significantly on the pretreatment of the supports. This is
exemplified in Fig. 1 for samples loaded with H 2 PdCl 4 .
They showed the sharpest peaks, whilst palladium acetate
gave broader signals in most cases (not shown), and
several maxima appeared with the tetrammine complex.
There was a much larger peak size when the carbon
surface carried chemisorbed oxygen or chlorine (-u, -ox,
-Cl samples) compared to the reduced surface (heat-treated
in hydrogen, inert gas, or ammonia; -H, -HT, -am). The
TPR peaks occurred at a lower temperature with the
Fig. 1. TPR curves for differently pretreated Anthralur and AR
carbons loaded with H 2 PdCl 4 (100 mmol g 21 ). *, Sample loaded
with 100 mmol g 21 [Pd(NH 3 ) 4 ](NO 3 ) 2 .
samples supported on oxidized carbons than with the
samples on a reduced carbon surface. Close inspection
shows, however, that also in the latter case there is a slow
hydrogen consumption already at the temperature of the
peaks observed with the oxygen-containing samples.
Clearly, both the reduction of the palladium species and
the reaction of hydrogen with surface functional groups are
responsible for the hydrogen consumption. As soon as
some metallic palladium is formed, dissociatively adsorbed
hydrogen can move by a spillover mechanism [40] over
the support surface to sites of chemisorbed oxygen or
chlorine and reduce them in competition with the reduction
of the remaining Pd n 1 species [10]. A decrease of acidic
surface groups on treatment with hydrogen of Pd- or
Pt-loaded oxidized activated carbon is confirmed by the
selective titration and has been observed already at 420 K
[41].
Sometimes, a negative peak near 350 K was also seen. It
obviously results from decomposition of the interstitial
palladium hydride phase (b-phase) [42–44] formed from
metallic palladium already generated in the preparation of
the catalysts or during the initial flushing with hydrogen at
room temperature. The negative TPR signals were much
smaller or not discernible when oxidized or chlorinated
carbons were used as the support (-u, -ox, -Cl) or when the
tetrammine complex or palladium acetate were applied,
independently of the pretreatment of the carbons.
3.3. CO chemisorption
In the present work, a chemisorption stoichiometry of
one CO molecule per surface Pd atom is assumed. It is
well known [45] that CO is adsorbed in a bridging mode
on well-defined crystal faces of large Pd crystals with a
CO / Pd s ratio of 0.5. The stoichiometry changes, however,
with decreasing particle size, because an increasing frac-
tion of the CO is linearly adsorbed, corresponding to a
stoichiometric ratio of 1 [33,46–48]. Therefore, it is
justified to assume a ratio of 1 for small particles (,5 nm),
although the calculated dispersions tend to be somewhat
underestimated for catalysts with larger Pd particles.
Krishnakutty and Vannice found that dispersion values for
Pd on carbon supports tend to be a little higher when
adsorption of CO is used rather than that of H 2 [16]. This
is explained by a contamination of the metal surface with
carbon atoms originating from the carbon support. Appar-
ently, CO adsorption is less inhibited than that of hydro-
gen, and the authors concluded that CO chemisorption is
preferable for the determination of exposed metal atoms in
the case of Pd / carbon catalysts [17]. On ZrO 2 -supported
palladium, CO reacts above |373 K to a solid solution of
C in Pd and CO 2 [49]. Continuous disproportionation
(Boudouard reaction) with deposition of carbon on the
metal surface occurs at higher temperatures, i.e. .550 K.
The interstitial carbon was found to be very reactive,
formation of CH 4 with H 2 begins at |400 K. Thus, the
 M. Gurrath et al. / Carbon 38 (2000) 1241 – 1255 1247

Boudouard disproportionation should not interfere with the

dispersion measurements at room temperature, and the Pd
surface should be free of carbon dissolved in interstitial
sites after exposure to H 2 at temperatures .400 K.
However, in view of the uncertainties in the reaction of
CO with Pd surfaces, the measured dispersion values
should be considered as apparent dispersions. Even if the
absolute values are not entirely correct, they reflect the
correct relative order of the dispersions.
