Carbon, Vol. 32, No. 5, pp.

759-769, 1994
CoDyright0 1994Elsevier Science Ltd
Pergamon Printed’k &eat Britain. All rights reserved
0008~6223/94 $6.00 t .OO

000%6223(94)E0029-X

REVIEW ARTICLE

SOME ASPECTS OF THE SURFACE CHEMISTRY OF

CARBON BLACKS AND OTHER CARBONS

H. P. BOEHM
Institut fi.ir Anorganische Chemie der Universitiit Miinchen, Meiserstrasse 1,
80333 Miinchen, Germany

(Received 4 January 1994)

Abstract-A review is given on the surface chemistry of carbon blacks and other carbons, in particular,
activated carbons. The main part is devoted to surface oxides with emphasis on the chemical methods
used in the assessment and identification of surface functional groups. Their formation under mild
conditions and the influence of water vapor and metal catalysts on the reaction with air (“aging” of
carbons) are described. Reaction with free organic radicals can be used for the functionalization of
carbon surfaces.
Key Words-Activated carbon, carbon black, surface chemistry, surface functionalization, surface
oxides.

1. INTRODUCTION curved in part, and there is pronounced cross-link-

Carbon blacks consist of spheroidal particles with a
pronounced ordering of the carbon layers (graphene
layers). The layers are wrapped around a very disor-
dered nucleus with a preferential orientation parallel
to the particle surface[i,2].
High-resolution TEM showed[3] that the layers
are bent and curved, following the surface. They
are larger, therefore, than the crystallite dimension
L, of 1S-2.5 nm, as determined from line broaden-
ing in X-ray diffraction. The spherical primary parti-
cles are fused to branched chain-like structures by
deposition of such layers.
Since carbon blacks are produced from hydrocar-
bons, the dangling bonds at the edges of the carbon
layers are saturated mostly by hydrogen. Often, one
finds large polycyclic aromatic ring systems on the
surface that can be extracted with hot solvents (e.g.,
xylene). One suspects, therefore, that there are also
still larger molecules on the surface that are insolu-
ble, and that there is a gradual transition in size
to the layers that can be recognized in HRTEM
photographs.
Other elements than hydrogen are also found in
carbon blacks. The most important of these is oxy-
gen. Whereas sulfur and nitrogen originate from the
oil precursor, oxygen can also be taken up during
carbon black formation or storage. Much more oxy-
gen is chemisorbed on heating carbon blacks in air
(or oxygen or by treatment with oxidizing media
such as HNO, or NaOCl solution. The surface ox-
ides formed in these reactions have a pronounced
effect on the surface properties of the carbons.
Activated carbons consist of small layers stacks
that are less regularly organized. They are also
ing. Due to the activation process, the layer packets
are separated by micropores, most of which seem
to be slit-shaped. Depending on the precursor, there
may also exist meso- and macropores. The color
blacks of high apparent surface area (BET surface
area) are microporous in a similar way.
The surface oxides are bound to the edges of the
carbon layers. It has been shown that basal planes
of graphite are attacked by molecular oxygen only
at their periphery or at defect sites such as vacan-
cies[4-61. Many oxygen-containing functional
groups have been detected in the surface oxides of
carbon. Other elements, in particular halogens, can
be chemisorbed on carbon surfaces.
The surface properties ofcarbon blacks and other
types of carbon are influenced to a large extent by
the foreign elements fixed on the surface, in particu-
lar by oxygen. This also affects the behavior of
carbon blacks in practical applications.
The present paper gives an overview of the func-
tional groups in surface oxides. The emphasis is on
the methods used for their identification because
some of the pertinent literature is now no longer
readily available. The experiments were performed
in part with carbon black, but activated carbons
have also been used because of their larger surface
areas and larger concentrations of surface groups.
Activated carbons were prepared from carbonized
sugar char, resulting in very pure carbon materials.
Charcoals produced from wood (Eponit) or peat
(Norit) were also used: they were extracted with
hot hydrochloric acid and washed with hot water
until no chloride could be detected. The carbon
blacks Corax 3 (furnace black) and CK3 (similar to
channel black) were obtained from Degussa. The

