Pergamon

Carbon Vol. 35, No. 12, 1799-1810, 1997 pp.

0 1997 Elsevier Science Ltd
Printed in Great Britain. All rights reserved
0008-6223/97 $17.00 + 0.00
PI I : MOOS-6223(97)00096-l
THE CHARACTERIZATION OF ACTIVATED CARBONS WITH
OXYGEN AND NITROGEN SURFACE GROUPS
S. BINIAK,~ G. SZYMA~~SKI,~* J. SIEDLEWSKI~ and A. SWI&TKOWSKI~
N. Copernicus University, Faculty of Chemistry, 87-100 Toruti, Poland
bMilitary Technical Academy, 00-908 Warsaw, Poland
(Received 3 Junuary 1996; accepted in revisedform 25 April 1991)
Abstract-The physicochemical properties and the surface chemical structure of the carbon materials
obtained by the modification of the commercial activated carbon D43/1 (Carbo-Tech, Essen, Germany)
were studied. The previously de-ashed activated carbon was subjected to the following modification
procedures: high-temperature treatment (1000 K) under vacuum; oxidation with cont. nitric acid; and
ammonia-treatment of annealed and oxidised carbons at high temperatures. The porous structure and
the surface area of the five different carbon samples obtained were estimated by means of mercury
porosimetry and from low-temperature nitrogen adsorption data. The thermogravimetric analysis and
the quantitative determination of surface functional groups by selective neutralisation of bases and
pH-metric titration were carried out. FTIR spectra (transmission) and X-ray photoelectron spectra (Cls,
01s and Nls) were obtained for all the carbon samples and compared with one another. The changes in
the porosity and the chemical properties of the carbon surface caused by the modification were analysed.
Some possible surface functional species, their structure and surface state are discussed. 0 1997 Elsevier
Science Ltd
Key Words-A. Activated carbon, B. modification, C. infrared spectroscopy, C. XPS, D. surface
properties.
1. INTRODUCTION
Increasing concern is being voiced about the levels
of toxic metals in the environment. It has led to more
stringent legislation and has prompted industry to
seek some more effective methods of pollution control
as permissible limits are reduced. In order to meet
these rigorous demands, researchers are faced with
the challenge of improving the performance of exist-
ing processes and developing new separation pro-
cedures. Adsorption processes, usually based on
activated carbon, have long been used in the water
and wastewater industry for the removal of colour,
odour and organic pollution [ 11. Activated carbons
are non-hazardous, processed carbonaceous products
with an intricate porous structure and an internal
surface area that is predominantly contained within
the micropores. Furthermore, their high stability
towards chemicals, radiation and heat, as well as
their rigid porous structure and mechanical strength,
give them undeniable advantages over polymeric
materials. There is a vast literature on the use of
activated carbon for the sorption of heavy metals
and radionuclides from aqueous solutions [ I-271. On
the other hand, the adsorption of metallic ions on
activated carbons from aqueous solutions is an
important process in the preparation of supported
metal catalysts; by regulating the factors affecting
adsorption, dispersion can be controlled, and as a
result, the metal particle size of the catalysts can be
controlled too [2,28]. In the adsorption of inorganic
*Corresponding author.
1799
compounds on activated carbons from aqueous solu-
tions, the chemical nature of the adsorbent, which is
determined by the quantity and the nature of the
surface complexes, generally exerts stronger influence
than the surface area and the porosity of the adsor-
bent [2,4,21]. It is well known that the sorption
properties of activated carbons are mostly influenced
by the presence of surface oxygen groups. They may,
depending upon conditions, enhance the sorption of
cations and/or anions from aqueous solutions
[ 18,211.
Next to hydrogen and oxygen, combined sulphur,
nitrogen, chlorine and other elements can be found
in carbon materials. They also affect the sorption
properties of carbons. The most important of them
all is nitrogen. The presence of nitrogen surface
groups considerably increases the carbon sorption
capacity towards anions [ 2 l-25,29].
Until now the sorption mechanism of inorganics
on modified carbons has not been clarified. It is
assumed that the sorption goes through ion-exchange
or complex formation [l-27,29]. However, some
experimental data suggest that the sorption may
result also from other processes, e.g. charge-transfer
reactions, physical adsorption of ion-clouds as
well as aqua- and hydroxo-complexes, interactions
between metal ions and n-electrons of aromatic struc-
tures (rc-d complexes) [4,8,21,26,27].
An attempt to ascertain the real nature of the
inorganic adsorbate-modified carbon surface inter-
actions requires information about the chemical char-
acter of a sorbent surface as well as its effect on the
1800 S. BI NI AK el ul
quantity and nature of adsorbed species. The litera-
ture data concern the investigations of miscellaneous
carbon materials with a different chemical character
and varied porous structure. All this makes it very
difficult to draw final conclusions about sorption
mechanisms. Therefore, the investigations of carbons
of the same origin, and with similar porosity, though
with some very different chemical properties, may
supply more reliable information about the character
of metal ion-carbon surface interactions. The aim of
our current research was to examine the changes in
the adsorption capacity towards transition metal
cations by the formation of various oxygen and
nitrogen surface functionalities on activated carbons
with similar porosity. The question of whether car-
bons with these surface complexes might be used to
advantage, not only in the separation or removal of
metal cations from aqueous solutions, but also in
some catalytic processes was investigated at the same
time [ 26,301. The characterization of carbon samples
with such different surface groups is the subject of
this work.
2. EXPERIMENTAL
2. I Curbon modljicution
Commercial granulated activated carbon D43/1,
obtained from Carbo-Tech Aktivkohlen GmbH
(Essen, Germany), was used in the present investiga-
tions. The carbon was de-ashed with cont. hydrotlu-
oric and hydrochloric acids by Korvers method [ 3 I]
and then desorbed under vacuum (lo- Pa) at 423 K
for 2 hours. The ashless activated carbon (D-NM )
was divided into three portions. The first one was
annealed under vacuum (IO-Pa) at 1000 K for 3
hours (D-HT), the second was oxidised with cont.
nitric acid at 353 K for 3 hours (D-Ox).
Subsequently, the two portions (D-HT, D-Ox) were
annealed in a stream of gaseous ammonia for 2 hours
at 1170 and 1070 K, respectively, and then cooled in
this stream (D-HT-N, D-Ox-N ). Afterwards, the
ammonia treated carbons were desorbed in vacuum
(lob2 Pa) at 400 K for 3 hours. All the prepared
samples were handled in ambient air.
