Journal of Colloid and Interface Science 333 (2009) 97103

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Journal of Colloid and Interface Science

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The effects of urea modication and heat treatment on the process of NO2
removal by wood-based activated carbon
Svetlana Bashkova, Teresa J. Bandosz
Department of Chemistry, The City College of New York, 160 Convent Avenue, New York, NY 10031, USA

a r t i c l e

i n f o

a b s t r a c t

Article history:
Received 17 November 2008
Accepted 26 January 2009
Available online 29 January 2009
Keywords:
Urea
Activated carbon
Nitrogen
Heat treatment
NO2 adsorption
NO

The removal of NO2 on urea-modied and heat-treated wood-based activated carbons was studied. From
the obtained results it was found that these modications, especially when done at 950 C, have a positive
effect on NO2 adsorption and on the retention of NO (the product of NO2 reduction by carbon). The
presence of moisture in the system enhances the removal of NO2 but negatively affects the retention
of NO. It is possible that the formation of active centers on the carbon surface and some increase in
the volume of supermicropores during the high temperature treatment play a signicant role in these
removal processes. The surface of the carbons was analyzed in terms of the pK a distributions. The
qualitative and quantitative analyses of the NO2 adsorption products were carried out by means of FTIR
and TA techniques, respectively. The main products found on the carbon surface were the NO3 and NO2
species.
2009 Elsevier Inc. All rights reserved.

1. Introduction
The two most prevalent oxides of nitrogen are nitrogen dioxide (NO2 ) and nitric oxide (NO). Nitrogen oxide emissions contribute to the formation of smog, acid rain, and particulate matter
through chemical reactions in the atmosphere [1]. Although NO is
a main component released into the atmosphere from the combustion of fossil fuels, it is easily converted to the more harmful
NO2 . The latter one could also form when the heat from res
and explosives combines nitrogen and oxygen from air. Thus, military personnel could easily be exposed to high concentrations of
NO2 in battleeld situations. Civilians could also be exposed as a
result of terrorist bombings or if trapped in a re. Long-term exposure to NO2 causes adverse health effects. Government industrial
health regulations limit workplace exposures to 5 parts per million
(ppm).
Therefore, the removal of NOx is extremely important and has
been a subject of interest of many research groups [215]. Although, a selective catalytic reduction (SCR) process has been
widely applied in the denitrication of ue gases [10,11], it has
disadvantages, which include high reaction temperature and unreacted reductants such as ammonia and hydrocarbons. As an effective alternative to SCR, activated carbons have been used. Recently,
Grzybek et al. [12] showed that modication of active carbon with
N-precursors such as gaseous ammonia (at high temperature) and
aqueous solution of urea (followed by curing in air or nitrogen at

Corresponding author. Fax: +1 212 650 6107.

E-mail address: tbandosz@ccny.cuny.edu (T.J. Bandosz).

0021-9797/$ see front matter

doi:10.1016/j.jcis.2009.01.052

2009 Elsevier Inc. All rights reserved.

350 C) led to an increase in NO conversion and selectivity to N2 .

More so, these authors showed that the modication with urea,
followed by curing in air or nitrogen resulted in much better NO
conversion and selectivity to N2 than that of the samples after the
high temperature ammonia treatment. Additionally it was shown
that NO conversion decreased when the temperature of the process was higher than 220 C. Shirahama et al. [13,14] used urea
supported on activated carbons for the reduction of NOx in air at
ambient conditions. They found that urea supported on activated
carbon effectively reduced both NO2 and NO to N2 and the reduction continued until the complete consumption of urea. In the case
of NO2 adsorption, humidity was found to extend the removal process by the formation of HNO3 over the activated carbon. Matzner
and Boehm [15] found that the amount of NO adsorbed at room
temperature increased with an increase in the nitrogen content of
activated carbon.
In the current work the removal process of NO2 is carried on
the activated carbons modied with urea and heat-treated at two
different temperatures, 450 C and 950 C. These kinds of modications introduce nitrogen into the carbon matrix. Thus, it is believed
that amides, protonated amides, aromatic amines and pyridine-Noxides dominate at low temperature (400700 C), while pyridines,
pyrroles, aromatic amines, quaternary nitrogen, and protonated
pyridines dominate at higher temperatures (>700 C) [16,17]. The
objective of this work is to study the adsorption/reduction of NO2
on the urea-modied activated carbons under the ambient conditions and to investigate the effect of nitrogen-containing groups
and heat treatment on the adsorption of NO2 and on the retention
of NO.