759
760 H.P.
experimental methods are outlined briefly; they are
quite simple, and details are described in the original
literature.
2. SURFACE OXIDES
2.1 General
Carbons, including carbon blacks, can show ba-
sic or acidic pH values in aqueous dispersions, A
good correlation between pH and oxygen content
of carbon blacks has been found[7]. The dispersion
is the more acidic, the higher the oxygen content
is. The acidic surface properties are due to the pres-
ence of acidic surface groups. Such carbons have
cation exchange properties. Carbons with a low oxy-
gen content show basic surface properties and anion
exchange behavior. The basic properties are as-
cribed to the presence of basic surface oxides, but
it has been shown that the 7~electron system of the
basal planes of carbon is sufficiently basic to bind
protons from aqueous solutions of acids&-IO].
2.2 Acidic s~r~uce oxides
The acidic surface oxides have been the subject
of many studies that have been summarized in sev-
eral reviews[l l-181. Figure 1 presents several struc-
tures of oxygen functional groups that might be
found at the edges of graphene layers. Carboxyl
groups (a) might give carboxylic anhydrides (b) if
they are close together. In close neighborhood to
hydroxyl groups or carboxyl groups, carbonyl
groups might condense to lactone groups (c) or form
lactols (d). Single hydroxyl groups (e) on the edge
of “aromatic” layers would be of phenolic charac-
ter. The existence of carbonyl groups is very plausi-
ble; they could come either isolated (f) or arranged
in quinone-like fashion (g). Obviously, other ar-
rangements could be envisaged for quinone-type
functions. Finally, oxygen could simply be substi-
tuted for edge carbon atoms (h); such xanthene- or
ether-type oxygen is very di~c~t to detect.
The groups (a) to (e) react more or less weakly
acidic. Evidence for their existence has been found
(a) lb)
(e) if)
Fig. 1. Possible structures of surface oxygen groups (see text).
BOEHM
by classical chemical detection methods, such as
esterification with hot methanol (acid-catalyzed),
formation of acyl chlorides with thionyl chloride or
formation of methyl esters of the carboxyl groups,
and methyl ethers of the phenolic hydroxyl groups
with diazomethane; see below. Methyl esters and
methyl ethers can be differentiated by their different
resistance towards hydrolysis. These reactions were
supplemented by observation of the changes in neu-
tralization adsorption behavior.
Obviously, the individual functional groups, such
as carboxyl groups, will exhibit a spread of their
dissociation constants, depending on the neigh-
boring groups, the size of the graphene layers, etc.
Yet the acidity constants of carboxyl groups, lac-
tones, or phenols differ over several orders of mag-
nitude (see ref. [I8]), and it was established that the
various types ofgroups can be distinguished by their
neutralization behavior. At a given pH of the adjoin-
ing aqueous medium, practically all carboxyl groups
will be dissociated to carboxylate with the counter
ions dispersed in the diffuse double layer. It has
been found that the most convenient way of de-
termining the concentration of free carboxyl groups
is to perform a neutralization adsorption experiment
with 0.05 M NaHCO, solution, separate the solu-
tion, and titrate the remaining Na+ ions (by adding
excess 0.05 M HCl to an aliquot, boiling off the
COZ, and back-titrate with standard NaOH). It was
shown that practically identical results are found as
with a pH-static titration to pH 8.2[19,20], or by
reaction with a solution of KI and KIO, and titration
of the liberated iodine[l2]. Such solutions establish
a constant pH of 7.5. With nonporous carbons, the
adsorption of diphenylguanidine agrees, too, with
NaHCO, consumption[8], Direct potentiometric ti-
tration suffers from very slow establishment of the
ion exchange equilibria, particularly at higher pH
values[l9-211. However, the fact that the acidity
constants cluster around discrete values can be
clearly seen in conductometric titration curves[22].
The best results were obtained with dilute NaOCH,
0 0
\\ *
C-O c-o 011
fd (h)
 The surface chemistry of carbon blacks and other carbons 761

0
‘C-O
OH

Fig. 2. Conductometric titration of oxidized graphite wear

solutions
dust with 0.05 M NaOMe in MeOH.

in methanol; an example is shown in Fig.

2. There are distinct breaks in the curves, and as
shown in Table 1, they agree quite well with the
neutralization values found with NaHCO, and
Na,C!03. In a very recent paper, Bandosz ef af.
described the analysis of titration curves that leads
to a resolution of the various acidity constants[23].
Lactones are weaker acids than free carboxyl
groups. This is clearly demonstrated by the fact
that the lactone ring in phenolphthaleine is opened
(purple color) by sodium carbonate, but not by bi-
carbonate. Therefore, 0.05 N Na,C03 solution is
suitable for the determination of carboxyl groups in
lactone-like binding. The formation of lactols (Fig.
Id) from aromatic carboxylic acids with neighboring
carbonyl groups is well known, for example, for 2-
benzoylbenzoic acid[24]:
The presence of analogous structures seems
quite plausible on the edge of a graphene layer:
-;:x!:-
It is generally assumed that phenolic hydroxyl
groups on the carbon surface react with strong
alkali (e.g., NaOH) analogously to free phenols.
Attempts have been made to verify by chemical
reactions the presence of such groups. An example
of such reactions is shown in Table 2. On reaction
with an etheric solution of diazomethane, CH2N2,
carboxylic acids form methyl esters of the acids,
and methyl ethers are produced from phenols.
Lactols form methyl esters, too[251. Ethers are
stable to hydroIysis by dilute acids, in contrast
to esters that are saponified. As shown in Table
2, the neutralization values with NaOH have de-
creased to those found with NaZCOj, and the
difference is equal to the methoxyl content re-
maining after hydrolysis.
Acyf chlorides are formed in the reaction with
thionyl chloride, SOCl,. At reflux temperature,
SOCI, decomposes slowly to Cl? and other products,
and therefore some chlorine is also bound by addi-
tion or by hydrogen substitution. Only part of the
fixed chlorine can be hydrolyzed with alkali; the
larger part is resistent even to hot I M NaOH. Only
the chloride that can be recovered by hydrolysis
with alkali was equivalent to the carboxyl groups
(Table 3). This is what one would expect for the
reaction

