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1 Introduction
In this Report of catalyst-preparation technology we have placed particular
emphasis on catalyst design as opposed to preparation. A properly designed
catalyst should have the essential attributes of activity, stability, selectivity,
and regenerability. These can be related to the physical and chemical proper-
ties of the catalyst, which in turn can be related to the variable parameters
inherent in the method used for the preparation of the catalyst. In the past
much of the literature on supported catalysts has not included this infor-
mation. In part this was due to the lack of techniques for physically and
chemically characterizing supported catalysts. Many advances have been
made in recent years in this area, as described in Chapier 2, so that the design
of supported catalysts has become a feasible activity.
In addition to a wide range of techniques for the preparation of supported
catalysts a substantial number of supports are available for such systems. In
this Chapter we highlight the technology of catalyst preparation and the role
of the support in its application. In Table 1 are listed the total U.S. sales of
catalyst support materials for 1977.
The predominence of alumina and zeolites is reflected in the literature on
the preparation of supported catalysts and hence in the contents of this
Chapter.
2 General Methods of Preparation for Supported Catalyst
Systems
The principal catalyst-preparation technique involves two stages. First,
rendering a metal-salt component into a finely divided form on a support
and secondly; conversion of the supported metal salt to a metallic or oxide
state.
The first stage is known as dispersion and is achieved by impregnation,
adsorption from solution, co-precipation, or deposition, while the second
stage is variously called calcination or reduction.’ It is brought about by a
thermal treatment in either an inert atmosphere or an active atmosphere
of either oxygen or hydrogen. When the active atmosphere is hydrogen the
process is known as reduction. Although calcination/reduction can cause
major problems in catalyst preparation on a large scale, it is a generalization
to say that once the metal species has been bound to the support surface its
B. Delmon, P. Grange, P. A. Jacobs, and G. Poncelet, ed., ‘Preparation of Catalysts 11’,
Elsevier, Amsterdam, 1979.
2 Catalysis
Table 1 US. sales of catalyst supports in 1977*
Catalyst support products U.S. saZes (% wt.)
Alumina 56.9
Zeolites 22.2
Monolith cordierite 7.9
Diatomaceous earth 7.5
Activated carbon 3.0
Silica gel 1.3
Silica/alumina 1.2
Total 100.0
* Adapted from Chem. Tech., 1979, April
We postulate that binding to the surface can be either direct, via metal-
metal bond, or indirect through a bridging ligand oxide ion or possibly a
bridging chloride or hydrogen atom. In general several of these surface
compounds will coexist and, in favourable circumstances, these can now be
identified and quantified by TPR.ll
In certain cases the surface of the support may be pre-modified to either
increase or decrease its absorptive capacity. Techniques for the former have
been thoroughly explored in the area of anchoring homogeneous catalyst
complexes and metal clusters. Since this subject has been amply reviewed16
we will not discuss it further. These techniques primarily involve pre-treatment
of the support surface with a compound that can serve as a bridging ligand.
Techniques for decreasing the absorptive capacity are also of importance and
these will be covered later in greater detail when we come to consider metal
location on a catalyst support.
A completely different type of interaction from the above, in all of which
the metal ends up attached to the support surface, is that in which the
support acts as a reactant to precipitate the active material in a highly dis-
persed form within its pore structure but not attached to the support.
Examples of this latter type of interaction would be the precipitation of a
metal hydroxide from an acidic impregnating solution by a strongly basic
support, e.g., a sodium X zeolite, and the precipitation by reduction to the
l6
J. M. Barret and A. K. Smith, in 'Fundamental Research in Homogenous Catalysis',
Plenum Press, New York and London, 1976,
Design and Preparation of Supported Catalysts 9
metal by strongly reducing supports, e.g., the aldehyde surface groups on
some activated carbons. Very little systematic work has been reported on this
type of interaction, but practically these types of interactions can be very
important. Most of the remainder of this part of our discussion will concern
ionic exchange behaviour during catalyst impregnation.
Thermal Treatments and Reduction of Adsorbed Species. - After impregna-
tion many catalysts require a thermal treatment and/or a reduction stage to
render the adsorbed metal species active. Thermal treatments may take the
form of low-temperature drying operations (up to 150 "C) simply to remove
water, although some decomposition of species such as chloroplatinic acid is
known to occur within this temperature range particularly on relatively
non-reactive supports such as silica gels [reaction (5)]. Treatments at tem-
peratures between 150 and 500°C are principally used to decompose the
adsorbed species to the metal or metal oxide [reactions (6), (7), and (S)] .