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S. Bashkova, T.J. Bandosz / Journal of Colloid and Interface Science 333 (2009) 97103

2. Experimental
2.1. Materials
A wood-based activated carbon BAX-1500 (MeadWestvaco Corporation) was used in this study. The initial sample was designated
B. The carbon was modied to introduce nitrogen into its structure. A 5 g sample was impregnated with urea by stirring it with a
saturated aqueous solution of urea (30 ml) for 5 h. Then it was
heated in nitrogen by raising its temperature (at 10 C/min) to
450 C and 950 C and holding it at these temperatures for 1 h.
The treated carbon samples were washed with water to remove
urea decomposition products and dried. The nitrogen-modied carbons were designated BU450 and BU950. Heat treatment (at
10 C/min) to 950 C was also applied to the initial BAX-1500 carbon and the product was designated B950.
2.2. Methods
2.2.1. Evaluation of NO2 sorption capacity
Evaluation of NO2 sorption capacity was conducted in a laboratory-scale, xed-bed reactor system. Carbon samples (12 mm
particle size) were loaded into the glass column, 370 mm long
by 9 mm diameter, such that the volume of the carbon bed was
about 2 cm3 (measured in a graduated cylinder). A dry air (DA)
or moist air (70%) (MA) with 0.1% of NO2 was passed through
the column of adsorbent. Downward gas and air ow rates were
controlled by ow meters (Cole Palmer). The breakthrough of NO2
and the concentration of NO were monitored using multiple gas
monitor with electrochemical sensors (RAE Systems, MultiRAE Plus
PGM-50/5P). The tests were conducted until the concentrations of
NO2 and NO reached the electrochemical sensors upper limit values of 20 ppm and 200 ppm, respectively. The experiments were
conducted at room temperature and atmospheric pressure with a
total gas ow rate of 0.45 L/min.
2.2.2. Surface area and pore size distribution measurements
The nitrogen adsorption isotherms on the carbon samples
were determined at 196 C using an ASAP 2010 instrument (Micromeritics). The samples were outgassed at 120 C to a constant
vacuum (104 Torr) immediately prior to the isotherm measurements. The specic surface area (S BET ) was calculated from the
isotherm data using the Brunauer, Emmet and Teller (BET) model
[18]. Total pore volume (V tot ), micropore volume (V mic ), mesopore
volume (V mes ), and volume of pores less than 1 nm (V <1 nm ) were
calculated using the density functional theory approach (DFT) [19].
2.2.3. Characterization of carbon surface chemistry
The surface chemical properties were evaluated using potentiometric titration procedure [20]. Automatic titrator (Metrohm,
DMS Titrino 716) was rst set to collect the equilibrium pH of
the sample. Carbon sample (0.1 g) was placed in a thermostatted (at 298 K) container, containing 50 ml of 0.01 M solution of
sodium nitrate, and equilibrated overnight. The equilibrated carbon
suspension was then acidied (pH  3.19) with hydrochloric acid
(0.01 N). The suspension was titrated with a standardized NaOH
(0.1 M) until its pH reached about 10. During the titration the suspension was continuously stirred and purged with nitrogen gas.
The surface chemistry was assessed assuming that the population of surface sites is described by continuous pK a distribution,
f (pK a ). The experimental data was transformed into a protonbinding isotherm, Q , representing the total amount of deprotonated sites.


Q (pH) =

q(pH, pK a ) f (pK a ) dpK a ,

(1)