2.2 Churacterisation of the modljied carbons
The porous structure of the carbons was deter-
mined from the nitrogen adsorption isotherm at 77 K
(by applying the D-R equation [32,33]) and by
mercury porosimetry (Carlo Erba 1500, Milan, Italy).
The adsorption measurements were conducted volu-
metrically in an automatic Gemini 2364 Sorptomate
(Micromeritics, Atlanta, USA). Prior to the adsorp-
tion measurements the carbon samples were heated
up to 473 K under a flow of 30 ml min- He for 3
hours. Subsequently, the samples were cooled under
helium to the ambient temperature and desorbed to
a residual pressure of 10e4 Torr or less,
Thermal analysis of the carbons was conducted in
an inert atmosphere (He, 20 dm3 h-), using an OD
102 derivatograph ( Paulik-Paulik-Erdy. Budapest)
in the 29331193 K temperature range. In addition,
the CO and CO, desorption profiles of the oxidised
carbon (D-Ox) were obtained by heating
(IO K min- ) 250 mg of a dry and finely-ground
sample from 293 to 973 K. The TPD profiles were
recorded using a home-built apparatus connected to
a quadrupole mass spectrometer (Dycor M200,
Pittsburgh, PA, USA) [34].
According to the Boehm method [35]. the acidic
group content was determined by neutralisation with
some bases of increasing strength; while the number
of basic groups was estimated by neutralisation with
0.05M hydrochloric acid. To make the second assess-
ment of the acidic and basic properties, the potentio-
metric titrations were carried out by means of the
point-by-point method [ 36.371. Known portions
of each carbon (0.5 g) were added to the mixtures
(50 ml each), containing various quantities of O.IM
NaCl, O.lM NaOH and O.lM HCl (pH=l-13) and
then shaken mechanically for 48 hours. The ionic
strength was kept constant (I=O.l). After the 48
hour period, the pH values of the suspensions were
determined using a glass electrode; an aliquot of the
supernatant liquid was then back-titrated with hydro-
chloric acid or sodium hydroxide.
The surface chemical composition of the samples
was determined by FTIR and X-ray photoelectron
spectroscopy. The XPS spectra were obtained with
an EscaLab 210 (V.G. Scientific Ltd.) photoelectron
spectrometer using unmonochromatised Al Kr radia-
tion (1486.6 eV). the source being operated at 15 kV
and 34 mA. The vacuum in the analysis chamber was
always better than 5 x IO- lo Pa. The survey scans
were collected from 0 to 1200 eV with a pass energy
of 50 eV. The high resolution scans were performed
over the 280-295 eV, 390%420eV and 5244545 eV
ranges with the pass energy adjusted to 20 eV. For
calibration purposes, the carbon Is electron bond
energy corresponding to graphitic carbon was refer-
enced to 284.5 eV. After the base line was subtracted,
the curve-fitting was performed using the non-linear
least-squares algorithm assuming a Gaussian peak
shape. This peak-fitting procedure was repeated until
an acceptable fit was obtained.
The transmission FTIR spectra of the carbon
samples were obtained using a Perkin-Elmer FHR
Spectrum 2000 spectrometer. The carbon-KBr mix-
tures in a ratio of 1:300 were ground under vacuum
in an agate mortar, then desorbed under vacuum
( 10m2 Pa) in order to eliminate moisture, and finally
pressed under vacuum in a hydraulic press. Before
the spectrum of a sample was recorded, the back-
ground line obtained was arbitrarily and automati-
cally subtracted. The spectra were recorded from
4000 to 450 cm-r at a scan rate of 0.2 cm s -, and
the number of interferograms with a nominal reso-
lution of 4 cm- was fixed at 100.
The characterization of activated carbons 1801
3. RESULTS AND DISCUSSION
3.1 Porous structure
The estimated pore volumes of the carbons
(Table 1) indicate that they possess a well-developed
porous structure. It is known that nitric acid treat-
ment or heating (in vacuum or in ammonia) may
cause considerable changes in a porous structure
[ 2 1,28,38-441. However, the obtained results indicate
that no great changes in the D-NM carbon result
from the applied modification procedures. The annea-
ling of the D-NM carbon in vacuum only slightly
enhances both the volume and the diameter of the
micropores. After the oxidation with nitric acid, the
micropore diameter increases slightly too, though the
total micropore volume decreases. The effect of
the nitric acid treatment is similar to that reported
for the other carbon materials [21,28,38-401. The
annealing of the carbon samples (D-NM, D-Ox) in
ammonia increases the volume of micropores as well
as their diameter. The observed increase of micropo-
rosity is in agreement with data for the other ammo-
nia treated carbons [40-441. The highest porosity of
the D-Ox-N sample confirms earlier reports [21,41]
that oxidation followed by annealing in ammonia
produces the greatest changes in a porous structure.
Heating under vacuum leads to the formation of
some new micropores, to the partial removal of meso-
and macropores owing to the loss of surface heteroat-
oms (mainly oxygen), and to an increase in the
structural order. Although oxidation also causes
some meso- and macropores to be removed, a number
of micropores subsequently become blocked. The
different results of heating in a stream of ammonia
are caused by additional activation [43]. In this case,
the amorphous carbon atoms are removed from pore
walls and edges; the presence of surface oxygen
complexes facilitates this process [21,41,45].
3.2 Thermal analysis
The de-ashed active carbon (D-NM ) is thermally
stable up to 793 K. At higher temperatures some
partial decomposition takes place owing to the
desorption of surface carbon complexes (Figs 1 and
2). Annealing under vacuum or in a stream of
gaseous ammonia enhances the thermal stability,
while oxidation diminishes it. Following annealing in
ammonia, the oxidised carbon is nevertheless the
most stable sample. This may suggest that nitrogen
atoms have been incorporated into the surface carbon
1
D-Ox
-__ D-NM
\
~-- D-HT
- D-HT-N
\
- D-Ox-N
I-
440 590 740 890 1040 II90
T WI
Fig. 1. TG curves of the modified carbons
layer. Carbons with built-in nitrogen atoms have
greater thermal stability [21,45].
The observed minimum on the DTG curves around
363 K is due to the desorption of the physically
adsorbed water. The high sorption of water on the
oxidised carbon (D-Ox) is the result of the strong
hydrophilic nature of the surface after its oxidation.