[Pd(NH3)4]+++ O2 -
HZPtCl, -PtC14
- PdO
+ 2HC1 (5)
(6)
[Pt(NH3)4]++
R~Cl3.5H20 - Pt
RuO~
Thermal treatment alone to form the metal is not always desirable and
(7)
(8)
[Pt(NH3)4]2+ -
and reduction stages of catalyst p r e p a r a t i ~ n . ~ - l ~
PtH+ + H+ etc. (9)
5 Ion-exchangeBehaviour
Two factors are of importance and are best discussed separately. First, we
need to examine the nature and ionic composition of the metal solutions
used to impregnate the support and secondly, the nature and concentration
T. A. Dorling, B. W. J. Lynch, and R. L. MOSS,
J. Cutul., 1971, 20, 190.
C. H. Bartholomew and M. Boudart, J. Cutul., 1972, 25, 173.
l9
I. R. Leith, CHEMSA, 1978,4, 72.
10 Catalysis
of the exchange sites on the catalyst surface. It would seem trite and un-
necessary to observe that one would expect poor results from trying to
cation exchange an anionic support and vice versa, if this were not in fact
what is so frequently attempted. Similarly one would not normally expect
to attempt cation exchange of protons at low pH or anion exchange of
hydroxyl ions at high pH and yet this again appears to be what is frequently
attempted. (One can see immediatly, however, that there are going to be
problems when one tries to co-impregnate two metals, one in a cationic form
and the other in an anionic form!)
For the purposes of the ensuing discussion we would indicate that of the
commonly used catalyst supports: (a) zeolites are strong cation exchangers;
( b ) silica is a weak cation exchanger; (c) alumina is a weak anion and cation
exchanger; ( d ) magnesia is a stronger anion exchanger; (e) carbon has peculiar
and variable properties tending to form charge-transfer complexes as an
electron donor, but it also can act as a weak cation exchanger by virtue of
acidic surface oxide groups.
Let us therefore review in general terms what is known about ionic absorp-
tion on surfaces.
Simple Cation Adsorption from Solution. - The relevant equation here is
(10). This equilibrium is largely determined by the pK, of the surface acidic
group and shifts to the right at a high solution pH. The affinity of the func-
tional group for the metal ion determines the relative adsorption strength
of the different metals and this is largely a function of the charge to radius
* Adapted from D. C. Kennedy, Chem. Eng., 1980, 12, 186 and reproduced by per-
mission
catalysing procedure and in general poor catalysts result. The main difficulty
is that the maximum metal dispersion is controlled by the surface area of
the monolith, which is extremely low (0.1-1 m2 g-’). Sintering takes place
rapidly because of the high crystallite density per unit. By multiple dipping,
base-metal oxide coats of greater dispersion can be obtained but adherence
of these coats is usually low.
By far the greatest effort with monolith catalyst preparation has been
devoted to methods (iii)and (iv).
(iii) Washcoating then catalysing. The washcoating of the monolith first
followed by a catalysing step is a direct application of the usual principle
of precious-metal pelleted-catalytic techniques, but (iv), the incorporation
of the catalyst into the washcoat medium either as a preformed catalyst or a
29
J . J . Burton and R. L. Garten, ed., ‘Adv. Mat. Catal.’, Academic Press, 1977.
30 J. J. Benbow and L. W. Lord, U.S.P., 3 824 196.
31 H. Berger, U.S.P., 3 533 753.
32 T. P. Koblynski and B. Taylor, U.S.P., 3 840 389.
33 D. J. Cassidy, M. Esper, and D. J . Ronnie, Ger. P.,DT 2 349472.
34 C. A. Leech and L. E. Campbell, in ‘Spinel Solid Solution Catalysts for Automotive
Applications’, Am. Chem. SOC. Spring Meeting, Los Angeles, California, 1974.