The chemisorption properties proved to be strongly
dependent on the reduction temperature. In the majority of
cases, more or less sharp maxima in the CO uptakes as a
function of the reduction temperature were seen in the
range 370–420 K, as exemplified for one of the samples in
Fig. 2(a). On the one hand, only small CO consumption
was observed after pretreatment of the samples in hydro-
gen at room temperature, and even a prolonged exposure to
hydrogen at this temperature had little effect. As Table 4
shows, an increase in the time of pretreatment up to 3 days
led to some increase in the CO uptake, but it was still
several times smaller than the value obtained for the same
sample after 1 h reduction at 423 K. Only in some cases, a
relatively high CO uptake after H 2 treatment at room
temperature has been observed. This occurred mainly with
catalysts derived from the tetrammine complex and is
illustrated in Fig. 2(b) for Norit-supported samples, for
which such a distinction was most pronounced. A plausible
reason might be that metallic palladium was already
formed to some extent by an internal redox reaction of the
tetrammine salt during drying after the impregnation step
(see Section 2.4). Reagan et al. have reported that
[Pd(NH 3 ) 4 ] 21 ions in Y zeolites are decomposed at |520
K in an inert atmosphere [50]. It has been indicated that
the reaction may take place at lower temperatures (|430
K) on carbon surfaces [51].
On the other hand, whatever the sample, there was
always a strong decrease in the apparent palladium disper-
sion upon reduction above 420 K, obviously due to
sintering of the metal. This is clearly seen in Fig. 2, and
also in Table 5. A significant decrease of the apparent Fig. 2. Apparent dispersion values (CO / Pd) as a function of the
dispersions was observed at 573 K and higher temperatures reduction temperature (treatment with H 2 for 1 h): (a) for H 2 PdCl 4
when the duration of the reduction treatment was extended on Ant-HT; (b) [Pd(NH 3 ) 4 ](NO 3 ) 2 on Nor-ox. The metal loadings
much beyond 1 h; this is in agreement with literature were 50 mmol g 21 (open symbols) and 200 mmol g 21 (filled
reports [9,12]. symbols).
In comparison to the reduction temperature, the nature
of the palladium precursor compound and the pretreatment
of carbon support had a smaller effect on the metal Table 4
dispersion, with their influence being comparable to that of CO chemisorption on a sample of palladium acetate supported on
other variables upon catalyst preparation. Table 6 lists the AR-u carbon (100 mmol g 21 ) and treated in a H 2 stream at
dispersion values for palladium on differently modified ambient temperature for different times
Ant- and AR-carbons. These catalysts were reduced at 420
Reduction time CO / Pd a
K, which seems optimal for ensuring complete reduction
but preventing significant sintering. Compared to analo- 2h 0.100
gous Ant-based samples in Table 5, the metal loading was 1 day 0.127
3 days 0.198
halved and the conditions of drying were milder to get a
a
higher dispersion of the palladium. Table 7 presents Equals 0.56 after reduction at 423 K for 1 h.
1248 M. Gurrath et al. / Carbon 38 (2000) 1241 – 1255

Table 5
Influence of reduction temperature on apparent dispersion of palladium (%) in Ant-based samples (Pd 200 mmol g 21 , final drying in vacuo
at 423 K prior to reduction for 1 h)
Support (CO / Pd)3100
T Red 5423 K T Red 5573 K
Palladium chloride as metal precursor:
Ant-u 58 19
Ant-ox 73 20
Ant-HT 64 20
Ant-H 34 14
Ant-am 35 20
Palladium acetate as metal precursor:
Ant-u 30 20
Ant-ox 27 19
Ant-HT 38 15
Ant-H 28 23
Ant-am 32 27
Ammine complex as metal precursor:
Ant-u 30 17
Ant-ox 27 18
Ant-HT 38 16
Ant-H 47 18
Ant-am 52 28

Table 6 the smallest dispersions (Tables 5 and 6). Relatively low

Apparent dispersion of palladium (%) in AR- and Ant-based dispersions of platinum have been observed earlier when
catalysts reduced under mild conditions (metal loading 100 the adsorbed [Pt(NH 3 ) 4 ] 21 complex was directly reduced
mmol g 21 , drying at 383 K, reduction at 423 K for 1 h) with hydrogen [5,7]. This is assumed to be due to the
Support (CO / Pd)3100 intermediate formation of a mobile species, probably
Precursor: PdCl 2 Pd(OAc) 2 [Pd(NH 3 ) 4 ](NO 3 ) 2 [Pt(NH 3 ) 2 H 2 ], that leads to easy agglomeration. The