The increase in water sorption on the heated carbon
(D-HT) after this has been annealed in ammonia
(D-HT-N) supports the previous findings [42,43] on
higher water sorption after ammonia treatment. This
increase indicates that heating in ammonia also gener-
ates new hydrophilic sites on the carbon surface
[42,43]. The minima on the DTG curves for the
D-NM and D-Ox carbons above 500 K (at 543 or
713 K) correspond to the maxima on the profiles of
Table 1. Surface characteristics of the modified carbons
Apparent Pore volume, V Micropore Micropore width,
surface area, (r>7.5 nm) volume, W, L
Activated carbon S,,, (m g-) (cm3 g-) (cm3 g-)
(nm)
D-NM 1131 0.521 0.462 1.622
D-HT 1133 0.503 0.473 1.632
D-HT-N 1178 0.523 0.487 1.749
D-Ox 1071 0.492 0.448 1.645
D-Ox-N 1153 0.551 0.478 1.792
1802 S. BINIAK et ul.
- D-HT
~ D-NM
- D-Ox
D-Ox-N
r
1 440 590 740 890 1040 1190
T W)
Fig. 2. DTG curves of the modified carbons
carbon oxides recorded during the TPD measure-
ments of the carbon D-Ox (Fig. 3). The evolution
of CO, is associated with carboxylic groups and their
derivates, such as lactones and carboxylic anhydrides,
while the CO evolution is attributed to the decompo-
sition of quinones, hydroquinones and phenols, and,
furthermore, the water loss is due to hydroquinones
and phenols [28,38-40,45,46]. These profiles are very
similar to those obtained earlier by other researchers
for different carbons [28,38-40,45,46]. According to
Otake and Jenkis [46], the maxima on the CO,
profile are due to the decomposition of carboxylic
groups. Some single groups decompose above 543 K;
at the same time the adjacent groups are dehydrated
to carboxylic anhydrides, which then decompose
at 713 K.
3.3 Acid-baseproperties
The results of the Boehm titration show that the
surface of the de-ashed carbon (D-NM) is ampho-
teric with a slight excess of acidic properties
(Table 2), which increase noticeably following the
oxidation of the carbon surface with nitric acid
(D-Ox). The much larger increase in sorption capac-
ity for carbonates than for sodium hydroxide or
ethoxide is indicative of the formation of many more
L
0 100 200 300 400 500 600 700
Temperature, deg.C
Fig. 3. TPD profiles of the oxidized carbon D-Ox
acidic surface structures. Annealing, especially heat-
ing in ammonia (D-HT-N, D-Ox-N), enhances the
basic properties of the carbons at the expense of their
acidic properties. In addition, after annealing in
ammonia, the sodium ethoxide capacity increases
more than hydroxide uptake. According to Boehm,
this indicates an increase in the concentration of
surface carbonyl groups [35,44]. The appearance
of these groups results from the chemisorption
of oxygen when carbons were stored in the pres-
ence of moisture at the room temperature [ 18,21,
35,42,44,45]. The higher concentration of surface
carbonyl groups on ammonia treated carbons sug-
gests their higher ability to chemisorb oxygen with
creating carbonyl moieties.
The shape of the pH-metric titration curve for the
D-NM carbon (Fig. 4) is typical for amphoteric
carbons [47] and indicates a nearly linear acid
strength distribution of acidic centres. There is only
a slightly marked inflection point for some weak
acidic groups (pK,- 7.5) (Fig, 5). The decrease in
the K, values of the acidic centres is compensated by
the increase in their number. The appearance of other
deflection points on the pH-metric titration curve for
the oxidised carbon (Figs 4 and 5) (p((,, -4.0, pKa2
-7.7, pK,,>12.0 and pK,=l2.1) supports the
results of the Boehm method that nitric acid treat-
ment creates differences in the acid strength as well
as the number of surface groups. The pK, values are
similar to those reported by other authors for various
carbons treated with nitric acid [44,45,48,49]. The
strong acidic sites (pK,, -4) can be ascribed to
carboxyl groups whereas the sites of weak acid
strength (pK,,> 12) to hydroxyl structures [27,48-
The characterization of activated carbons
Table 2. Acid-base properties of the modified carbons
Uptake (mval g-r)
1803
Activated carbon
PH
HCl NaHCO, Na,CO, NaOH C,H,ONa
D-NM 6.75 0.295 0.110 0.175 0.373 0.480
D-HT 10.07 0.420 0.0 0.010 0.134 0.223
D-HT-N 10.36 0.632 0.0 0.025 0.100 0.317
D-Ox 3.08 0.131 0.725 1.107 1.663 2.054
D-Ox-N 10.18 0.722 0.0 0.040 0.144 0.357
16
i
06
Fig. 4. pH-metric titrations curves for the modified carbons.
05-
0.4 -
03-
2, -
5
= 0.2 -
0.1 -
501. The deflection point at about pH =7.7 may
result from the presence of weak carboxyl groups as
well as from the presence of isolated phenolic
functionalities.
Annealing under vacuum also creates differences
in the acid-base strength of a carbon surface. After
heating in vacuum (D-HT), two types of basic
centres, with pK,,r =4.0 and pKbZ > 11, respectively,
are observed. The existence of at least two types of
surface basic groups with different basicity was earlier
reported by Arico et al. [47] and Zawadzki [ 511 for
various carbons. Subsequent heating in ammonia
of the D-HT carbon results in additional basic
groups. There are three types of basic centres with
pK,,r = 4.3, pKbz =6.6 and pKb3 = 10.7, respectively.
The heating in ammonia of the oxidized carbon
(D-Ox) has also led to the formation of such basic
centres (pK,,=4.1, pK,,=7.1 and pK,,=10.2).
According to some authors [35,44,50], the exis-
tence of pyrone-like structures, incorporated in a
carbon matrix, is responsible for basic properties of
oxygen containing carbons. As pyrones reveal a
vague basic character (pK, - 13) [52], the observed
presence of various types of basic sites with different
basicity indicates that pyrone-like structures are only
_._ ._..._. D-NM
- D-HT
,
D_HT_N
I-
. . . . . . . . . ,,_&_N
__._.._. D-Ox
0.0 ; , I I I I 8 I I 1 I
0 2 4 6 8 IO 12 14
PH
Fig. 5. Differential plots of pH-metric titrations curves for the modified e;~rb~ws.