where q(pH, pK a ) is a fraction of the deprotonated sites having a

certain pK a at a certain pH.
The solution to this equation was obtained using the SAIEUS
numerical procedure [20] and gave the spectrum of acidity constants for the sample.
The pH of the adsorbent surface was obtained by mixing a sample of a carbon (0.4 g) with distilled water (20 ml), stirring the
suspension overnight to equilibrate, and then measuring the pH of
this suspension.
The Fourier transform infrared spectroscopy (FTIR) procedure
was carried out on a spectrometer (Thermo Electron Corporation,
Nicolet 380) using a smart diffuse reectance mode. The samples
were ground and mixed with potassium bromide. The spectrum
was collected 96 times and corrected for the background noise.
The surface chemistry of the carbons was also analyzed by
thermo-gravimetric analysis (TGA) using TA Instruments thermal
analyzer (SDT 2960) with a nitrogen ow rate of 100 cm3 /min
and a heating rate of 10 C/min.
3. Results and discussion
The outlet concentration curves of NO2 and NO for B, B950,
BU450, and BU950 carbons are presented in Fig. 1. An almost
immediate release of NO was noticed for all the carbons, which
proves the reduction of NO2 to NO by the carbon matrix [3,4,8].
Although an immediate emission of NO was found for the carbons run in a dry air, the time spent to reach the concentration of
200 ppm was considerably longer in a dry air than in a moist air.
Among the investigated carbon samples, BU950 exhibited the best
performance for retention of NO. This behavior of BU950 could
be explained by the high amount of quaternary nitrogen groups
(29%) found by XPS for this carbon sample [21]. These nitrogen
groups in combination with the pyrrole nitrogen groups (26% for
BU950 [21]) were found to have the highest charge mobility and
the best donoracceptor properties in a carbon matrix [22]. The
extra -electrons of quaternary nitrogen could be transferred from
the higher energy states to the adsorbed NO molecules and lead
to the formation of dimeric hyponitrite ions, ON=NO [23].
The latter species are likely to be formed inside the narrow micropores, where they are directly affected by the adsorption led of
the pore walls on both sides. These species are also highly reactive
and could easily oxidize the carbon surface and facilitate the formation of N2 by the existing NN bond [15]. The smaller amount
of quaternary nitrogen found for the carbons heat-treated at about
500 C [17] is likely to be responsible for the shorter retention of
NO on BU450.
The introduction of nitrogen into B carbon by the urea impregnation and heat treatment could also be responsible for the improved performance of this carbon in the adsorption of NO2 from
a dry air. For BU950, NO2 was released from the carbon surface
only after about 30 min of adsorption. The lack of physically adsorbed NO2 during the rst 30 min of the adsorption run could be
attributed to its immediate reduction to NO [3]. The trend in NO2
breakthrough curves in Fig. 1A suggests the higher NO2 adsorption
on the nitrogen-containing carbons than on the carbons without
modications. This likely indicates the participation of quaternary
nitrogen in the process of NO2 adsorption, where NO2 and NO are
adsorbed on the positively-charged nitrogen centers and can further be reduced to N2 or oxidized by oxygen or superoxide ions,
formed from the adsorption of O2 on the positively charged nitrogen centers [15,16], to NO3 .
In the desorption runs (when NO2 gas was turned off), the
outlet NO2 concentration decreased fast in the beginning, indicating a strong retention of NO2 on the surface, but stabilized later,
suggesting a slow release of NO2 species weakly adsorbed in the
carbon pore system.

S. Bashkova, T.J. Bandosz / Journal of Colloid and Interface Science 333 (2009) 97103

99

Fig. 1. The outlet concentrations as a function of time for B, B950, BU450, and BU950 of: (A) NO2 in dry air, (B) NO in dry air, (C) NO2 in moist air and (D) NO in moist air.

The process of NO2 adsorption/reduction is more complex in

a moist air. Water has a catalytic effect on the oxidation of carbon, which is generally attributed to the reaction of NO2 and H2 O
leading to the formation of some amounts of nitric (HNO3 ) and
nitrous (HNO2 ) acids, which enhance the overall carbon oxidation
rate [6,7].
On the other hand, it was found by Mochida and coworkers
[5] that the air of high humidity (80%) reduces the adsorption of
NO. Therefore, it is likely that the presence of moisture, along with
the large amount of NO formed (from the oxidation of carbon and
the decomposition of HNO2 intermediate [2,6,7]), resulted in a fast
release of NO. Besides, the nitrogen-containing groups will likely
be oxidized by HNO2 /HNO3 intermediates and will no longer be
available for the adsorption of NO. In fact, the outlet concentration
of NO for all the carbons run in a moist air reached its maximum
of 200 ppm within the rst 8 min of adsorption (Fig. 1D).
The outlet concentration curves of NO2 in a moist air have
rather complex shapes (Fig. 1C). A decrease in the outlet concentration of NO2 after about 100150 min of NO2 adsorption can
be related to the oxidation of NO2 to NO3 and the adsorption of
the latter species on the positively-charged nitrogen centers. The
formation of NO3 is enhanced by the presence of water, which
facilitates the formation of HNO3 via the decomposition of nitrous
acid:
3HNO2 HNO3 + 2NO + H2 O