35 M. Shelef and H. S. Gandhi, Platinum Met. Rev., 1974, 18,2.
16 Catalysis
soluble catalyst component, is taken from base-metal catalyst-manufacturing
practice. Washcoats usually consist of high area (50-250 m2 g-') oxides, e.g.,
A1203, Si02, Ti02, Zr02, etc., together with bonding agents such as hydrous
alumina, silica, etc. Much of the practice of washcoat manufacture is devoted
to ensuring that the hydrous oxide forms a strong bond between the wash-
coat components. Monolith porosity and the physical and chemical nature of
the monolith surface play a large part in ensuring washcoat a d h e r e n ~ e . ~ ~
Washcoats are not simple dispersions of insoluble oxides in water, but are
complex mixtures whose chemical and physical properties are modified by
the addition of acids, etc., milled for prolonged periods to obtain slips that
have sharply defined rheological properties. Once the monolith has been
coated, usually by a dipping technique, it is drained, dried at 100 O C , and
then fired to between 400 and 750°C to develop the bonds essential to its
adherence. Washcoating can be accomplished by dipping monoliths into
solutions of metal salts in water or organic liquids, then firing to develop the
oxide. This procedure is slow in that it requires multiple dipping and is not
generally used industrially. Mixed coats of successive oxide layers, e.g., Al2O3
and Si02, can be built up by this method, however, the process is not easy
to control .37-39
Methods of catalysing the washcoat can be very simple ones of dipping the
washcoated monolith in solutions of metal ions, but great care has to be
taken to ensure that the bonding properties of the washcoat are not destroyed
by the treatment. By far the best practice is to use the exchange properties of
the washcoat material with suitable metal salt solution^.^*^^ Once impreg-
nated it is usually necessary to employ a thermallreductive treatment to
convert any precious-metal species to the metallic state.
(iv) Incorporating catalysts into the washcoat. The method of incorpor-
ating the catalyst into the washcoat inevitably leads to poor utilization of
the catalytic material as some of it will be buried deep within the washcoat,
and some of it will be covered by bonding agents. The process of adjusting
the rheological properties of the washcoat can give rise to dissolution and
relocation of catalytic components. The method has, however, been used
with complex barium ruthenate ,35 and copper chr0mite.4~
6 Catalyst Case Studies
It is the purpose of this Section to review some of the more significant
recent papers on catalyst preparation particularly with regard to some of
36
C. Keith, P. Kenan, and D. Bair, U.S.P., 3 565 830.
37 G. F. Foster and H, E. Meissner, Ger. P., DT 2 317 560.
38
E. W. Albers and G. C. Edwards, U.S.P., 3 730910.
39 M. W. Pepper, J. P. DeLuca, R. P. Rhodes, and L. S. Bernstein, SOC.A u t o . Engineers,
1975, Paper 750684.
40 J. C. Summers and S. A. Ausen, J. Catal., 1978, 52,445.
41
B. Harrison, J. Heffer, and F. King, Preprints 7th Int. Congr. on Catalysis, B 2 Tokyo,
1980.
42 P. K. Gallagher, D. W. Johnson, J . P. Remika, F. Schrey, L. E. Trimble, E. M. Vogel,
and R. J. H. Voorhoeve, Mater. Res. Bull, 1975, 10, 529.
43 R. D. Shoup, K. E. Hoekstra, and R. J . Farrauto, 'Thermal Stability o f Copper
Chromite Auto Exhaust Catalyst', Am. Cer. SOC.Annual Meeting, Chicago, Illinois,
April 29, 1974.
Design and Preparation of Supported Catalysts 17
the points raised in our earlier discussion. We have already commented upon
the fact that none of these workers give details or evidence of surface charac-
terization of the supports that they used. This does not militate against the
usefulness of many of the results, as in most cases the same support was used
and the studies concerned changes in impregnating solution. A further criti-
cism of much of this published work is that in many cases no conscious effort
was made to control or note the pH of the impregnating solutions. This is
certainly a most important preparation variable and one that in any industrial
catalyst preparation must be very carefully controlled if reproducible cata-
lysts are to result. The initial reaction that pH measurement is impossible
when using a dry impregnation based upon the more usual incipient wetness
technique is a specious argument, as the titratable acidity or basicity of both
the impregnating solution and support used are generally measurable. Even
details of the pH of the impregnating solutions used and their possible vari-
ation would be useful information.