authors obtained higher dispersions when the Pt tetra-
Ant-u 71 61 27 mmine complex was first thermally decomposed under
Ant-ox 70 54 15 helium prior to complete reduction with hydrogen. The
Ant-H 28 45 19
palladium tetrammine complex shows an analogous be-
Ant-am 66 37 19
Ant-Cl 68 64 5 havior [52]. Such a positive effect of the preceding
AR-u 68 56 2 decomposition of the tetrammine complex is visualized in
AR-ox 55 23 16 our case as well. One can compare the data presented in
AR-H 46 15 18 Tables 5 and 6 for Ant-supported catalysts reduced at 423
AR-am 58 47 31 K; if palladium acetate serves as the metal precursor, the
AR-Cl 21 25 6 dispersions of the samples in Table 5 appear appreciably
smaller than those in Table 6, but quite the opposite is seen
for samples prepared from the tetrammine complex. As the
catalysts in Table 5 have a higher Pd loading and were
available data for Nor-supported samples differing in the subjected to outgassing at a higher temperature before
pretreatment of the support. reduction, one should expect in this case a more pro-
The use of the tetrammine complex tended to result in nounced decomposition of the supported tetrammine com-
Table 7 plex in the drying stage. A higher extent of the decomposi-
Apparent dispersion of palladium (%) on oxidized and heat- tion of the complex at a higher loading can also explain the
treated Norit (metal loading 200 mmol g 21 , final drying at 423 K, higher apparent Pd dispersion in samples with Nor-ox as
reduction at 523 K for 1 h)
the support [Fig. 2(b)] upon changing the Pd loading from
Support (CO / Pd)3100 50 to 200 mmol g 21 , irrespective of the reduction tempera-
Precursor: PdCl 2 Pd(OAc) 2 [Pd(NH 3 ) 4 ](NO 3 ) 2 ture.
The only certain effect of carbon surface treatments,
Nor-HT 22 30 33 well-reproducible upon repeated preparations, was a small-
Nor-ox 35 37 25
er dispersion of palladium on the carbons modified in
 M. Gurrath et al. / Carbon 38 (2000) 1241 – 1255 1249

hydrogen (Ant-H and AR-H), provided that the dispersion

on the initial carbon was high. To some extent this was
found also after treatment with chlorine. In other cases, the
results proved inconclusive, being dependent on the parent
carbon and variables in the catalyst preparation. For
instance, both PdCl 2 - and, to a lower extent, Pd(OAc) 2 -
derived samples showed a higher dispersion on oxidized
Norit (Table 7). The same was noticed for Ant-based
samples in Table 5 (first column), provided that they were
prepared from PdCl 2 but not Pd(OAc) 2 . At the same time,
according to the data in Table 6, oxidation of the original
Ant and AR carbons gave rise to a negative rather than a
positive effect on the palladium dispersion.

3.4. Cyclohexene hydrogenation

Catalytic tests have been made for samples which were

reduced under mild conditions and are characterized in
Table 6. The activity data are presented in Fig. 3 as a
function of the apparent palladium dispersion. (If not
stated otherwise, we refer here and later to the catalytic
activity with respect to the mass of catalyst, in contrast to
specific or intrinsic activity which are related to surface
metal atoms only.) Also tested were catalysts supported on
Sibunit carbon which were prepared under the same
conditions as the samples on Ant and AR carbons from
Table 6. The catalytic tests for the 1%Pd / Sib-u catalysts
prepared from palladium chloride, acetate, and the tetra-
mmine complex exhibited activity values of 2300, 2300
and 1100 cm 3 H 2 per minute and gram catalyst, respective-
ly.
The catalytic activity per surface Pd atom proved to be
dependent mainly on the nature of the metal precursor and
the starting activated carbon, but not on the pretreatments
of the carbons. For catalysts with similar Pd dispersion, it
increased in the order PdCl 2 ,Pd(OAc) 2 |
[Pd(NH 3 ) 4 ](NO 3 ) 2 and Ant,AR,Sib. As for the carbon
surface treatments, our results suggest only tentatively a Fig. 3. Catalytic activity in cyclohexene hydrogenation as a
function of apparent dispersion (CO / Pd): (a) for Pd /Ant; and (b)
lower intrinsic activity of Pd(OAc) 2 -derived catalysts on
Pd /AR catalysts from Table 6. Open circles, Pd tetrammine
the untreated and Cl 2 -treated supports and an increased complex as the metal precursor; solid circles, PdCl 2 ; stars,
activity of catalysts prepared on oxidized carbons. Pd(OAc) 2 .