Table 1. Comparison of the breaks in conductometric titration with

neutralization values (titration with 0.05 M Na+OMe- in MeOH)

1st NaHC03 2nd Na?CO,

break uptake break uptake
Sample peq/g Feq/g peq/g CLeq’g

Corax 3a, H.T. 1400°C 65 56 85 92

ox. with (NH,),S,Os
Corax 3” H T. 3000°C 10s 99 145 134
ox. v&h &MnO,
Graphite wear dust 205 181 350 363
ox. with air at 420°C

“Corax 3 = furnace black (Degussa).

762 H. P.BOEHM

;:k+ -
determined with NaHCO,. It is known that phthalic
COCI acid is converted to phthalic anhydride in the reac-
tion with thionyl chloride. The acyl chloride must
2NaOt-l
have been formed in this case from the lactone-type

ir-
carbonyl functions.
Another attempt to identify carboxyl groups used
COO-No+
the Friedel-Crafts reaction with dimethylaniline and
t Na+CI- the Schmidt rearrangement, a special type of the
Curtius rea~angementr26~. In both reactions, the
carboxyl groups were first converted to acyl chlo-
However, with NaOEt in some cases the consump- ride by reaction with thionyl chloride. After treat-
tion was less than with the carbon before chlorina- ment with dimethylaniline and anhydrous aluminum
tion (see Table 3), although one would expect an chloride in hot nitrobenzene as a solvent, and ex-
unchanged consumption, as was observed with the traction with dilute hydrochloric acid, water, and
other samples: ethanoi, the nitrogen content corresponded to the
acyl chloride content after ~hlorination[Z6~. The
neutralization value with NaHCO, was decreased
COCI by an equivalent amount, whereas the neutralization
+ NaOEt - of the other groups was unchanged within experi-
i_x mental limits. The results presented in Table 4 can
be explained by the reaction sequence
COOEt
Ph-NMe,
+ Na+CI- R-COOH + R-COCl-
3
h
R-CO-C,H,-NMe,.
A plausible explanation is that anhydrides of two
neighboring carboxyl groups had formed, which
The Schmidt rea~angement involves reaction of the
form ester plus carboxylate:
acyl chloride with an aicoholic solution of sodium
0 azide, NaN,. The resulting acyl azide decomposes
to form a urethane, which is stable in acidic media,
Z, but decomposes with alkali to give an amine. Thus,
+ NaOEt - again, the carboxyl groups are destroyed:
,O
~ c
NaNl
II
R-COOH + R-COCl----+ R-CON,2
0
COO-No+ +H,O
R-NH-COOEt -
-CO,,-EtOH R-NH2'

cx COOEt
The reaction was followed by determinations of
The loss in NaOEt consumption corresponded the nitrogen and ethoxy contents, as well as the
quite well to half the content of carboxyl groups changes in neutralization behavior after each step.

Table 2. Influence of reaction with di~omethane on the neutralization behavior of oxidized carbons
(the activated carbons from carbonized sugar char were oxidized with 0, at 400°C)

Neutralization in peqig 0CH3

content
Treatment NaHCO, Na$O, NaOH pmol/g

Sugar char, H.T. 950°C

after oxidation 200 430 720 0
methylated with CHzNz - - 720
methylated and hydrolyzed with 210 410 410 290
hot HCI solution
diff.: 310

Sugar char, H.T. 1100°C

after oxidation 160 320 690 0
methylated with CH,N, - - 720
crethylated and hydrolyzed with 170 320 330 380
hot HCl solution
diff.: 360
 The surface chemistry of carbon blacks and other carbons 163

Table 3. Neutralization behavior of oxidized carbons after reaction with thionyl chloride (oxidation with OZ at 400°C)

Change in consumptn.
after SOCI? reaction
Group Group Hydrolyzable
I” II” Cl NaOH NaOEt
Sample peq/g peqig peqlg peq/g peq/g

Sugar char 160 150 160 +I80 0

H.T. 1100°C
Sugar char 230 210 210 +200 0
H.T. 1100°C
Eponit 870 430 +410 0
H.T. 1100°C
Activ. sugar char 600 460 480 +450 -340
H.T. 950°C
Activ. sugar char 600 350 350 +350 -310
H.T. 950°C
Eponit, 660 680 520 +580 -340
add. activation

“Group I = NaHCO, neutralization.