Alumina-supported Catalysts. - Because of the long standing commercial
importance of platinum/alumina catalyst much work has been done in this
area. Many workers have been concerned with varying the dispersion and
metal placement by using chloroplatinic acid in conjunction with a competing
anion. Hence the use of HNO,, HF, and HCl," citric HNO, and
H O A C , ~and HCl and ethanolamine4' have all been reported. Aboul-Gheit4'
used an ion-exchange technique with a three-fold excess of solution. In such
a case the metal salt has to diffuse into the catalyst pellet from the excess of
solution; the results are reproduced in Figures 1 and 2. In these Figures the
metal dispersion was measured by hydrogen chemisorption and a strong
correlation was noted between metal dispersion and metal distribution. For
the case of HCl additions the metal penetrated more deeply into the support
structure and became better dispersed as the chloride concentration increased.
Without chloride the metal was very poorly dispersed and was found on the
pellet's exterior surface. Despite this poor dispersion the ready accessibility
gave quite an active catalyst.
For ethanolamine, the dispersion, distribution, and activity all increase but
at the higher pH the metal is completely displaced towards the pellet interior.
This leaves a marginal zone devoid of metal and a marked decrease occurs in
both activity and dispersion, as diffusional resistance becomes more impor-
tant and as the surface concentration of metal in the pellet interior increases.
These effects may readily be explained by the high pH of the external solu-
tion, which would tend t o reduce the anionic-exchange capacity of the
support.
Cationic exchange of platinum as F't(NH3)4(OH), with alumina has also
been reported.22 Here, in contrast to the above results, metal adsorption
only occurred at a high pH, greater than 9. A particularly interesting aspect
44
R. W. Maatman, Ind. Eng. Chem., 1959, 51, 913.
45 E. Michalko, U.S.P., 3259454, 3259 589; J. C. Summers and L. L. Hegedus, J.
CataL, 1978,51, 185.
46
G. N. Maslyanskii and B. B. Zharkov,Kinet. Catal., 1971, 12, 699.
4'
A. K. Aboul-Gheit, J. Chem. Tech. Biotechnol., 1979,29, 480.
18 ciztalysis
100 - 100
~8 0 - 80
8
.-0
L
ul h
g6 0 - 60 e?
.-
ul
-0
.-s
-
7 ul
240
a,
1io ;
E
s
-
L L
020
U
20 g
8 a,
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U C
X
W
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I I
of this work was the comparison with NHB absorption on the same alumina,
which occurred readily at a lower pH, i.e., above 7. Apparently the cationic
affinity, generally taken as a function of the ionic charge density, is less for
the more bulky platinum ion than for the ammonium ion despite the higher
cationic charge of the former.
A very wide range of co-ingredients for chloroplatinic acid impregnation
100 100
v
.-5 80 . 80
v)
L h
G) 0
-
cz
ul v
;60 $
60 .-
c
L
ul
m
U
G)
40 40
r u
0
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a,
U I
I
c
m
0)
X
W
I
0 I
I I I I I I I 0
2 3 4 5 6 7 8 9
pH of impregnating solution
Figure 2 Effect of monoethanolamine concentration on the distribution and dispersion
of platinum in alumina and on the hydrogenation activity of the prepared
catalysts
(Reproduced by permission from J. Chem Tech. Biotechnol., 1979, 29,480)
Design and Reparation of Supported Catalysts 19
0 1 0 1 0 1
Radial P o s i t i o n f r o m Center r / R
N
c
22 Ca t a b sis
Table 5 Rhodhm depth profiles on y-A1203
pel1ets4l (pellet diameter 3 500 pm)*
Maximum dep th
270
900
1100
1100
Uniform
Uniform
100
200
* B. Harrison, J. Heffer, and F. King, Preprints 7th
Int. Congr. on Catalysis, B2, T o k y o .
of adsorption with the rate of ligand displacement from the complex anion
rather than with simple anionic exchange. Qualitatively the trends to be
expected would be similar. Their results are given in Table 4, which shows the
percentage extent of metal adsorption after 60 min.
Results for a more extended series of rhodium complexes have also been
given recently41 (see Table 5). These workers also discuss the poor metal
dispersion that can result from a too rapid adsorption and the build up of
high localized metal surface concentrations.
Uniform impregnation of ruthenium can be obtained47 with ruthenium
chloride in the presence of citric acid; the acid is competitive with the very
strongly adsorbed complex ruthenium ion although as we saw earlier& citric
acid will completely displace the chloroplatinate anion.