A more detailed analysis of the data met with complica-
tions, as the course of the kinetic curves (rate vs. time)
appeared not to be identical for all the samples. Usually, catalysts remained essentially the same, however, if ac-
the catalysts showed some deactivation with time-on- tivities displayed in the second or third runs were com-
stream (as with the Pd /AR-H catalyst in Fig. 4, data pared, i.e. at longer residence times of the catalysts in the
marked by open symbols). The decrease in rate during the reaction mixture.
first run varied from sample to sample and, in some cases, The catalytic performance was virtually the same when
even an increase of the rate was seen (as with the second reagents (cyclohexene and hydrogen) and solvent from
catalyst, Pd /AR-Cl, in Fig. 4, open symbols). For evalua- different sources or with additional purification (repeated
tion, the activity shown in the first run at 30% conversion distillations, passing through a column with activated
for cyclohexene was taken. The initial activity in this run alumina or Pd / Pt catalyst) were used. The non-identical
could differ from the presented values by up to620%, and changes in catalytic activity with time should thus be
the activities in subsequent runs (with addition of a new attributed to chemical effects (restructuring of the active
portion of cyclohexene) comprised 80–100% of the values centers) rather than to the presence of poisoning con-
determined in the first run. The order in activity of the taminants in the reaction mixture.
1250 M. Gurrath et al. / Carbon 38 (2000) 1241 – 1255

Fig. 4. Examples of kinetic curves for catalysts in cyclohexene

hydrogenation. Open symbols represent first runs and filled
symbols repeated runs with the same catalysts (with addition of a
new portion of cyclohexene 5 min after completion of prior run).
Both catalysts from [Pd(NH 3 ) 4 ](NO 3 ) 2 .

Analysis of the presented data and results of special

experiments prove also that macrokinetics (diffusion limi-
tations) play a minor role, if any, in the observed differ-
ences of the samples in catalytic activity. In Fig. 5(a) one
can see data for two catalysts, Pd /Ant-ox and Pd /AR-u,
which differed in activity per gram approximately in a 1:2
ratio. In this case, an increased quantity of the Pd /Ant-ox
catalyst was loaded into the reactor to produce a reaction
rate similar to that observed with the Pd /AR-u catalyst,
and the catalytic performance in the second runs is shown
in Fig. 5(a), i.e. for catalysts which have already ap-
proached the steady state in the reaction mixture, as the
true dependence of the rate on conversion may be masked
in the first runs by catalyst activation / deactivation. One
can see that the decline in the reaction rate with increasing
conversion (i.e. with decreasing concentration of the
organic substrate) is approximately the same for both
catalysts. The reaction rate was fairly constant at the
beginning and decreased significantly only when the
conversion reached 70–80%. Fig. 5(b) shows subsequent
(third) runs with the same catalysts in which the ex-
perimental conditions were extended. These runs were
begun as usual, i.e. 0.4 ml of cyclohexene were added to
the reaction mixture after consumption of all the cyclohex-
ene in the preceding run. However, an additional quantity
of cyclohexene was added in these third runs at the time
indicated by arrows, corresponding to 35% conversion of
the original cyclohexene loading. It is clearly seen that
such an increase in the cyclohexene concentration had no
significant effect on the catalytic activity.
Diffusional limitations with respect to the supply of the
Fig. 5. (a) Reaction rate in second runs as a function of cyclohex-
ene conversion; Pd /AR-u and Pd /Ant-ox as catalysts (both from
PdCl 2 ). (b) Subsequent runs with the same catalysts. At the point
of |35% conversion (indicated by arrows) an additional quantity
of cyclohexene (0.5 cm 3 ) was added during these runs.
second reagent (hydrogen) would be more likely, due to its
low solubility in common organic solvents and a positive
order of the reaction rate with respect to the concentration /
pressure of H 2 (the order is equal to 0.5 for cyclohexene
hydrogenation on Pd catalysts [53]). To check the absence
of such limitations in our case, fresh PdCl 2 -derived
samples on Anthralur and AR supports with similar metal
dispersion have been prepared and tested in the hydro-
genation of cyclooctene (using the same technique as in
cyclohexene hydrogenation but with the use of ethanol as
the solvent [20]). The reactivity of cyclooctene is more
than an order of magnitude lower than that of cyclohexene,
and thus the rate of hydrogen consumption per gram of
 M. Gurrath et al. / Carbon 38 (2000) 1241 – 1255
catalyst is much smaller. If strong diffusion limitations
with regard to hydrogen were responsible for the observed
difference in catalytic activity in the hydrogenation of
cyclohexene for the catalysts on different supports, one
should expect disappearance or, at least, a strong decrease
of such differences upon hydrogenating cyclooctene. The
difference remained at the same level, however. The
activities shown by the freshly prepared Pd /Ant (67%
dispersion) and Pd /AR (|60% dispersion) catalysts were
equal to 450 and 1300 cm 3 min 21 g 21 , respectively, in the
hydrogenation of cyclohexene, and to 12 and 38 cm 3
H 2 min 21 g 21 , respectively, in the hydrogenation of
cyclooctene on the same catalysts. It should be also noted
that the volume of mesopores, which are mainly involved
in the reagent transport to the active phase, is larger for
Ant (Table 1), than for AR, but only the Pd /Ant catalysts
exhibited the lowest activity, see Fig. 3(a) and (b).