Group II = NarCO,-NaHCO, neutralization

The results are a bit complicated because lactones
may form ethyl esters,and carbonyl groups may re-
act with NaN, in hot ethanol. When the reaction
was performed at room temperature, one nitrogen
atom was taken up, and one carboxyl function was
lost for each acyl chloride group formed origi-
nally[26,27].
Phenols are very weak acids, neutralized by
NaOH solutions. In contrast to carboxylic acids,
they can be reacted with 2,4-dinitrofluorobenzene
(DNFB) or with p-nitrobenzoyl chloride (p-
NBC)[26]. As shown in Table 5, the bound quanti-
ties agree very well with the difference between
NaOH and Na&Os consumption.
Using a still stronger base than NaOH, sodium
ethoxide, Na+OEtt, in ethanol, additional groups
are detected. We have shown[26] that equivalent
quantities of Nat and OEt- are bound by the car-
bons in this reaction. The assumption that this is
due to the formation of sodium salts of hemiacetals
from carbonyl groups
is based on identical conversions after reaction with
hydroxylamine that lead to oximes (Table 6).
The carbonyl groups are susceptible to reduction
with nascent hydrogenl261. This results in a de-
crease of NaOEt consumption. After reaction with
zinc and hydrochloric acid, the sodium ethoxide
uptake was reduced to that of sodium hydroxide in
some cases. In one such case, the weakly acidic
carboxyl function (neutralized by Na*CO,) had in-
creased in acidity and reacted with NaHCO,, too.
This observation points to an interrelationship be-
tween the carbonyl groups and neighboring carboxyl
groups. The quantity of active carbonyl groups was
also reduced after reaction with NaBH, or LiAlH,.
Pairs of carbonyl groups arranged at the periph-
ery of the graphene layers in such a way that a
system of conjugated double bonds can be formally
drawn in, will behave similar to quinone func-
tions. Reduction peaks in cyclovoltammetry experi-
ments have been ascribed to such quinone func-
tions[28-311. Also, some chemical evidence for
their existence has been presented[32,33].
In our early experiments we observed that fre-
quently equivalent quantities of the various groups
are found after strong oxidation that results in partial
gasification of the carbons. This observation led us
to speculate on a model in which carboxyl groups,
lactols, and phenols are grouped in immediate prox-
imityl341. It was thought that this surface complex
is an intermediate step in the removal of carbon
atoms from the layer edge. It must be stressed,

Table 4. Results of the Friedel-Crafts reaction with dimethylaniline

(from refs. 126,271)

NaHCO? N content
neutralization Cll after after
reaction w. reaction w.
before after SOClz Ph-NMe*
Sample peqig yeqlg peq/g pmol/g

Eponit ox. with OZ 460 280 230 220

Eponit 590 280 310 330
ox. with (NH&&Ox
764 H.P. BOEHM

Table 5. Reactions of phenolic surface groups on oxidized carbons

(oxidation with O2 at 400°C)

Difference Hydrol.
NaOH- resistent Conversion with
Na2C03 OCH,
uptake gr. DNFB p-NBC
Sample weoig fimol/g wmol/g ~molig

Carbon black CK3 320 330 130 290

Activ. sugar char 610 620 620 -
H.T. 950°C
Sugar char, H.T. 1100°C 420 430 420 -
Activ. sugar char 390 - 370 400
H.T. 1100°C

