J. Phys.
IV France 117 (2004) 57-63
EDP Sciences, Les Ulis
DOI: 10.1051/jp4:2004117009
Characterization of activated carbons by FT-IR/PAS and TPD
J. Ryczkowski1, S. Pasieczna1, J.L. Figueiredo2, M.F.R. Pereira2
and T. Borowiecki1
1
University of Maria Curie-Sklodowska, 20-031 Lublin, Poland
2
Laboratorio de Catalise e Materiais, Departamento de Engenharia Quimica, Faculdade
de Engenharia, Universidade do Porto, 4200-465 Porto, Portugal
Abstract. Commercial carbon NORIT and carbon xerogel samples were modified in an oxidizing atmosphere
(wet and dry oxidation) and than subjected to physico-chemical characteristic, including temperature-
programmed desorption (TPD) of CO and CO2, and spectroscopic analysis. Surface changes due to oxidation
procedure were monitored by FT-IR/PAS.
1. INTRODUCTION
Carbon materials are finding an increasing number of applications in catalysis, either as supports
for the active phases, or as catalysts on their own. Their performance is determined both by their texture
and surface chemistry [1]. An example of specific carbon materials are aerogel/xerogel carbons [2]. They
are unique mesoporous materials having high surface area (400-1100 m2/g) offering a wide range of
applications in super-capacitors, fuel-cells, filters, catalyst supports, etc. [3,4].
In the case of activated carbons, the texture may be adapted to suit the situation by adequate choice
of the activation procedure. In particular, it is possible to prepare carbons with different proportions
of micro, meso and macropores [5].
On the other hand, the nature and concentration of surface functional groups may be modified by
suitable thermal or chemical post-treatments [2,6-9]. Oxidation in the gas or liquid phase can be used to
increase the concentration of surface oxygen groups, while heating under inert atmosphere may be used to
selectively remove some of these functions. Carboxyl, carbonyl, phenol, quinone, and lactone groups,
have been identified on carbon surfaces [10,11].
A variety of experimental techniques has been used to characterize these functional groups, such as
chemical titration methods [10], temperature-programmed desorption (TPD) [6], X-ray photoelectron
spectroscopy (XPS) [6,12] and infrared spectroscopy methods (FT-IR, DRIFTS, FT-IR/PAS) [6,13,14].
The desired result with all FT-IR (Fourier transform infrared) sampling techniques is to obtain
an absorbance spectrum of the sample as quickly and easily as possible. In many cases, however, direct
analysis of “as received” samples by transmission or reflection methods is not practical because the
sample either transmits inadequate light to measure or it lacks suitable surface or particle size conditions
for reflectance spectroscopies.
The measurement of IR spectra of carbons obviously presents a non-trivial challenge to the
spectroscopist. The dispersion of a finely divided carbonaceous solid in an IR transparent (e.g., KBr)
diluent (matrix) so as to record its transmission or diffuse reflectance spectrum may be successful.
However, the preparation of a well mixed sample is sometimes difficult or even impossible [15].
Photoacoustic spectroscopy (PAS) is unique as a sampling technique, because it does not require that the
sample be transmitting, and has low sensitivity to surface condition [15,16]. FT-IR/PAS allows the analyst
to obtain useful data for net carbons while to eliminating the need for this sample preparation step.
Therefore, it is not surprising to find that a significant number of research teams have successfully used
this technique to study carbons during last years. Carbons (in addition to elemental carbons) are samples
with very high (up to 90%) carbon contents such as chars, soots, and cokes. Since several types of
58 JOURNAL DE PHYSIQUE IV
functional groups exist in these substances, viable FT-IR/PA spectra of these carbons are readily
obtainable.
The aim of the conducted studies was to check the suitability of the PA measurements in an infrared
region for monitoring changes of the carbon surfaces modified in an oxidizing atmosphere (wet and dry
oxidation) in order to introduce different oxygen surface complexes, and to compare obtained results with
the TPD studies as well as physico-chemical characteristic of the examined samples.
2. EXPERIMENTAL
2.1 Samples preparation
Detailed samples preparation were described earlier [2,6,9]. A brief summary of the examined samples
is given in Table 1.