1804 S. B~N~AK et cd
partly responsible for the carbon basicity. The pres-
ence of the relatively strong basic sites with pK,
about 4 on the carbon surface may result from the
molecular adsorption of oxygen. There is XPS [42]
and IR [ 5 I ] evidence that oxygen can adsorb molecu-
larly on carbon surfaces to form superoxide ions
0;. These ions can either form surface complexes or
consume protons from solution in order to eventually
form water [ 511 or hydrogen peroxide [ 501. The
stabilized superoxide ion 0; can act as a strong
Briinsted base. It may even deprotonate some acids
that are weaker than water [53]. The more pro-
nounced basic properties of ammonia treated carbons
result from the presence of additional basic sites
(PKb2-
7). These basic sites are probably some nitro-
gen structures incorporated into the carbon matrix
during ammonia treatment. The presence of various
surface nitrogen moieties on carbons annealed in
ammonia was observed by Stiihr et al. during XPS
measurements [42,54].
3.4 XPS dutu
The XP survey spectra of the investigated carbons
indicate the presence of three distinct peaks due to
carbon, nitrogen and oxygen. The high-resolution
01s spectra (Fig. 6) reveal the presence of three
peaks corresponding to C=O groups (Peak 1. BE=
530.4k530.8 eV), C-OH and/or C-O-C groups
(Peak 2, BE=532.4-533.1 eV), and chemisorbed
oxygen and/or water (Peak 3, BE= 534.8-535.6 eV)
[ 55-60). The Cls spectra have each been resolved
into six individual component peaks (Fig. 7) repre-
senting carbidic carbon (Peak 1, BE=282.6-
282.9 eV), graphitic carbon (Peak 2. BE=284.6-
285.1 eV), carbon present in alcohol or ether groups
(Peak 3, BE = 286.3-287.0 eV ), carbonyl groups
(Peak 4, BE=287.55288.1 eV ), carboxyl or ester
groups (Peak 5, BE= 289.33290.0 eV ), and shake-up
satellite peaks due to n-rc* transitions in aromatic
rings (Peak 6, BE=291.2--292.1 eV) [55559,61,62].
The peaks in the 286.33287.5 eV region (Peaks 3 and
4) may also have resulted from the presence of C-N
structures [56,58,59,61]. The Nls regions indicate
the presence of several different species on each
carbon (Fig. 8). However, the interpretation of peaks
in the 393.0-396.7 eV region is very difficult due to
the paucity of appropriate literature data. The low
binding energies may suggest the presence of nega-
tively-charged nitrogen species. According to the
existing literature data, the peaks with the binding
energy of 395.6-396.7 eV (Peak 2) can be ascribed
to nitride-like species [63366], or aromatic N-imines
[67,68]. The presence of the peaks in the range of
3966398 eV was also reported by other authors [54].
The peaks with higher binding energies can be
ascribed to pyridine-like structures [ 58,59,69%75]
(Peak 3, BE=398.4-398.8 eV), pyrrolic [59,69-781
or amine moieties [42.54,56-581 (Peak 4, BE=
400.1-400.4 eV ). pyridine-N-oxides [ 37,50-53,699
751 (Peak 5. BE=402.1L402.6 eV), shake-up satel-
LI OL
D- HT
BE(eV)
Fig. 6. XP 01s core level spectra of the modified carbons.
( 1) C= 0: (2) C-OH. C-O-C; (3) chemisorbed water or
oxygen.
lites [ 591 (Peak 6, BE=404 eV ) and chemisorbed
nitrogen oxides [56,57,63,79] (Peak 7. BE=
404.9S405.6 eV).
According to Figs 6 and 7, carbonyls and alcohols
(or ethers) are the most numerous carbon-oxygen
The characterization of activated carbons
1805
6. 1041
I
4. 104
2. 104
0
D- HT
5
4.10- D-HT-N
2 6. 104
D-Ox
4. 104
2. 104
0
4.104
3. 104
2. 104
1. 104
0
295 290 205 280
BE(eV)
Fig. 7. XP Cls core level spectra of the modified carbons.
( 1) Carbidic; (2) graphitic; (3) C-OH, C-O-C, C-N; (4)
C ~0, C-N; (5) COOR (R = H, alkyl); n-n* shake up satel-
lites.
functional groups on the nonmodified carbon
(D-NM). The groups are hydrated to a high degree.
The Nls region was fitted by four peaks (Fig. 8).
The main peak at 400.1 eV (Peak 4) suggests the
presence of pyrrolic-like species [59,69-781 or pyri-
600
400
200
0
z
-
3000
2000
1000
0
3000 - D-Ox-N
405 400
BE(eV)
395 390
Fig. 8. XP Nls core level spectra of the modified carbons.
( 1) Unknown; (2) nitridic or aromatic N-imine-like species;
(3) pyridinic; (4) pyrrolic; (5) pyridine-N-oxides; (6) shake
up satellites; (7) chemisorbed nitrogen oxides.
dones [73,75]. Pyridone exists in two tautomers with
the carbonyl form (lactam) as the most abundant.
Hence, the chemical environment of the nitrogen
1806 S. BINIAK et cd
atom in pyridone is similar to that in pyrrolitic-N
[ 731. In addition, some peaks are observed at binding
energies of 393.0, 396.7 and 404.0 eV (Peaks 1, 2 and
6, respectively). As mentioned above, the contribu-
tions of the two remain quite uncertain. Probably.
the peak at 396.7 eV could be due to nitride-like
species [63-661 or aromatic N-imines [67,68]. The
third peak at 404 eV is due to shake-up effects [59].
Heating of the nonmodified carbon (D-NM ) under
vacuum leads to a drop in the concentration of
surface oxygen and nitrogen functional groups and
a change in their distribution. The number of alcohol
(or ether) groups increases relatively at the expense
of carbonyl groups (Figs 6 and 7). The surface oxides
appear due to the chemisorption of oxygen or water
(at room temperature) at reactive centres formed
during heating. Moreover, annealing either destroys
surface pyrrole- and pyridone-like species or trans-
forms them (Fig. 8, Peak 4) into pyridine-like func-
tional groups and pyridine-N-oxide species (Fig. 8,
Peaks 3 and 5). This effect is similar to that observed
by Wojtowicz (691 and Pels [73] for annealed coals
as well as by Stanczyk and coworkers [75] for
carbonized nitrogen-containing model compounds.
According to these researchers and also Kelemen
et al. [70], the pyridine-N-oxide species consists of
pyridine structures combined with oxygen resulting
from the post-heating oxidation of the pyridine func-
tional groups during storage in air.