4. Discussion
4.1. Influence of carbon pretreatments
In contrast with what we expected at the beginning of
this study, the results show a rather small effect of the ratio
of acidic and basic surface sites on the dispersion and
catalytic activity of carbon-supported palladium, and also
of incorporation of nitrogen or chlorine heteroatoms in the
carbon surface. It may only be noticed that the reductively
treated carbons (-H, -am, -HT) contain some palladium in
a metallic or easily reducible form after the deposition of
PdCl 2 (as evidenced by a negative TPR peak in the
low-temperature region, Fig. 1), and there is a tendency for
the palladium to show a lower dispersion on the carbons
heat-treated in hydrogen (-H in Tables 5 and 6). On the
other hand, the oxidized carbons (-ox) tend to exhibit a
higher intensity of the TPR peaks at elevated temperatures,
and to induce also a slightly higher catalytic activity. These
trends are consistent with other data (not reported) which
we have for Pd catalysts on other carbon supports or
prepared in somewhat different conditions.
There is little doubt that the exact position and intensity
of the TPR peaks in the elevated-temperature region are
determined in a significant way by the reaction of hydro-
gen generated by spillover with surface oxides or chlorides
and, thus, not much information with regard to the
palladium can be obtained from the TPR curves above 400
K. As for the formation of metallic palladium at low
temperature, the following two mechanisms seem equally
possible. (1) Solutions of salts or complex compounds of
precious metals have oxidizing properties. In consequence,
they will react with carbon surfaces creating surface oxides
in a similar way as other oxidants, e.g. nitric acid,
hypochlorite, or peroxodisulfate ions [29]. The surface
oxidation reaction is accompanied at the same time by a
reduction of the precious metals to a lower valency (e.g.
1251
Pt II ) or the metallic state, as has been repeatedly described
[8,9,51,54–58]. The reductive power of the carbon de-
creases with increasing surface oxidation, and the extent of
surface oxidation depends also on the nature of the
oxidant, its concentration, pH and temperature; e.g.
[Pt(NH 3 ) 4 ] 21 at pH 8.5 will not be reduced by carbon
[51]. (2) Alternatively, there can be a partial hydrolysis of
the precursor metal complex during catalyst preparation
and this will result in the deposition of easily reducible
oxide or hydroxide species on the support surface. Some
oxide species of palladium and platinum are known to
undergo reduction with hydrogen already below room
temperature [43,59–61]. Such a reaction has been reported
even at |173 K [62]. This hydrolysis will also be
facilitated on a reductively treated surface. Removal of
chemisorbed oxygen will raise the concentration of basic
surface sites which favors the hydrolytic reaction as the
sites can bind the acid (HCl or HOAc) formed in the
hydrolysis and, thus, participate in the equilibrium. Forma-
tion of relatively large metal or metal oxide particles prior
to the reduction in hydrogen might cause a poor dispersion
of the catalysts. However, Fig. 1 shows clearly that the
intensity of the negative TPR peaks was rather small in
every case, and that, therefore, only a minor part of the
palladium chloride was converted to the metal in the
preliminary stages of the TPR experiments.
While it has been reported that high metal dispersions
could be obtained after ion exchange with surface oxygen
groups [6], further studies showed disappointingly low Pt
dispersions on oxidized carbon surfaces [51,57,63]. This
was assumed to be due to the thermal decomposition of
many surface groups, namely carboxyl groups, at relatively
low temperatures, i.e. above 470 K. When these groups are
destroyed, the fixed small metal particles (or unreduced
precursor) will become mobile on the surface and will
agglomerate to larger particles [51,63].