Very few results have been published on other metals, but again those
that have been are in good agreement with our overall general picture. Hence
in a study of nickel catalysts prepared from NiC12 and Ni(N03)2 metal
uptake increased rapidly above pH 5, being independent of the anion.49
This is indicative of simple cation exchange and metal placement could be
varied by suitable pH adjustment with either N b O H , giving a surface impreg-
nation owing to strong absorption, or H N 0 3 , giving a core impregnation.
A recent paperm on the co-impregnation of copper and chromium from
their nitrate solutions again follows the pattern of simple cation exchange
- with the higher valent Cr3+ ion being much more strongly adsorbed and
indeed capable of displacing the Cu2+.The competitive situation was such as
to exclude the close proximity of these two metals. These results could have
important ramifications in the preparation of uniform bimetallic catalysts.
Silica Catalysts. - Little problem is to be expected from depositing metals
by simple cation exchange onto the surface of silica gel with appropriate
control of pH to control the depth of metal penetration. Many high-surface-
49 M. Komiyama, R. P. Merrill, and H. F. Harnsberger, J. Catal., 1980, 6 3 , 3 5 .
50 H. -C. Chen, G. C. Gillies, and R. B. Anderson, J. Catal., 1980, 6 2 , 3 6 7 .
Design and Preparation of Supported Catalysts 23
100 -
-m
I
Ion Exchanged
-
Ea 80 -
C
'E 60
EL
.-2
r
E
0 40 -
al
13,
rn
2
f 20,
0
I
r, 5
Platinum, wt%
area silica gels are so hydrophillic, however, that large support particles will
tend to fracture under the mechanical and thermal stresses generated by
sudden wetting. For this reason, and in order to improve control of metal
placement, the gel is often chosen to be in a partially dehydroxylated form
made either by thermal pretreatment or in one of the other ways used for
deactivating the surface, as discussed earlier.
Silica is a poor support on which to attempt the dispersion of metals in an
anionic form. This was clearly shown22 some time ago (1968) in work in
which a catalyst prepared by cation exchange using [Pt(NH&I2+ was com-
pared with one made by simple impregnation with H2PtC16. Similar results
have been reported more recently (1976)51 for which Keller's complex was
used for cationic exchange. In both cases, as shown in Figure 4, high disper-
sions resulted from the cation-exchange procedure and the more simple
impregnation procedure with platinum in its common anionic form was
ineffective, particularly at the higher metal loadings.
One way of overcoming this limitation has recently been described." In
this procedure a dried chloroplatinic-acid-impregnated silica gel is thermally
pyrolysed at 625 K. It was shown that the divalent platinum halide formed
under these conditions was sufficiently volatile and reactive as to react subse-
quently with and become dispersed on the support surface.
51
J. -P. Brunelle, A. Sugier, and J . F. Le Page, J. Catal., 1976, 43, 273.
24 Catalysis
2 ‘t 8
Platinum content (wt%)
The redox behaviour of these zeolite supported metals has been used to
good advantage” as a very quick and simple test to characterize the metal
dispersion and hence the location of the metal. Three extreme cases have
been differentiated, atomically dispersed metal in the pore structure, larger
aggregates within defects of the crystalline lattice, and very large aggregates
on the external surface of the zeolite crystals. These are characterized in
terms of their increasing ease in reducibility and decreasing ease of oxidiz-
ability in the order given.
Ruthenium-Zeolite Catalysts. - This is taken as an example of some of the
problems and difficulties that can be encountered and have to be overcome
in the preparation of a zeolite supported catalyst. There is at present very
much interest in using highly dispersed ruthenium catalysts for Fischer-
Tropsch synthesis. It has recently been found that the maximum chain
growth in the synthesis reaction is strongly affected by the crystallite size
of the ruthenium metal. The smaller the crystallite size the lower in general
is the molecular weight of the synthesis product. Specifically it has been
found that maximum gasoline should result if the crystallite size can be
controlled in the range of 3-4 nm.” Conceivably this can be achieved with
the aid of zeolite supports.