however, that very frequently other distributions
of acidic surface functions are observed, especially
after relatively mild oxidation treatments. In the
more recent literature, such equivalences of differ-
ent surface groups are rather rare. With carbon
blacks, there are often fewer carboxyl groups than
reactive carbonyl groups. In the early stages of oxi-
dation with solutions of (NHJ2S205, KMnO,, etc.,
at room temperature, only weakly acidic carboxyl
groups and reactive carbonyl groups are formed
(lactol functions)[271. Oxidation with concentrated
nitric acid often produces acidic compounds of rela-
tively small size that go into homogenous solution
on treatment with dilute alkali[20].
Usually the carbons contain more oxygen than
can be explained by the detected functional
groups[12,35,36]. This oxygen is usually ascribed to
ether-type oxygen (Fig. lh) without further proof.
Determination of active hydrogen by reaction
with methyl magnesium iodide or lithium methyl
was found to be low compared to the content of
carboxylic and phenolic groups on carbon black
Spheron 6, whereas good agreement was found with
agraphite[37]. The reason is that part of the methane
may be adsorbed on the carbon black surface.
Therefore, with higher-surface-area carbons, active
hydrogen can only be determined by isotope ex-
change. Table 7 shows that the contents of active
hydrogen agreed quite well with the NaOH uptake
with carbon black, as well as with a graphite wear
dust produced by milling graphite under argon[22].
2.3 Basic surface oxides
Basic surface oxides are always present on a
carbon surface. When a carbon is heated to ca.
1000°C in vacua or under an inert gas, the existing
surface compounds are almost quantitatively de-
composed. When this carbon is exposed to dry oxy-
gen after cooling to room temperature, some oxygen
is chemisorbed. After submersing this carbon under
aqueous acids, the same quantity of oxygen again
is taken up, and approximately one equivalent of
acid per chemisorbed oxygen atom is bound at the
same time (Fig. 3)[39]. The bound anion of the acid
can be exchanged for other anions. Water is a suffi-
cantly strong acid, and OH- ions are bound when
the reaction is conducted in pure water, giving rise
to an alkaline pH of the dispersion. Some H202 is
formed during the second chemisorption reaction,
but carbon surfaces catalyse its decomposition and
it decomposes rapidly[39,40]. The chemisorbed HCl
or H,O are desorbed on outgassing in vucuo, even
at room temperature[41].
Garten and Weiss, who studied the basic surface
oxides in the 195Os[42,43], ascribed the basic prop-
erties to chromene-like structures. Voll and Boehm
concluded on the basis of a few chemical reactions
that y-pyrone-like structures, as shown in Figs. 4
and 5, are more plausible[44]. The ether-type oxy-
gen can easily be replaced by nitrogen in the reaction
with ammonia. The hydroxyl groups can be methyl-
ated with diazomethane, whereas the anion ex-
change property is preserved.

Table 6. Reactions of carbonyl groups on oxidized carbons (oxidation

with 0, at 400°C if not stated otherwise)

Fixed N
Difference Bound after react.
NaOEt-NaOH -0Et with
uptake groups NH20H
Samnle ueolg pmol/g peq/g

Sugar char, H.T. 95O”C, 670 680 660

CO*-activated
Sugar char, H.T. 1100°C 480 460 430
Eponit, H.T. 1100°C 630 640 580
(ox. with (NH&S20s)
Carbon black CK3 210 180 -
 The surface chemistry of carbon blacks and other carbons 765

Table 7. Active hydrogen on oxidized carbon surfaces. In the Zerewitinov method, the volume of
methane that forms in the reaction with a solution of CH,MgI is measured. The isotope exchange was
performed by exchange with deuterium from D20, as described in detail in ref. [38].

Surface NaOH
area Method of Active H uptake
Sample m?!g determination fimolig i-=q&

Graphite wear dust

ox. with air at 420°C 275 isotope exch. 670 580
ox. with NaOCl 345 isotope exch. 1040 1025
ox. with (NH4)2S?08 330 isotope exch. 1440 1650
Corax 3 n.d. Zerewitinov 130 200
ox. with (NH&SI08
Corax 3, H.T. 1100°C n.d. Zerew~tjnov 228 206
ox. with (NH&O8
Corax 3, H.T. 1400°C n.d. Zerewitinov 94 123
ox. with (NH&O8