Annealing of the heat-treated carbon (D-HT) in
ammonia further reduces the surface oxide concen-
tration and simultaneously increases the number of
surface nitrogen moieties, especially of pyridine struc-
tures. The increase in concentration of pyridine-like
moieties is followed by disappearance of pyrrolic
structures (Fig. 8, Peak 3). According to Stiihr and
Boehm, the new pyridine-like structures result from
the replacement of ether-like oxygen by -NH- in the
reaction with NH, in elevated temperatures, with
subsequent dehydrogenation to pyridine- or acridine-
like nitrogen on the periphery of the carbon layers
~421.
The considerable intensity of the peak, attributed
to water in the condensed phase, in the 01s region
for the oxidised carbon (Fig. 6, Peak 3, BE=
535.6 eV) indicates that, as in the case of the nonmod-
ified carbon D-NM, the surface of the oxidised
carbon is also highly hydrated. The Nls spectrum
indicates that the nitric acid treatment of the non-
modified carbon (D-NM) brings about the formation
of pyridine structures and pyridine-N-oxide species
(Peaks 3 and 5, BE = 398.4 and 402.4 eV, respectively)
at the expense of pyrrolic functional groups and
negatively-charged species (Fig. 8, Peak 2, BE=
396.7 eV; Peak 1, BE=393.0eV). After oxidation,
the peak with the lowest binding energy (Peak 1)
disappears completely.
As in the case of the D-HT carbon, heating of the
oxidised carbon (D-Ox-N) in ammonia not only
reduces the quantity of surface oxides but also
changes the concentration and distribution of surface
nitrogen species (Fig. 8). A further increase in
the concentration of pyridine structures (Peak 3)
coincides with the simultaneous disappearance of
nitride- or imino-like structures (Peak 2, BE=
396.4-396.7 eV). The relative intensity of the peak
at 402.5 eV (Peak 5) also decreases, whereas the
intensity of the peak at 400.4 eV, ascribed to pyrrolic
structures (Peak 4), remains nearly constant. This
indicates that the oxidation of a carbon sample before
its ammonia treatment at high temperatures, in con-
trast to the preliminary heating in vacuum, leads to
the formation of pyridinic as well as pyrrolic moieties.
However, pyridones, which have the same binding
energy as pyrroles may also be present on the surface.
The formation of pyridinic and pyrrolic moieties is
supported by the results of Jansen and Van Bekkum
[74,80]. According to them, these cyclic structures
result from the conversion of surface amides, imides,
lactams (a carbonyl form of pyridones) and nitriles
at high temperatures. Such groups are generated
during the ammonia treatment of oxidised carbon at
about 473 K [51,74,80,81]. The increase in the
number of nitrogen species incorporated into the
carbon lattice, especially of pyridine-like structures
during the ammonia treatment, followed by the
increase of carbon basicity may suggest that these
functionalities are responsible for the more pro-
nounced basic character of the ammonia treated
carbons.
3.5 FTIR data
In spite of the fact that the IR measurement
procedure applied here (i.e. the method of sample
preparation, background subtraction and band exten-
sion) makes it impossible to compare quantitatively
either the FTIR spectra, obtained for different car-
bons, or the relative intensities of the respective
bands, the recorded spectra clearly indicate which
individual surface structures may be present or absent
[40.51.82].
In all the recorded spectra, in the 3600-
3200 cm- range (Fig. 9), a band of O-H stretching
vibrations, due to the existence of surface hydroxylic
groups and chemisorbed water, was observed. The
asymmetry of this band at lower wave numbers
indicates the presence of strong hydrogen bonds
[14,51,83385].
The same band shape of O-H stretching vibrations
of ammonia treated carbons (D-HT-N, D-Ox-N)
supports the XPS results that N-H (amine) structures
are not formed during this treatment.
The presence of absorption bands characteristic
of CH, or CH2- structures (2956, 2921, 2851,
1468, 1340 and 460 cm-) in all the spectra (Fig. 10)
suggests the existence of some aliphatic species
[ 14,28,39,40,51,81-881 on the carbons.
The spectrum of the D-NM carbon is similar to
the reported spectra of other carbons derived from a
wide variety of sources [ 14,28,39,40,51,82--86,891.
The characterization of activated carbons 1807
,/
,.: :
: :
: i
; :
c -
Z
2 _
0
5
I
I ,... :
, -_-.,.
i :
\ ._._._.-...--
\
, : : \
., \
I, ,:
: : \ 5
: \
\
11
1
,,i 1 .,4
1, , 1
I,
: :: ,, ., . / ,, d
L4
\
..____----
.I.,
,;,, f.., :,c ::
. 1,
.__.._.._.._ . . . . . . . .-.
4000 3600 3300 2800 2400
WAVE NUMBER (cm-1
Fig. 9. Transmission FTIR spectra of the modified carbons
in the 4000-2400cm- region. (a) D-NM, (b) D-Ox, (c)
D-HT, (d) D-HT-N, (e) D-Ox-N.
Below 2000 cm-i the FTIR spectrum for the D-NM
carbon (Fig. 10) exhibits absorptions typical of
oxygen and/or nitrogen species. The presence of
bands at i) 171Ocm-, ii) 1645cm- and iii)
1560 cm- can be attributed to the stretching
vibrations of C=O moieties in i) carboxylic, ester,
lactone [ 14,285 1,s l-931; ii) quinone and/or ion-
radical structures [ 14,28,40,51,84,88]; and iii)
conjugated systems such as diketone, ketoester,
and keto-enol structures [82-8587,891. The
complicated nature of the absorption bands in
the 1750-1700cm-, 1650-1610 cm- and 1570-
1520 cm- regions suggests that bands due to aro-
matic rings and double-bond vibrations ( 1500, 1600
and 1650 cm-, respectively) overlap the aforemen-
tioned C=O moiety bands as well as the bands
due to nitrogen-containing species. A band due to
the vibrations of pyridine-like structures or cyclic
amides (lactams) (-C==N-) may appear in the
1610-1480 cm- region [40,51,80,81,87]. Another
broad band in the 1470-1380 cm- range consists of
a series of overlapping absorption bands that can be
ascribed to carboxyl-carbonates structures [ 5 I,8 l-
83,881, the deformation vibrations of surface
t
t
~ 1:
., i
e
. . :
.