Several possible reasons may be cited for the small
effect of surface coverage of the carbons on the properties
of the catalysts studied in the present work. First, it can
partly be attributed to limitations of the applied technique
for the determination of true Pd dispersion and, secondly,
to some uncertainty in the activity values, as mentioned in
Section 3.4. In particular, this seems responsible for the
scattering of experimental points seen in Fig. 3 for
catalysts prepared from the same Pd salt. Thirdly, one
should take into account the strong influence of the
reduction temperature indicated by the sharp peak of Pd
dispersion vs. temperature in Fig. 2(a). In Table 6 and Fig.
3 catalysts are compared which have been reduced at 423
K. This temperature has been chosen as the standard one,
as it can be considered sufficient for the reduction of at
least the major part of palladium, whereas a higher
temperature already led to substantial decreases in both CO
uptakes and catalytic activity. However, the optimal tem-
perature for achieving the highest Pd dispersion is not
necessarily the same for different catalysts.
1252 M. Gurrath et al. / Carbon 38 (2000) 1241 – 1255
Besides these masking factors, it seems reasonable to
suggest the occurrence of compensation phenomena. The
first one refers to the surface sites capable of anchoring
metal complexes and stabilizing the supported metal
against sintering. Even in the original form (-u), the
activated carbon surfaces carry a sufficiently large number
of such sites, as Pd dispersions as high as 60–70% could
be obtained with proper adjustment of the other prepara-
tion conditions. The anchoring occurs by different mecha-
nisms, however. If some of the anchoring sites are
destroyed during a treatment, the number of the remaining
ones could still be sufficient to bind the complex, at least at
a Pd loading of 0.5–2 wt.%, as used in the present work.
Alternatively, the metal precursor is bound, more or less
effectively, by newly created groups. For instance,
H 2 PdCl 4 probably interacts with olefinic p-fragments of
the surface by exchange of Cl ligands [15], but the
[PdCl 4 ] 22 anion might also be bound in acidic media by
ion-exchange on protonated oxygen-containing surface
groups. Carboxyl groups seem most suitable to bind by
ion-exchange the positively charged [Pd(NH 3 ) 4 ] 21 com-
plex, in particular at relatively high pH values. If these
groups are destroyed by heat treatment under ammonia, the
complex may be adsorbed by ligand exchange with the
newly created N-containing groups on the modified sur-
face. As a consequence, the Pd dispersion can be retained
at the same level. Only if there is a very strong decrease in
the number of active sites on the carbon surface, as upon
heat-treatment in hydrogen which saturates radical sites
and generates inert CH x fragments at the expense of
olefinic groupings and acidic centers, does a drop in Pd
dispersion become apparent.
Secondly, catalysts pass through several stages during
their preparation and the surface groupings act in coopera-
tion with other factors. A positive or negative influence of
the carbon treatment in one stage might be compensated in
subsequent steps. For example, the spontaneous reduction
of the metal precursor upon contacting the carbon surface
or its hydrolysis on the surface (see above) might lead to
formation of massive particles of a metallic or oxidic
phase, respectively, i.e. to a low dispersion of the pal-
ladium. However, the same processes could give rise to
numerous metallic or easily reducible particles capable of
serving as metal nuclei upon further reduction of the
samples with hydrogen. This should be of advantage for
obtaining a high dispersion. Even the treatment of the
carbons in hydrogen or chlorine might give rise to a
positive effect, as the hydrophobicity of the surface
produced by such treatments facilitates removal of water
during catalyst reduction, thus diminishing its detrimental
effect [64] on metal dispersion. Such a complex interplay
of different factors prevents a clear understanding of the
effect of the carbon treatments and is probably the main
reason for the discrepancies existing in the relevant
literature. Certainly, the role of different characteristics of
the carbon support must be considered in connection with
all other parameters and conditions used in the catalyst
preparation. In particular, it may be important that all
catalysts studied in the present investigation contained
relatively small quantities of palladium (0.5–2 wt.%) and
all supports, even those designated as ‘untreated’ (-u), had
undergone some aging and some sort of thermal treatment
before being used as supports for the palladium salts.