As mentioned earlier, hydrochloric acid is also
adsorbed on the basal planes of carbons and graph-
ite[8-IO]. This is due to the basic character of aro-
matic 7r electrons. Also in Fig. 3, the HCI adsorption
isotherm is a little higher than the oxygen-uptake
curve. By potentiomet~c titration two types of pro-
ton-binding sites were found on a carbon fiIm1451.
One corresponded to a base with a mean basicity
constant pKb = 6.6, while the second site was a
very weak base (pKb > 11)[451. Table 8 shows that
some hydrochloric acid is adsorbed even on graphite
powders with a very small surface area of the prism
faces. The acid uptake did not correlate well with
the BET surface areas, however. Papirer et nl.[36]
observed, in contrast, that the concentration of ba-
sic groups on oxidized carbon blacks was propor-
tional to the surface area. They concluded further
that one of the oxygen atoms of a pyrone group is
quite heat-resistant, and is desorbed as CO and CO1
only between 800°C and 950°C. It was confirmed
that one oxygen atom is fixed at 100°C for each basic
site formed.
Oxidized carbons always contain basic sites in
addition to the acidic functions. However, their
quantity is usually less than with the original carbon.
It was found that the acid take-up increased when
acidic groups on Pd- or Pt-loaded carbons were re-
duced in hydrogen at 80-500°C (see Fig. 611461.Hy-
drogen is chemisorbed as H atoms on Pt or Pd, and
can diffuse from the metal surface to the surface of
the support (hydrogen spillover)[47]. This provides
a relatively mild way of reducing surface oxides, as
compared to hydrogen treatment of the metal-free
carbons, which becomes effective only above
4OO*C.The carboxyl groups/lactols were more sus-
ceptible to reduction than the phenofic groups[48].
Obviously, basic surface groups form at the same
edge sites as acidic groups, but their quantity re-
mains lower than that of the destroyed acidic sites.
2.4 Sp~ctroscopi& rn~~~o~s
There have been numerous attempts to study the
surface groups by spectrometric methods, espe-
cially by infrared spectroscopy. This is made very
difficult by the strong IR absorption of carbon. The
first confirmation of the presence of carboxyl groups
was found with dispersions of highly oxidized fine-
particle-size color blacks[49-5 I I. Progress was
made by application of the ATR technique[52] and
especially by FT spectrometers[53,54]. Adsorption
peaks at ca. 1000 cm-’ and ca. 1200 cm-’ indicate
the presence of C-O single bonds. The spectrum
of HOOK-oxidized “graphitized” Thornel carbon
fibres showed peaks at 1705, 1730, and 1750 cm-‘,

Fig. 3. 0, and HCI consumption on immersion of out-

gassed aciivated carbon from sugar char in dilute hydro- (1) (n)
chloric acid. (Outgassing at 95O”C, HCI adsorption by pH-
metric titration to constant pH). Fig. 4. Proton addition to y-pyrone-like structures.
746 H. P. BOEHM

Table 8. Adsorption of HCI from 0.05 M solution on graph-

ites and carbon blacks

Surface area HCI uptake

m*/g EiLeo/g

Graphites
Kropfmiihl AF (natural) 13 2s r 2
Lonza KS 75 (synthetic) 7.5 34
Lonza KS 15 14
Lonza KS 75/KM 42 ::
Carbon blacks
CK3 77 40
Corax 3 84 36
Corax 3, H.T. 9OO’C 87 64
Corax 3, H.T. 3000°C 62 27

Fig. 5. Possible structures of basic surface sites on a

graphene layer, derived from the y-pyrone structure.
which were assigned to free carboxyl groups, esters,
and lactone groups, respectively[54]. An absorption
at 1640 cm-’ was explained by carbonyl groups situ-
ated near hydroxyl groups (enols). However, we
observed the same frequency with violanthrone (di-
benzanthrone), a polycyclic system with nine con-
densed rings and two carbonyl groups. An extended
review on this subject has been published[45], but
unfortunately there are not many studies on carbon
black surfaces.
X-ray photoelectron spectroscopy (XPS, ESCA)
has also been used for oxidized carbons, mainly
carbon fibres. Due to the high electronegativity of
oxygen, the 0 1s signal is not very sensitive to the
way in which the oxygen is bound. One fmds essen-
tially two different binding energies for oxygen sin-
gly and doubly bonded to carbon[SS]. More informa-
tion can be gained from satellites of the C Is peak
at higher binding energies[55,56]. The shifts from
the main peak range from 1.6 eV for carbon atoms
bonded to OH groups to 4.0 eV (carboxyl groups
or esters) and even higher. XPS is not very accurate
for quantitative determinations, and it is used mainly
in studies of low-surface area carbons such as car-
bon fibers.
Thermodesorption spectroscopy is not very well
suited for the determination of the functional
groups. Carboxylic groups are least stable, and they
decompose with formation of C02. However, this is
not possible when carboxylic anhydrides are formed
first, and they will produce CO2 plus CO in this

Acidic surface groups 1 psq/gf Basic surface groups [peq/‘gf

450 T-_q,i

\
350
r;l
: \ t
I \ \

250 350
O--U Norit, ox o.,.o Norlt, ox
1
,50 ) y Nod:' ox-to,,, , 1~ 250 1 TNorl:' ox-:,,t , , D