Table 1. Brief characteristic of studied samples
Sample Treatment Comment
No description
2 Carbon NORIT GAC oxidized with 6M HNO3, 3h oxidation treatment is described
by Faria et al. [9]
3 Carbon xerogel oxidized with air synthesis and gas phase activation
CX-12 of a high-density carbon xerogel
is decribet by Samant et al. [2]
A NORIT ROX 0.8 activated carbon
(pellets of 0.8 mm diameter and 5 mm
4 Carbon NORIT ROX oxidized with 5% O2, length) was used after oxidation
T = 425oC, 10h, treatment in the gas phase in order to
achieve the desired burn-off
(BO; BO = 21.5%) [6]
A NORIT GAC 1240 PLUS activated
5 Carbon NORIT GAC without any treatment carbon was used as supplied
(0.42<d<2 mm) [9]
2.2 Textural characterization
The textural characterization of the materials was based on the N2 adsorption isotherms, determined
at 77 K with a Coulter Omnisorp 100 CX apparatus. The micropore volume (Wmicro) and mesopore surface
area (Smeso) were calculated by the t-method, using the standard isotherms for carbon materials proposed
by Rodriguez-Reinoso et al. [17]. The adsorption data were also analyzed with the Dubinin equation. In all
cases, a type IV deviation was noted [18]. Two micropore structures were taken into account, and the
corresponding volumes, W01 and W02, were calculated [18]. The Stoeckli equation [19] was used to
estimate the average micropore width of the smaller pores (L1), using a value of 0.34 for the affinity
coefficient of nitrogen.
2.3 Surface chemistry characterization
2.3.1 TPD
TPD profiles were obtained with a custom built set up, consisting of a U-shaped tubular micro-reactor,
placed inside an electrical furnace. The mass flow rate of the helium carrier gas (69 µg/s) and the
temperature program from room temperature (RT) to 1100ºC at a heating rate of 5ºC/min were controlled
with appropriate equipment. The amounts of CO and CO2 desorbed from the activated carbon samples
(100 mg) were monitored with a SPECTRAMASS Dataquad quadrupole mass spectrometer. The masses
monitored for all samples were 2 (H2), 16 (O), 18 (H2O), 28 (CO) and 44 (CO2).
9th WORKSHOP ON PHOTOACOUSTICS AND PHOTOTHERMICS 59
2.3.2 pHpzc
For the determination of the pHpzc of the samples [20] 50 cm3 of 0.01M NaCl solution was placed
in a closed Erlenmeyer flask. The pH was adjusted to a value between 2 and 12 by adding HCl 0.1M
or NaOH 0.1M solutions. Then, 0.15 g of each AC sample was added and the final pH measured after 48h
under agitation at room temperature. The pHpzc is the point were the curve pHfinal vs pHinital crosses the line
pHinitial = pHfinal.
2.4 Elemental analysis
The materials were also characterized by elemental analyses, with a CARLO ERBA EA 1108 Elemental
Analyzer.
2.5 Spectroscopic measurements
FT-IR/PAS spectra were recorded at a resolution of 8 cm-1 using a Bio-Rad Excalibur FT-IR
spectrometer and a MTEC300 PA accessory (Figure 1), in the range of mid IR – MIR (4000-400 cm-1).
Infrared spectra were normalized with the A NORIT GAC 1240 PLUS activated carbon. Before each data
collection, the PA cell was purged with dry helium for 5 min. For each measurement 1024 scans were
acquired.
3. RESULTS AND DISCUSSION
3.1 Textural characterization
The textural characterization of the activated carbon samples based on the results of nitrogen
adsorption is presented in Table 2. The original activated carbon NORIT ROX (not shown in Table 2)
has similar textural and surface chemistry properties to the original NORIT GAC (Sample 5) [6].
Table 2. Physico-chemical data of the investigated samples
Sample Elemental analysis (wt. %) Wmicro Smeso W01 W02 L1 SBET pHpzc
C H N S O* (cm3/g) (m2/g) (cm3/g) (cm3/g) (nm) (m2/g)
2 78.5 0.8 0.3 0.7 19.70 0.353 91 0.303 0.048 1.1 909 2.7
3 66.7 0.4 0.0 0.0 32.90 0.140 601 - - 1.2 954 2.9
4 89.7 0.3 0.6 0.0 9.34 0.537 167 0.459 0.083 1.4 1400 3.9
5 94.9 0.3 0.2 1.0 3.60 0.367 125 0.312 0.058 1.1 972 9.7
* obtained by difference
The oxidation treatment in liquid phase (Sample 2 vs Sample 5) shows no significant impact on the
texture of the carbon material, the volume of micropores and surface area of mesopores showing just a
slight decrease. Gas phase oxidation increases the micropore volume, the mesopore surface area and the
average width of the micropores (Sample 4 vs Sample 5). Carbon Xerogel (sample 3) is a mesoporous
material. Based on the elemental analysis data it can be noticed that sample 3 (oxidized with an air) exhibit
the largest oxygen content, next is sample 2 (wet oxidation, Table 1), and the lowest amount is in the case
of oxidation with 5% O2 (sample 4). This ought to be confirmed by TPD (carbon oxides formation) and
spectroscopic measurements (the presence of an appropriate oxygen groups on the examined carbon
surfaces).
60 JOURNAL DE PHYSIQUE IV
3.2 Surface chemistry characterization
Figure 1 shows the TPD spectra of the materials tested.
a) b)
Figure 1. TPD spectra before and after different oxidizing treatments: a) CO evolution, b) CO2 evolution.