4.2. Influence of the porosity of the supports
In contrast to the small and variable effect of the surface
treatments, the catalysts showed a significant difference in
intrinsic activity, depending on the activated carbon from
which they were prepared, i.e. Ant, AR or Sib. AR-based
catalysts are 2–3 times as active as Ant-supported ones
(Fig. 3), and Sib-based catalysts are superior (|1.5 times)
to those supported on AR. The same order of activity has
also been found for Pt catalysts on these supports [19]. In
view of the small effect found of the surface functional
coverage on the catalyst properties, the differences in
activity for catalysts on supports of different origin should
be ascribed to differences in their porous structure. How-
ever, the porous structure of the supports could not affect
significantly our experimental results by way of a diffu-
sional factor, as the results of the special experiments with
cyclooctene gave strong evidence against a predominant
role of diffusional limitations. We have to conclude that a
steric but not a diffusional factor is responsible for the
observed differences in activity for the catalysts supported
on the Ant, AR and Sib carbons.
Apparently, a part of the smallest Pd particles was
blocked in micropores. Small metal particles in narrow
slit-shaped pores of the activated carbons may form flat
interfaces with opposing walls of the pore, leaving only a
part of the metal surface accessible to the relatively bulky
organic substrate in the catalytic process. The catalytic
activity proved to be the lowest for palladium on Ant,
which contains particularly narrow pores, but the highest
in the case of Sibunit, which is distinguished by a low
degree of microporosity and a lack of narrow micropores
(Table 1). We have thus to assume that the narrower the
pores are in the support, the higher is the probability of
inaccessibility of the metal particles.
Such a pore effect provides an easy explanation for the
lower intrinsic activity of PdCl 2 -derived catalysts. Evident-
ly, the small and more planar molecules of H 2 PdCl 4 can
penetrate deeper and into smaller pores than the more
bulky precursors, [Pd(NH 3 ) 4 ](NO 3 ) 2 and trimeric
[Pd(OAc) 2 ] 3 (in solvents of relatively low polarity). The
probability for the pore effect must therefore be the highest
with palladium chloride as the metal precursor. As might
be expected, the catalytic activities of the PdCl 2 -derived
catalysts differed most clearly from the other ones when
Anthralur was used as the support, which is distinguished
by the narrowest pores [Fig. 3(a) and (b)]. At the same
time, catalysts on mesoporous Sibunit, being prepared
 M. Gurrath et al. / Carbon 38 (2000) 1241 – 1255
from PdCl 2 and Pd(OAc) 2 and having similar dispersion,
showed equal catalytic activity.
The possibility of encapsulation of the active phase in
microporous supports has long been recognized but exam-
ples of experimental verification are scarce. The molecular
sieving effect has been detected for special types of carbon
supports (carbon fibers) [65] or special methods of catalyst
preparation (such as incorporation of a metal compound in
the carbon precursor prior to carbonization) [66–70]. The
data collected in the present study show the blocking to
occur even if common activated carbons and commonly
accepted conditions of catalyst preparation are used.
It is sometimes assumed that little metal is deposited in
the micropores of activated carbons because they are more
or less inaccessible to the typical metal complexes used as
precursors. However, this assumption is obviously not
valid when the pores are slit-shaped and the complexes are
planar. Besides, there is good opportunity for the metal to
penetrate into the micropores during thermal treatments of
the samples, when the complexes begin to lose their
ligands, especially in the reduction step.
4.3. Effect of the reduction temperature
TPR data published in the literature give evidence for
rather a broad range of the conditions necessary for the
reduction to the metallic state of supported metal com-
pounds [61]. There are examples where the reduction of
carbon-supported platinum metals with hydrogen is per-
formed at 570 K and higher temperatures [5,16], but other
authors consider treatment even at ambient temperature to
be sufficient to obtain the metallic state (see Ref. [12]).
Palladium is an easily reducible metal and it has been
reported [60] that palladium oxide is reduced already at
|293 K. However, the required temperature is dependent
on several factors, in particular, on the nature of the metal
complex and its dispersion state. Platinum oxide was
reduced at a substantially lower temperature than the
chloride complex or a partially hydrolyzed chloride com-
plex [60]. Thus, the reduction at room temperature may be
limited and the fraction of the surface metal atoms
underestimated by CO chemisorption. Indeed, the catalysts
in Fig. 2(a) are characterized by negligible CO uptakes if
pretreated in H 2 at ambient temperature (see also Table 4).
The necessity of treating the samples at an elevated
temperature before CO chemisorption is consistent with
the results of the TPR study which always showed
hydrogen consumption at elevated temperatures (Fig. 1).
The somewhat lower temperature for the peak maxima in
CO chemisorption can hardly be surprising; in this case,
the samples have been pretreated for 1 h at each tempera-
ture and the pretreatment was made in pure hydrogen,
whereas the TPR technique required for a high dilution of
hydrogen with an inert gas and a temperature ramp.