..,,
I. I .,.,.,.,.,. ,.,.-j
7100 2coo IX00 1600 1400 I200 1000 8ot.J 6(W) 400
WAVE NlJMBER [cm-1
Fig. 10. Transmission FTIR spectra of the modified carbons
in the 2250&450cm- region. (a) D-NM, (b) D-Ox, (c)
D-HT, (d) D-HT-N, (e) D-Ox-N.
hydroxyl groups [ 5 1,83,87], in-plane C-H vibrations
in various surface C=C-H structures [ 14,51,81,90],
and C-N-- vibrations in heterocyclic structures
[81,87].
The overlapping peaks which form an absorption
band in the 1300-1000 cm- region, can be assigned
to ether (symmetrical stretching vibrations), epi-oxide
and phenolic structures existing in a different struc-
tural environment [ 14,51,81-84,86,88,90,91]. This
absorption may also result from the presence of
tertiary nitrogen species (C-N stretching vibrations
at 1250 cm-) incorporated into the carbon structure.
Cyclic compounds containing conjugated C=C
and C=N may be responsible for the absorption
observed at 800 cm- [81,82,87]. Absorption below
800 cm- can be assigned to out-of-plane deforma-
tion vibrations of C-H groups located at the edges
of aromatic planes [81-83,87,90,91].
The FTIR spectra of the oxidized carbon D43/1
(Figs 9 and 10) are quite similar to those obtained
for various carbon materials oxidized with nitric acid
[28,39,40,51,82,83,85,88,89].
As for other carbon materials [ 28,39,40,5 1,82,89],
after oxidation of the nonmodified carbon (D-NM)
1808 S. BINIAK et al
with nitric acid (D-Ox) a new band characteristic of
carbonyl moieties in carboxylic anhydrides appears
in the 1850-1800cm~ region [51,81,82,87,88,90-
931, and simultaneously increases the intensity of the
carbonyl functional group band in carboxyl (U
1710 cm-) diketone, ketoester and keto-enol struc-
tures (ca 1572 cm-i) as well as the band in the
1350- 1150 cm- region, characteristic of the CO
stretching and O-H bending modes [ 14,51,81-
84,86,88,90,91] (e.g. ether, lactone, epi-oxide, car-
boxy1 and phenolic structures).
The FTIR spectra of the annealed carbons (D-HT,
D-HT-N, D-Ox-N) (Figs 9 and 10) are similar and
confirm the results of the acid-base titrations
(Table 2) in that annealing under vacuum or in
ammonia diminishes the content of oxygen surface
complexes, especially that of strongly acidic surface
groups. There the band typical of carboxylic struc-
tures disappears and the bands of the remaining
surface oxygen complexes diminish considerably.
These changes are followed by an increase in the
intensity of the bands below 950 cm- i, characteristic
for out-of-plane deformation vibrations of CH
groups in aromatic structures [51,81,82,87].
1
I-
,
h ,
The presence of a small band at 1720 cm for the
D-HT carbon can be assigned to pyrone-like struc-
tures [52,87]. Subsequent annealing of the D-HT
carbon in ammonia diminishes further the intensity
of the band at 1635 cm-i, assigned to quinone and/
or ion-radical structures [ 14,28,40,51,84,88].
Simultaneously, the ammonia treatment enhances
slightly the intensity of the bands in the regions
1600-1250 cm-i and 1000-750 cm- (Fig. 11).
Similar results were also observed for the oxidized
carbon heated in ammonia (D-Ox-N). An increase
in the intensity of the bands in those regions at 1330
and 880 cm-i, respectively, characteristic of pyridine,
pyridine-N-oxide or pyridone structures [40,80,87]
supports the XPS results that ammonia treatment
incorporates nitrogen into the carbon aromatic lattice
with formation of pyridine-like structures.
2100 2000 18rKl 1600 1400 I100 1000 x00 flno 400
WAVE NUMBER [cm- 1
Fig. 1 I, Difference spectra of the heated carbons.
enhances the basic properties of the carbons at the
expense of their acidic properties. At least two types
of basic centres are observed. Probably, the role of
basic sites may be played by superoxide ions and
pyrone-like structures. After ammonia treatment
there appears the third type of basic sites - pyridine-
like structures.
4. CONCLUSIONS
The spectroscopic data (FTIR, XPS) indicate that
carbonyls and alcohols (or ethers) are the most
abundant carbon-oxygen functional groups on the
nonmodified carbon (D-NM ). Besides the surface
oxygen complexes, a number of different nitrogen
functional groups (predominantly pyrrole-like (or
pyridone) and pyridine-like species) were also
observed.
The surface modification procedures applied to The oxidation of the nonmodified carbon with
de-ashed carbon (D-NM) (heating in vacuum or cont. nitric acid (D-Ox) considerably increases the
ammonia, oxidation with nitric acid) lead to carbon concentration of surface oxides, which are mainly
samples with a very different chemical nature and a located at the edges of aromatic planes. A band that
similar porous structure. Some increase in the micro- is typical of carbonyl moieties in carboxylic anhy-
pore diameter and volume is observed, but only after drides appears, and there is an increase in the band
oxidation does the micropore volume decrease. intensities of carbonyl moieties in carboxyl, keto-
During ammonia treatment the carbon samples are ester and/or keto-enol structures and in the bands
additionally activated. The carbons heated in ammo- of surface ether and hydroxyl functional groups. In
nia display the highest thermal stability. The thermal addition, nitric acid treatment also gives rise to
analysis and XPS data also indicate that all samples pyridine structures and pyridine-N-oxide species at
(especially the de-ashed carbon and its oxidised form) the expense of pyrrolitic moieties. Probably, the
contain considerable amounts of moisture. Oxidation pyridine-N-oxide species consist of pyridine struc-
with cont. nitric acid leads to a greater number of tures combined with oxygen resulting from the post-
acidic surface structures and with higher acid strength heating oxidation of the pyridine functional groups
as well. However, annealing, especially in ammonia, during storage in air.
The characterization of activated carbons 1809
The FTIR and XPS spectra for the annealed
carbons (D-HT, D-HT-N and D-Ox-N) support the
results of the acid-base titrations (Table 2) in that
annealing under vacuum or in ammonia reduces the
content of surface oxygen complexes, especially of
strong acidic surface groups. Annealing under
vacuum also leads to the destruction of surface
pyrrole-like species or their transformation into pyri-
dine-like functional groups and pyridine-N-oxide
forms, its concentrations increase further after heat-
ing in ammonia. However, preliminary oxidation of
the sample with nitric acid, before ammonia heating,
results also in the formation of pyrrole-like structures.