(2)

or by oxidation of NO2 with the active OH radicals. The nitric acid

will then dissociate to form NO
3.
As to BAX carbon, its stabilization in concentration of NO2 could
likely be explained by the oxidation of carbon surface by HNO2 /
HNO3 intermediates and the formation of ONO2 and ONO
complexes.
C + HNO3 C(O) + HNO2 ,

(3)

C(O) + HNO3 CONO2 + OH ,

(4)

C(O) + HNO2 CONO + OH ,

(5)

where C is the carbon active site.

In fact, both NO2 and NO3 species were found by XPS, tting
the N 1s core level spectra to BAX carbon oxidized with HNO3
[21]. Furthermore, an increase in the concentration of NO2 after
about 300 min of NO2 adsorption could be associated with the
complete oxidation of the carbon active centers involved in the reactions with HNO3 and the lling of the pores with the products
of NO2 adsorption. It is also interesting that the outlet concentrations of NO2 , at the point where they decrease after the initial
increase, are lower for the modied carbons than for the initial B
carbon. This proves the positive effect of quaternary nitrogen on
BU450 and BU950, and the positive effect of active carbon centers
on B950 in the adsorption of NO2 from a moist air.
The pH values along with NO2 breakthrough capacities of the
activated carbons before and after the adsorption of NO2 are sum-

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S. Bashkova, T.J. Bandosz / Journal of Colloid and Interface Science 333 (2009) 97103

Table 1
NO2 breakthrough capacities and surface pH values for the carbon samples.
Sample

pHin a /pHE b

NO2 breakthrough capacity

(mg/g)

BDA
B950DA
BMA
B950MA
BU450DA
BU450MA
BU950DA
BU950MA

6.0/2.4
7.2/2.3
6.0/1.9
7.2/1.6
7.0/2.2
7.0/1.9
7.0/1.9
7.0/1.8

35
23
71
93
45
135
66
140

a
b

pH of the initial carbons (before the NO2 adsorption).

pH of the exhausted carbons (after the NO2 adsorption).

Table 2
Surface area, pore volumes, and mean pore width of activated carbons examined.
Sample

S BET
(m2 /g)

V tot
(cm3 /g)

V mic
(cm3 /g)

V mes
(cm3 /g)

V <1 nm
(cm3 /g)