Reduction at higher temperatures provokes a decrease in
the Pd dispersion, however. It attracts attention that the
1253
decrease appeared strong even at rather moderate tempera-
tures, such as 450–500 K. Heal and Mkayula [12] also
described a drop in the apparent dispersion of Pd / C
catalysts from 78% to 18% (they assumed a CO asd /
Pd surface ratio of 0.5) when the reduction was performed at
457 K instead of 298 K. Meanwhile, many literature
references for carbon-supported Pd catalysts, e.g. Refs.
[71–74], report a rather small effect of temperature on the
metal particle size if the treatments are performed below
500–600 K. Typically, a temperature of more than 700–
800 K is required for a significant enlargement of the
particles within short times.
A strong decrease in CO uptakes after reductive treat-
ment of our Pd / C catalysts at temperatures slightly above
the optimal one took place independently of which acti-
vated carbon was used as the support and which Pd
complex was used as the metal precursor. Such a behavior
is quite different from that of analogous Pt / C samples
which showed stability in the same temperature range (at
least at 420–620 K [19]). Such a difference deserves
special study. Perhaps, the drop in apparent dispersion for
palladium at 450–500 K is caused not only by sintering of
the metal but also by other reasons, e.g. deeper penetration
of palladium into the pores (so that part of the metal
surface becomes inaccessible not only to the organic
molecules but also to CO) or formation of surface or even
bulk carbides (due to an interaction between palladium and
the amorphous part of the carbon support).
Whatever the reasons, such a strong effect of tempera-
ture on the properties of Pd / C catalysts calls for extreme
caution when using these catalytic systems and choosing
methods for their investigation (e.g. chemisorption mea-
surements in a static system with preliminary high-tem-
perature outgassing of the samples). This lower thermal
stability of palladium is reflected in the poorer knowledge
on Pd / C catalysts as compared to Pt / C. It might also
explain why carbon-supported palladium catalysts, while
demonstrating excellent properties in hydrogenation re-
actions and other processes relating to fine organic syn-
thesis, did not find application in high-temperature pro-
cesses. Although the route into this field is not closed for
Pd / C catalysts, special carbon supports must probably be
developed for such applications.
5. Conclusions
1. Treatment of activated carbons with oxygen, hydrogen,
ammonia, chlorine or by heating them in an inert gas
provides a means of smoothly varying the surface
chemistry of carbon supports. The conditions of the
treatment can be so adjusted that the accompanying
changes in the porosity of the supports are reduced to a
minimum. The influence of the state of the carbon
surface, e.g. its coverage with functional groups, on the
1254 M. Gurrath et al. / Carbon 38 (2000) 1241 – 1255
dispersion of the active phase proved comparable,
however, to the effect of the nature of the metal
precursor and other conditions used during catalyst [6]
preparation.
[7]
2. The capability of surface Pd species to chemisorb
carbon monoxide is a non-trivial function of the reduc-
tion temperature. Pretreatment of the supported metal [8]
precursor in hydrogen at ambient conditions does not
ensure reduction of all palladium species and results [9]
usually in negligible CO uptakes. Quite a slight increase [10]
in the reduction temperature appears sufficient, how-
ever, to produce the highest apparent dispersions. A [11]
further increase in the reduction temperature, even a
relatively small one, has a very strong detrimental effect
on the accessible metal surface. Tentatively, this can be [12]
[13]
ascribed to sintering of the supported metal particles but
also to their penetration into narrow pores and / or
coverage of the metal surface with a carbonaceous [14]
contamination by interaction with amorphous parts of
the carbon or surface functional groups. The optimal [15]
reduction temperature proved to be near 400 K with the
metal precursor compounds and conditions of catalyst [16]
preparation used in this investigation. [17]
3. The microporosity of traditional activated carbons [18]
should be regarded as a disadvantage rather than a merit
in their use as catalyst supports. According to the [19]
results obtained, quite a high dispersion of the metal
[20]
proves achievable on such supports but does not
guarantee a proportionally high catalytic activity. While
[21]
being accessible to small molecules of carbon monox-
ide, the active sites localized in narrow pores are not [22]
easily accessible to more bulky molecules of organic [23]
substrates, and the steric hindrance for the organic
substrates to contact the active sites means that part of
the supported metal is lost for catalysis. [24]
[25]
Acknowledgements [26]
Financial support from Deutsche Forschungsgemein- [27]
schaft and Fonds der Chemischen Industrie is gratefully
acknowledged.
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