It is established [6] that during a TPD experiment, in the absence of mineral matter effects or
diffusional limitations (secondary reactions), CO2 peaks result from the decomposition of carboxylic acids
at low temperature (below 400ºC), or lactones at higher temperatures (around 650ºC); carboxylic
anhydrides originate both CO and CO2 (released at about 550ºC); CO peaks result from phenols
and ethers (released around 700ºC) and carbonyl/quinone groups (released around 850ºC). Schematically
it is presented in Figure 2.
From Figure 1 it can be observed that
the HNO3 oxidative treatment (Sample
2) originates the highest amount of
carboxylic groups and, comparing to the
original carbon (Sample 5) there is also
an increase in the amounts of the other
surface oxygen-containing groups. The
air oxidation treatment (Sample 4 vs
Sample 5) originates mainly phenol and
carbonyl/quinone groups (released as
CO at high temperatures), as well as
lactones and carboxylic anhydrides.
Sample 3, an air oxidised carbon
xerogel, generates the highest amount of
Figure 2. Temperatures of CO and CO evolution from surface oxygen surface groups.
2
oxygen groups (based on the data from TPD experiments).
The pHpzc and elemental analysis results presented in Table 2 agree with the results obtained by TPD:an
increase in the amount of oxygen content and a decrease in the pHpzc with the increase of the amount of
oxygen surface groups. The pHpzc was expected to decrease with the increase in the amount of the surface
groups, since the majority of these groups have an acid character. Sample 5 had the highest pHpzc value
followed by Sample 4 and Sample 3, which have progressively more oxygen surface groups. Sample 2 has
the lowest pHpzc as a result of the large amount of strong acid groups (those released as CO2 at low
temperature).
3.3 Spectroscopic results
The interpretation of the spectra is complicated by the fact that each group originates several bands at
different wavenumbers, therefore each band may include the contribution from various functional groups
exist on the carbon surface (Figure 3). In the preliminary studies all recorded spectra were normalized with
9th WORKSHOP ON PHOTOACOUSTICS AND PHOTOTHERMICS 61
the carbon black reference provided by MTEC Photoacoustics [14]. For the studies presented now IR
spectra were normalized with the A NORIT GAC 1240 PLUS activated carbon (Sample 5).
Figure 3. IR assignments of oxygen groups on carbon surfaces [6,21,22].
Inspection of Figure 1 provide supplementary information for the spectroscopic results. It is evident that in
the case of Sample 2 its surface is mostly covered by the carboxyl groups. There are other functional
groups contained oxygen but they are present in lower amount (in comparison to the carboxyls). A band
with a maxima located at 1612 and 1587 cm-1 (Figure 4a) can be attributed to the stretching associated
with the presence of quinone. A broad band centered around 1260 cm-1 is associated with C-O stretching
in ethers, lactones, phenols and carboxylic anhydrides. Bands characteristic for aromatic carboxylic group
is located below 1000 cm-1 (not shown in Figure 4) [22]. In the range 1000-400 cm-1 there can be observed
strong (475 and 459 cm-1), medium strong (551, 522 and 498 cm-1), medium (977, 932 and 902 cm-1),
medium-weak (742 and 688 cm-1) stretching which can be attributed to the presence of the aromatic
carboxyls on the surface of examined sample.
Figure 4. FT-IR/PAS spectra of the examined samples: a) sample 2, b) sample 3, c) sample 4.
Sample 3 oxidized with air contains the highest amount of oxygen (Table 2). TPD experiments (Figure 1)
and recorded spectrum (Figure 4b) suggest the presence of lactones, anhydrides, phenols, ethers and
quinones. A strong, well resolved band with a maximum located at 1611 cm-1 can be attributed to the
presence of the large amount of compounds contained carbonyl groups.
62 JOURNAL DE PHYSIQUE IV
In the case of Sample 4 (Figure 4c) band located at 1590 cm-1 suggest the presence and the dominating
effect of the quinones. This statement is supported by the relative intensity of the bands located at 1590
and 1243 cm-1. The first one is more intensive than the second, and is in the range of stretching vibrations
characteristic for quinones. Band at 1243 cm-1 is associated with C-O stretching, which is characteristic for
different groups contained oxygen.
4. CONCLUSIONS
Based on the results obtained the following conclusions can be drawn:
• wet activation of the studied samples creates surface species contained oxygen mostly in the form
of carboxyls,
• dry activation predominantly create species contained oxygen in stable form (their decomposition in
TPD experiments proceeds at higher temperatures in comparison to those formed during wet
activation),
• FT-IR/PAS spectrum of the wet activated sample is characterized by the presence mostly carboxyls
on its surface,
• spectra of the dry activated samples suggest the presence C-O stretching vibrations which nature is
predominantly characteristic for oxygen containing surface groups, others than carboxyls, and
• interpretation of the recorded PA spectra is strongly supported by the TPD experiments.
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