0 100 200 300 400 500 0 100 200 300 400 500

Temperature [“C ]
Fig. 6. Reduction of acidic surface sites on treatment with hydrogen (left side) and concurrent increase
in basic surface sites (right side). Open symbols: Activated carbon Norit, oxidized with 0,: Filled
symbols: Norit loaded with 200 pmol/g of platinum (80% dispersion at 150°C; there was some smtering
at higher temperatures).
 The surface chemistry of carbon blacks and other carbons
case. The TDS patterns for CO* and CO are affected
by the type of carbon used, the oxidation conditions,
and the way the TDS experiment is carried out[35].
The probability of secondary reactions of the
evolved gases is drastically enhanced with porous
carbons. Especially in micropores, CO* might react
with the carbon surface to give CO, and at lower
temperatures CO might react with surface oxygen
complexes to give CO,[57].
2.5 Oxidation under mild conditions
Formation of surface oxides is an activated pro-
cess. It has been shown that no oxygen is chemi-
sorbed at low temperatures (below 200 K) on freshly
produced carbon surfaces[58]. Surface oxidation
with molecular oxygen is fairly rapid above 3Oo”C,
but obviously surface oxides must be formed more
slowly at lower temperatures. This phenomenon of
“aging” of carbon materials (activated carbons and
carbon blacks) is well known in the relevant indus-
tries. The isoelectric point of a carbon black heat-
treated at 1500°C shifted from pH > 10.5 to pH
5.8 after one year’s storage in ambient air[59]. The
presence of water vapor significantly accelerates the
surface oxidation[60-621. The surface becomes
more hydrophilic when covered with surface oxides,
and the adsorption properties of activated carbons
are greatly affected[60,62].
We have treated an activated carbon (Norit) and
a furnace black (Corax 3) either in a drying oven at
110°C in ambient air or in air of 70% relative humid-
ity at 60°C. The increase in acid surface functions
was determined by titration with 0.05 N NaOH. As
is shown in Fig. 7, acidic surface groups are formed
in both cases with creation ofrelatively many pheno-
lit groups[48]. The rate of their formation decreases
gradually, but the surface was not saturated even
after 70 days. With humid air the oxidation was
much faster with the activated carbon, although the
reaction temperature was lower. With the carbon
black, slightly fewer acidic groups were found
after reaction in moist air at 60°C than in air of
low relative humidity at 110°C. Very likely this
difference arises because much more water is
NaOH uptnke Norit NaOH uplnke comx
@mWgl .. @mWgl
. .
&lo
.- l .
I ,I
-time+
Fig. 7. Formation of acidic surface groups during low-
temperature oxidation of an activated carbon (Norit) and
a furnace black (Corax 3); open symbols. For comparison,
the same carbons loaded with 200 pmol/g of palladium
were also studied (filled symbols).
767
adsorbed in the micropores of the activated carbon
than on the more hydrophobic surface of the
nonporous carbon black.
For comparison, we also studied the same car-
bons after loading with 200 pmol/g of palladium by
incipient-wetness impregnation with H2PdCl,. Al-
though it is known that palladium catalyses the gas-
ification of carbons with oxygen above 350”C[63],
the catalytic effect observed at 60-110°C (Fig. 7)
was impressive. It was very significant with the car-
bon black.
Liquid oxidizing agents are often used for the
production of acidic surface oxides. Concentrated
nitric acid is usually used at its reflux temperature,
and-as shown above-solutions of (NHJ2S208,
NaOCl, or KMnO, can be used at room tempera-
ture. Puri also found surface oxidation with KBrO,
or even KNO, solutions[64]. Therefore, it is not
surprising that carbon surfaces can also be oxidized
with metal cations of a sufficiently high oxidation
potential. It has been observed that hydrated Ag+
ions are reduced to metallic silver[65-671. Analo-
gously, PdCI:- ions are reduced to Pd0[48], and
iron(III) ions are reduced to iron(I1). Using a series
of different metal ions, Fu et al. showed experimen-
tally that the extent of oxidation depends on the
redox potential of the system, which is dependent
not only on the element, but also on temperature,
pH, and the presence of complexing ions[67]. After
oxidation with a weaker oxidizing agent, additional
surface oxides can be produced by action of
stronger oxidants[67].
2.6 Influence of surface oxides on the
surface properties
Surface oxides provide hydrophilic sites on a
hydrophobic surface. A high concentration of che-
misorbed oxygen makes a carbon black hydrophilic,
and it disperses very well in water. The dissociation
of carboxylic surface groups facilitates the disper-
sion by creating a negative surface charge[l4]. Car-
bon blacks oxidized with ozone form spontaneously
colloidal dispersions on immersion in water[68]. The
polar and the hydrophobic parts of a carbon black
surface can be separately determined by microcalor-
imetric determination of the heat of reaction for