Acknowledgement.s-The authors extend their gratitude to
Mr J. Sobczak and Prof 2. Karpinski, Institute of Physical
Chemistry of the Polish Academy of Sciences, ul. Kasprzaka
44/52, PL-01-224 Warszawa, for the XPS and TPD measure-
ments, respectively. This work was partially supported by
the Polish Committee for Scientific Research, project No. 3
P405 001 05.
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
23.
REFERENCES
Abassi, W. A. and Streat, M., Sepur. Sri. Technol.,
1994, 29, 1217.
Bautista-Toledo, I., Rivera-Utrilla, J., Ferro-Garcia, M.
A. and Moreno-Castilla, C., Carbon, 1994, 32, 93.
Qadeer, R. and Hanif, J., Carbon, 1995, 33, 215.
Rivera-Utrilla, J. and Ferro-Garcia, M. A., Ads. Sci.
Technol., 1986, 3, 293.
Ferro-Garcia, M. A., Rivera-Utrilla, J., Rodriguez-Gor-
dillo, J. and Bautista-Toledo, I., Carbon, 1988, 26, 363.
Reed, B. E. and Nonavinakere, S. K., Sefar. Sci. Tech-
nol., 1992, 27, 1985.
Redd, B.E. and Matsumoto, M., Separ. Sri. Technol..
1993, 28, 2179.
Dobrowolski, R., Jaroniec, M. and Kosmulski, M.,
Curbon, 1986, 24, 15.
Kahn, M. and Khattak, Y. I., Carbon, 1992, 30, 957.
Rivera-Utrilla, J. and Ferro-Garcia, M. A., Carbon,
1987, 25, 645.
Petrov, N., Budinova, T. and Khavesov, I., Carbon,
1992, 30, 135.
Qadeer, R. and Hanif, J., Carbon, 1994, 32, 1433.
Leyva-Ramos, R., Fuentes-Rubio, L., Guerrero-Coro-
nado, R. M. and Mendoza-Barron, J., J. Chem. Biotech-
nol., 1995, 62, 64.
Macias-Garcia, A., Venezuela-Calahorro, C., Gomez-
Serrano, V., Espinosa-Ma&la, Carbon, 1993,31, 1249.
Jayson, G.G., Sangster, J. A., Thompson, G. and Wil-
kinson, M. C., Carbon, 1993, 31, 487.
Couhlin, R. W. and Ezra, F. S., Environ. Sci. Technol.,
1968, 2, 291.
Nandi, S. P., Walker, P. L., , JrFuel, 1971, 50, 345.
Cookson Jr, J. T., in Carbon Adsorption Handbook, ed.
P. N. Cheremisinoff and F. Ellerbusch. Ann Arbour
Sci. Pub]., Ann Arbour. 1978, pp. 241-279.
McDougall, G. J. and Hancock, R. D., Minerals, Sci.
Effg., 1980, 12, 85.
Jankowska. H., Swiatkowski, A., Oscik, J. and Kusak,
R., Carbon, 1983, ,21, 117.
Jankowska, H., Swiatkowski, A., Starostin, L. and
tawrinienko-Omiecynska, J., Adsorption of Ions on
Activated Carbon, PWN, Warsaw, 1991 (in Polish).
Abotsi, G. M. K. and Scaroni, A. W., Carbon, 1990,
28, 79.
Jankowska, H., Starostin, L., Pinkas, K. and Przybyt-
niak, G., Przem. Chem., 1985, 64, 429.
24.
25.
26.
27.
28.
21.
30.
31.
32.
33.
34.
35.
36.
37.
38.
39.
40.
41.
42.
43.
44.
45.
46.
47.
48.
49.
50.
51.
52.
53.
54.
55.
56.
57.
58.
Cruywagen, J. J. and de Wet, H. F., Polyhedron, 1988,
7, 547.
Cruywagen, J. J. and Pienaar, A. T., Polyhedron, 1989,
8, 71.
Swiatkowski, A., Szymanski, G. and Biniak, S., in Fun-
damentals of Adsorption, ed. M. D. Le Van, Kluwer
Academic Publishers, Boston, 1996, pp. 9133920.
Tarkovskaya, I. A., Okislennyj Cgol, Naukova Dumka,
Kiev, 198 1.
Suh, D. J., Park, T.-J. and Ihm, S.-K., Curbon, 1993,
31, 427.
Jankowska, H. and Starostin, L., Przem. Chem., 1983,
62, 624.
Szymariski, G. S., Biniak, S. and Rychlicki, G., Zeszyty
Naukowe AGH, Chemia, 1993, 25, 139.
Korver, J. A., Chem. Week blad, 1950, 46, 301.
Dubinin, M. M., Carbon, 1988, 26, 97.
McEnaney, B., Carbon, 1987, 25, 69.
Lomot, D., Juszczyk, W., Pielaszek, T., Kaszkur, Z.,
Bakuleva. T.N.. Karuinski. Z.. Wasowicz. T. and
Michalik,J., New J. &em., 1995: 19,263.
Boehm, H. P., in Advances in Catalysis, Vol. 16, ed. D.
D. Eley, H. Pines and P. B. Weisz, Academic Press.
New York, 1966.
de Bruin, W. J. and Van der Plas, T., Rev. Gen. Caout.,
1964, 41, 453.
Hamieh, T. and Siffert, B., Colioids und &&es, 1991,
61, 83.
Krishnankutty, N. and Vannice, M. A., Chem. n/later.,
1995, 7, 754.
Moreno-Castilla, C., Ferro-Garcia, M. A., Joly, J. P.,
Bautista-Toledo, I., Carrasco-Martin, F. and Rivera-
Utrilla, J., Lungmuir, 1995, 11, 1386.
Vinke, P., van der Eijk, M., Verbree, M., Voskamp, A.
F. and van Bekkum, H., Carbon, 1994, 32, 675.
Jankowska, H. and Starostin, L., Przem. C/tern., 1985,
64, 305.
Stohr, B., Boehm, H. P. and Schlogl, R., Curbon, 1991,
29, 707.
Tomlinson, J. B., Freeman, J. J. and Theocharis, C. R.,
Carbon. 1993, 31, 13.
Boehm, H. P., Carbon, 1994, 32, 759.
Pm-i, B. R., in Chemistry und Physics of Carbon, Vol. 6,
ed. P. L. Walker. Marcel Dekker. New York. 1970.
pp. 191-282.
Otake, Y. and Jenkins, R. B., Carbon, 1993, 31, 109.