V mic / V tot

B
BDA
BMA

2116
1593
1385

1.23
0.87
0.74

0.50
0.44
0.39

0.73
0.43
0.35

0.12
0.15
0.15

0.41
0.51
0.53

B950
B950DA
B950MA

1591
1528
1364

0.84
0.81
0.73

0.42
0.40
0.38

0.42
0.41
0.35

0.19
0.18
0.19

0.50
0.49
0.52

BU450
BU450DA
BU450MA

1835
1653
1389

1.04
0.93
0.77

0.46
0.41
0.39

0.58
0.52
0.38

0.13
0.13
0.15

0.44
0.44
0.51

BU950
BU950DA
BU950MA

1533
1477
1402

0.81
0.80
0.75

0.40
0.39
0.40

0.41
0.41
0.35

0.19
0.19
0.19

0.49
0.49
0.53

marized in Table 1. It is apparent from these data that NO2 breakthrough capacities of the carbons in a dry air were smaller than
the corresponding NO2 capacities in a moist air, with the highest
capacity found for BU950. The pH values of the carbons after the
adsorption of NO2 were between 1.6 and 2.4 with the lower values
received in a moist air. These low pH values are likely the result
of oxidation of the carbon surface by HNO3 and the formation of
acidic nitrogen oxides.
The structural parameters of activated carbons in terms of the
surface area, pore volume distribution and relative microporosity
(V mic / V tot ) are presented in Table 2. From these data, it is seen
that the surface area, total pore volume, and micropore volume of
the carbons decreased after the heat treatment and urea modication. Nevertheless, some increase in the volume of supermicropores (V <1 nm ) [24] was noticed for the high temperature treated
carbons. A decrease in the porosity of B carbon upon the high temperature treatment is due to the fact that the initial B carbon was
prepared at a low temperature.
Putting aside a role of nitrogen and a possible contribution of a
mineral matter (the ash content of BAX is about 3%), two carbons
were chosen for comparison, B and B950. Analyzing the performance of these carbons for the adsorption of NO2 in a dry air,
no signicant changes were noticed. In fact, some decrease in the
capacity of NO2 upon the heat treatment was found. On the contrary, the retention of NO signicantly increased. Such an increase
in the retention of NO upon the heat treatment could mostly be
related to the removal of oxygen functional groups and the formation of active sites on the carbon surface [5,25]. However, some
contribution from the supermicropores, which were found to increase the adsorption of NO on the activated carbons and activated
carbon bers [23], is also possible. When moisture is present in
the system, the active sites are likely to be covered by water [5]
and/or oxidized by the products of NO2 adsorption, and therefore,
no longer be involved in the adsorption of NO. On the other hand,

a moist air has a positive effect on NO2 breakthrough capacity of

B950. It is apparent from Fig. 1C that for this carbon the outlet
concentration of NO2 went down from about 18 ppm at 100 min of
adsorption to about 8 ppm at 300 min of adsorption. This behavior
is similar to the urea-modied carbons and is likely related to the
oxidation of NO2 to NO3 and the retention of the latter species on
carbon active centers. More so, this process is enhanced when the
active centers are located inside the pores and will proceed until all of the pores are lled with the products of NO2 adsorption.
From Table 2 it is observed that the volumes of pores for the heattreated carbons with or without nitrogen did not change much
after the adsorption of NO2 . This is likely due to the fact, that prior
to the nitrogen adsorption, the carbon samples were heated in the
oven at 100 C and then outgassed at 120 C to a constant vacuum
(104 Torr), during which the water and weakly adsorbed NO, NO2 ,
NO3 , HNO2 and HNO3 were likely desorbed from the surface. However, some decrease in the volumes of total pores and an increase
in the relative microporosity after the adsorption of NO2 , especially
for B and BU450, could be due to the oxidation of carbons and formation of the new surface groups mainly within the mesopores.
The surface chemistry of the carbons is presented in Fig. 2 in
terms of the pK a distributions, where the number of peaks for
each sample is related to the degree of its surface heterogeneity.
Obviously, B carbon is quite heterogeneous, having both carboxylic
groups (pK a < 8) and phenolic groups (pK a > 8) on its surface
[26]. However, after the heat treatment of this carbon, the intensities of these peaks decreased. More so, the urea treatment
introduced nitrogen-containing functionalities to the carbon sur+
face, some of which (NH+
2 , NH ) could be found in a pK a range of
9 to 10 [26]. Thus, the heterogeneity of B carbon heated at 450 C
is higher than the heterogeneity of its high-temperature-treated
counterpart, which could be related to the abundance of nitrogencontaining functionalities on the former one. Furthermore, after
the adsorption of NO2 , especially in a moist air, the intensities of
the peaks increased. This interesting behavior is most likely the
result of oxidation of the carbon surface by HNO2 /HNO3 . In fact,
after the adsorption of NO2 from a moist air, the pK a distribution
of B carbon looks very similar to the pK a distribution of the same
carbon after its oxidation with HNO3 [21].
The effects of urea impregnation, thermal modications, and
NO2 adsorption on B carbon are seen in the FTIR spectra (Fig. 3).
The peak at 1714 cm1 corresponds to the carboxyl C=O stretching
of non-aromatic carboxylic acid or lactone structures [16,27,28].
The band at about 1600 cm1 is likely the combination of C=C
stretching vibration of the aromatic ring structures (1590 cm1 )
and conjugated systems such as diketone, ketoester, quinone
(15501680 cm1 ) and carboxylate structures (1380 cm1 )
[16,27,28]. The broad band from about 1300 cm1 to about
1000 cm1 is probably due to COC lactone structures, stretching
CO vibrations of phenol structures and ethers and bending OH
modes of phenol structures [16,27,28]. An increase in the intensities of all these bands after the adsorption of NO2 came from the
oxidation of the carbon surface by the products of NO2 adsorption.
The reaction of oxygen-containing groups with urea followed
by the heat treatment at 450 C decreased the band at 1714 cm1
but increased the band at 1600 cm1 , which now could be associated with the pyridinic or amide structures [16,28]. The band at
1250 cm1 is possibly due to CN stretching vibrations incorporated into the carbon structure [16,27,28]. The heat treatment at
950 signicantly reduced the above-mentioned bands. The band
at 1600 cm1 for B950 could now be assigned to the quinone
and/or ion-radical structures [16,28].
After the adsorption of NO2 , one major absorption band at 1385
cm1 was found for all the carbons. Such band was also reported
by Shirahama and coworkers in the case of NO2 adsorption on
the activated carbon bers, and was assigned to the asymmetric