the preferential adsorption of n-butanol (for polar
sites) and n-dotriacontane, C,*H, (for the unpolar
surface), on the carbons immersed in n-
heptane[69].
The carboxylic groups on oxidized carbon sur-
faces produce cation exchange properties, and car-
bons always exhibit an anion exchange capacity be-
cause basic surface oxides are always present when
carbons have been exposed to the atmosphere.
However, the concentration of basic surface sites
is relatively small, whereas considerable cation ex-
change capacities can occur. This can have conse-
quences for the application of color blacks in print-
ing inks, paints, etc.
The surface charge of carbons and the zeta poten-
768 H. P. BOEHM
tials in aqueous dispersions are determined by the
nature of the surface groups and the pH. Tempera-
ture and the concentration of non-potential-de-
termining ions have a smaller effect (provided there
is no specific adsorption). The isoelectric point of
a color black, Printex U, was found at pH 4.5 2
0.2. After heat treatment under N, at llOO”C, that
is, thermal destruction of most surface oxides, it
shifted to pH 8.8; after treatment at 1500°C it was
at pH > 10.5, and even higher after graphitization
at 27OO”C[59]. On oxidation with air at 37O”C, new
acidic functions were formed with a consequent shift
of the IEP to pH 5.7 after 2 h and pH < 3.0 after
60 h. These measurements were performed by elec-
trophoresis, but mass titration provides a conve-
nient way to determine IEPs if sufficient quantities
of material are available[70].
3. BINDING OF NITROGEN AND HALOGENS
Carbon blacks contain small concentrations of
nitrogen. This is very likely bound substitutionally
at the edges of the graphene layers. Nothing is
known about the solubility of nitrogen in the interior
of graphene layers (e.g., in graphite). It is well
known that diamonds frequently contain substitu-
tionally dissolved nitrogen.
On treatment of carbons with ammonia at ele-
vated temperatures (e.g., 600-9OO”C), nitrogen is
bound[71-731. This reaction has been studied with
carbon blacks as well as with activated carbons.
Photoelectron spectra show two main nitrogen N
1s signals. The peak with a binding energy of ca.
400 eV is assigned to amine-type nitrogen, and the
signal at 398-399 eV is generally explained by pyri-
dine- or acridine-type nitrogen[71,73]. These studies
have been performed mainly because the catalytic
activity of carbons (e.g., in oxidation reactions) is
drastically increased by incorporation of nitrogen.
At temperatures above 600°C some carbon is gasi-
fied in the reaction with NH,, and microporosity
develops. But also at 6Oo”C, there is an increase in
HCl neutralization, indicating that new basic surface
sites, presumably amine groups, were formedl741.
Halogens react with carbon blacks by sub-
stitution of hydrogen, and hydrogen halide is
evolved. Donnet reported that all hydrogen was re-
moved from the surface of carbon black Vulcan
6 after treatment with chlorine at 75O”C[15]. The
maximum chlorine uptake was observed at 450-
5OO”C[13,75,76]. The bound chlorine is hydrolyzed
only to a small part by hot 1 M sodium hydrox-
ide[76], but it can be removed by heating in hy-
drogen[77,781.
A study of chemisorption of chlorine at 500°C
has been performed using a carbon black and carbon
cloth that had been outgassed at 1000°C to remove
all chemisorbed oxygen and most of the hydro-
gen[77]. It was concluded that chlorine reacts step-
wise; first it is chemisorbed by addition, possibly
to double bonds. Subsequently, in the major step,
it is bound substitutionally with HCl evolution, and
finally it removes hydrogen as HCl without Cl
chemisorption.
Bromine can be chemisorbed in a similar way,
but the bound quantities are lower.
4. REACTIONS WITH FREE RADICALS
The surfaces of carbons react with free radicals,
and this reaction can be used for the grafting of
functional molecules or polymers to the carbon sur-
face. The fixation of 2-isobutyronitrile radicals,
(CH&-CN, on the carbon surface can be easily
determined from their nitrogen content[79]. The rad-
icals are produced by heating a solution of azo-di-
isobutyronitrile. Similarly, the carbons react with
3,5-dichlorobenzoyl peroxide or lauryl peroxide.
The radicals seem to attack especially quinone-type
functions, and radicalic sites may be produced on
the carbon surface[80]. Benzoate groups are found
on the surface after reaction with dibenzoyl perox-
ide, and these can be hydrolyzed to surface phenolic
groups[81].
Polystyrene can be grafted to carbon black sur-
faces by starting radicalic polymerization in styrene
solutions in the presence of carbon blacks. It has
been found that carbon blacks with quinone oxygen
inhibit polymerization initially until all quinone is
converted to hydroquinone[8 1,821. Prior hydroge-
nation of the quinone groups eliminates the inhibi-
tion period. These and other grafting reactions are
well described in Donnet’s review[l5].
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