Arico, A. S., Antonucci, V., Minutoli, M. and Gior-
dano, N., Carbon, 1989, 21, 337.
Bandosz, T. J., Jagiello, J., Contescu, C. and Schwarz,
J. A., Curbon, 1993, 31, 1193.
Jagietto. J., Bandosz, T. J. and Schwarz, J. A., Carbon,
1994, 32, 1026.
Leon y Leon, C. A., Solar, J. M., Calemma, V. and
Radovic, L. R., Carbon, 1992, 30, 797.
Zawadzki, J., in Chemistry and Physics of Carbon,
Vol. 21, ed. P. Thrower, Marcel Dekker, New York,
1988, pp. 1477380.
Mlochowski, J., Chemistry of Heterocyclic Compounds,
PWN, Warsaw, 1994 (in Polish).
Sawyer, D. T., Ox_vgen Chemistry, Oxford University
Press, London, 1991,
Boehm, H. P., Stiihr, T., de Rincorn, A. R. and Ter-
eczki, B., Fuel, 1984, 63, 1061.
Proctor, A. and Sherwood, P. M. A., Carbon, 1983,
21, 53.
Desimoni, E., Casella, G. I., Cataldi, T. R. I., Salvi, A.
M., Rotunno, T. and Di Croce, E., Sur$ Interface Anal.,
1992, 18, 623.
Darmstadt, H.. Roy, Ch. and Kaliaguine, S., Carbon,
1994, 32, 1399.
Kozlowski, C. and Sherwood, P. M. A., Curbon. 1986,
24, 357.
1810 S. BINIAK eta1
59.
60.
61.
62.
63.
64.
65.
66.
67.
68.
69.
70.
71.
72.
73.
74.
75.
76.
Xie, Y. and Sherwood, P. M. A., Appl. Spectrosc., 1989,
43, 1153.
Atamny, F., Bloecker, J., Dubotzky, A., Kurt, H.,
Timpe, O., Loose, G., Mahdi, W. and Schloegl, R.,
Mol. Phys., 1992, 76, 851.
Reis, J., Botelho, A. M., Rego, D., Lopes Da Silva,
J. D. and Soares, M. N., J. Mater. Sci., 1995, 30, 118.
Albers, P., Deller, K., Despeyroux, B. M., Schaefer, A.
and Seibold, K., J. Cutal.,-1992, 133, 467.
Lin. J.. Wee. T. S.. Huan. A. C. H. and Tan. K. L..
J. Vuc. Sri. Technoi., 1994, A12, 2074.
Onyrinka, E. C., Appl. Spectrosc., 1993, 47, 35.
Hendrickson, D. N., Hollander, J. M. and Jolly, W. L..
Inorg. Chem., 1969, 8, 2642.
Bertoti, I., Mohai, M., Sullivan, J. L. and Saied, S. 0..
Appl. Surf: Sci., 1995, 84, 357.
Catteau, J. P., Lablache-Combier, A., Grimblot, J.,
Nastasi, M. and Streith, J., Tetrahedron, 1975, 31,2909.
Tsuchiya, S. and Seno, M., Chem. Phys. Lrtt.. 1978,
54, 132.
Wojtowicz, M. A., Pels, J. R. and Mouhjn, J. A.. Fuel,
1995, 74, 507.
Kelemen, S. R., Gorbaty, M. L. and Kwiatek, P. J.,
Energy Fuels, 1994, 8, 896.
Pels, J. R., Nitrous Oxide in Cool Combustion, Ph.D.
Thesis, Delft University of Technology, The Nether-
lands, 1995.
Piwowarska, Z., Stanczyk, K. and Dziembaj, R., Cocrl
Sri. Technol., 1995, 24, 1693.
Pels, J. R., Kapteiin, F., Mouliin, J. A., Zhu, Q. and
Thomas, K. M:, C&bon, 1995, 33, 1641.
Jansen, R. J. J. and van Bekkum, H.. Carbon, 1995.
33, 1021.
Staticzyk, K., Dziembaj, R., Piwowarska, Z. and Wit-
kowski, S., Curhon, 1995, 33, 1383.
Hamilton, L. E., Sherwood, P. M. A. and Reagan, B.
M., Appl. Spectrosc.. 1993, 47, 139.
17.
78.
79.
80.
81.
82.
83.
84.
85.
86.
87.
88.
89.
90.
91.
92.
93.
Buckley, A. N., Coil. Surf: A. Phys. Eng. Aspects, 1994,
93, 159.
Wallace, S., Bartle, K. D. and Perry, D. L., Fuel, 1989,
68, 1450.
Kozlowski, C. and Sherwood, P. M. A., Carhon, 1987.
25, 751.
Jansen, R. J. J. and van Bekkum, H., Carbon, 1994,
32, 1507.
Meldrum, B. J. and Rochester, C. H.. J. Chem. Sot.
Faraday Trans., 1990, 86, 1881.
Meldrum, B. J. and Rochester, C. H., J. Chem. So<,.
Faraduy Trans., 1990, 86, 861.
Acedo-Ramos, M., Gomez-Serrano, V., Venezuela-
Calahorro, C. and Lopez-Peinado, A. I., Specrrosc.
Lett., 1993, 26, 1117.
Gomez-Serrano, V., Acedo-Ramos, M., Lopez-Pei-
nado, A. J. and Venezuela-Calahorro, C.. Fuel. 1994.
73, 387.
Hontoria-Lucas, C., Lopez-Peinado, A. J., Lopez-Gon-
zalez, J. De D., Rojas-Cervantes, M. L. and Martin-
Aranda. R. M.. Carbon. 1995, 33, 1585.
OReilly, J. M. and Mosher, R. A.\ Curbon. 1983,21,47.
Socrates, G., Infrared Charucteristic Group Frequencies,
2nd edn. John Wiley and Sons, Chichester, 1994.
Fanning, P. E. and Vannice, M. A., Curhon. 1993, 31,
721.
Selhtti, C., Koenig, J. L. and Ishida, H.. Curhon, 1990.
28, 221.
Meldrum, B. J. and Rochester, C. H., J. Chem. Sot.
Faruduy Truns., 1990, 86, 2997.
Meldrum, B. J. and Rochester, C. H., J. Chrm. Sot.
Furuday Trans., 1990, 86, 3647.
Nakahara, M., Asai, S., Sanada, Y. and Ueda. T.,
J. Muter. Sci., 1995, 30, 5667.
Nakahara, M. and Sanada, Y., J. Mater. Sci., 1995,
30, 4363.