Various authors have reported differing attempts to prepare ruthen-
ium zeolites by cationic exchange using, for example, [Ru(H20),]
N ~ ] and [ R u ( H N ~ )*
[ R u ( N H ~ ) ~ 2+,61 ~ ]62 cationic complexes. Results ob-
taineda using the hexa-aquo complex [ R U ( H ~ O ) ~are shown in Table 6 .
]~+
Exchange was carried out for 18h in solutions buffered at pH 6.5 except
for the more acid-resistant mordenite sample. Significant metal adsorption
was observed in all cases but this was accompanied by extensive hydrolysis,
which in effect reduced the cationic charge owing to the ligand replacement
of H 2 0 by OW. Spectroscopic examination indicated that in all cases the
spectra agreed with those to be expected from a Ru* ion in distorted octa-
hedral co-ordination. No attempt was made in this work to reduce the ruthen-
ium or to characterize the resulting metal dispersion.
59 P. A. Jacobs, in ‘Catalysis by Zeolites’, Proceedings of an International Symposium,
ed. B. Imelik, Elsevier, 1980.
6o B. Coughlan and W. A. McCann, J. Chern, SOC.,Faraday Trans. I , 1979,75, 1969.
61 C. A. Clausen and M. L. Good, Inorg. Chem., 1977,16, 816.
62 J . J. Verdonck, P. A. Jacobs, M. Genet, and G. Ponceiet, J. Chem. SOC., Faraday
Trans. 1 , 1980, 76,403.
Design and Preparation of Supported Catalysts 27
The RuY samples prepared from [Ru(NH,),] 3+ were thoroughly charac-
terized62 by XRD, TEM, i.r., and the combination TPO/TPR technique55
for characterizing crystallite sizes. Highly dispersed ruthenium within the
zeolite cavities was obtained even by heating in an inert atmosphere owing
to autoreduction by the ammonia released by decomposition of the complex.
This would appear to be a fairly general phenomenon when using ammine
complexes. Further heating in hydrogen resulted in crystallite growth, particu-
larly in the presence of water, to a size which was bigger than the crystallite-
cage size. These crystallites were apparently still contained within localized
defects within the zeolite lattice produced by localized hydrolytic decom-
position of the lattice structure. Some of the crystallite growth would appear
to be caused by hydrolysis of the zeolite surface complex and growth of small
oxide crystallites. Oxidation of the highly dispersed ruthenium above 400 K
led to the growth of very large crystallites on the external surface of the zeolite
crystals, which is due to the reactivity of the highly dispersed ruthenium and
the volatility of the ruthenium oxides.
Carbon-supported Catalysts. - Preparation of catalysts on carbon is very
dependent on the available surface area, and supports can be divided into two
broad categories:
(i) the low surface area supports with little or no pore structure such as
graphite carbon blacks, graphitized carbon blacks, and non-activated or low
activated carbons from carbonized synthetic fibres, e.g. , polyacrylonitrile,
etc. (surface area varies from 50-250 m28-l support material);
(ii) the high area supports such as activated charcoals and channel black
carbons, whose surface area varies from about 500-2500 m2 8-l support
material. In general, the high area arises from the development of a porous
structure within the carbon particles. As surface area rises there is a ten-
dency for the average pore diameter to fall and the supports with the highest
area are predominantly microporous (< 25 a).
This dependance on area arises from the density of functional groups on
the surface. For highly orientated surfaces6, such as graphite or the graphitized
carbon blacks, where surface functional groups occur only at the edges of
graphite planes, the density of functional groups is extremely low.
With less orientated carbons (turbostratic carbons) with a much higher
density of graphite edge planes and tetragonal carbon atoms, functional
group density is much higher, and in some carbons oxygen content can reach
as much as 12%. Catalysing carbons, if one is to believe the published litera-
ture, is still more of an art than a science, principally because few authors
have connected the surface chemistry of carbon with the dispersion of the
metal. Even where this is so, and for instance the ion-exchange properties
of a carbon have been used to obtain high dispersion of the metal ions,
little attention has been paid to the reduction stage and only moderate
metal dispersions have resulted.
50 .1 0 0
40 . 90
f
0
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a, m
0.
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.-
c
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m
E I
.-+Jz 20 7'1 ;
-am u-
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u
rg
VI
3
0' :
lfl .6n
50
Figure 5 Effect of degree of bum-off on the surface area and degree of dispersion of a
1%platinum on graphitized carbon black