S. Bashkova, T.J. Bandosz / Journal of Colloid and Interface Science 333 (2009) 97103

Fig. 2. The pK a distributions of B, BU450, BU950, and B950 carbons before and after the adsorption of NO2 from dry and moist air.

Fig. 3. The FTIR spectra of B, BU450, B950 and BU950 carbons before and after the adsorption of NO2 from dry and moist air.

101

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S. Bashkova, T.J. Bandosz / Journal of Colloid and Interface Science 333 (2009) 97103

Table 3
The amount of NO2 adsorbed from breakthrough tests and the weight loss of activated carbons after the adsorption of NO2 from a thermal analysis.
Sample

%NO2
breakthrough

%Weight loss
(30200 C) TA

BDA
B950DA
BU450DA
BU950DA
BMA
B950MA
BU450MA
BU950MA

3.5
2.3
4.5
6.6
7.1
9.3
13.5
14.0

3 .8
3 .4
5 .0
13.0
45.2
40.2
41.0
45.0

CO attributed to the decomposition of phenol, ether, carbonyl, and

quinone functional groups [28].
The peaks in a temperature range of 500 to 1000 C for the activated carbons impregnated with urea could be related to the decomposition of pyrrolic, pyridone or pyridinic nitrogen as a molecular nitrogen or HCN [17,30]. The high temperature peak of B950
could be attributed to the release of C=O groups of the conjugated ketone or quinone structures [28]. After the adsorption of
NO2 from a dry air the rst peak on the DTG curves in Fig. 4
represents the removal of water and physically adsorbed NO2 and
NO [2]. The same peak may also represent the removal of HNO3
for the adsorption of NO2 from a moist air. Furthermore, an appearance of the new peaks in a 200500 C temperature range for
the carbons run in a moist air may correspond to the decomposition of carboxylic groups, carboxylic anhydrides and/or lactone
groups [28], formed by the oxidation of carbon surface with HNO3 .
When the comparison was done between the amount of NO2
adsorbed from breakthrough tests and the weight loss of carbons
after the adsorption NO2 from a thermal analysis, the good balance was observed only for B and BU450 after the adsorption of
NO2 from a dry air (Table 3). For these carbons it is likely that
NO2 is weakly adsorbed on the surface and is desorbed as NO2
upon heating. However, for BU950 run in a dry air and for all the
carbons run in a moist air the weight loss from TA is higher than
the percent of NO2 from breakthrough tests. It is clear that in such
cases a variety of products is present on the surface of carbons as
a result of NO2 adsorption. The most likely species to be present
on the surface are NO3 , C(ONO2 ) complexes, H2 O, O2 and HNO3 .
4. Summary

Fig. 4. The DTG curves in N2 of B, BU450, BU950, and B950 carbons before and after
the adsorption of NO2 from dry and moist air.

stretching vibration of NO3 [4]. The appearance of two other bands

at 1350 cm1 and 1540 cm1 for B and BU450 after the adsorption of NO2 from a moist air can be respectively ascribed to the
symmetric and asymmetric NO2 vibrations of NO2 [27]. Interestingly enough, both of the latter peaks were also identied by FTIR
on BAX carbon oxidized with HNO3 [21]. The appearance of another band at 830 cm1 along with an increase in the intensities
of the bands at 1640 and 1260 cm1 are commonly attributed to
organic nitrates (RONO2 ) [10,29].
The surface chemistry of activated carbons studied was also analyzed based on the differential thermogravimetric (DTG) curves
(Fig. 4) obtained from the thermal analysis runs in nitrogen. The
DTG curve of the initial B carbon reveals three peaks at 80 C,
700 C and 900 C. The rst peak (at about 80 C) is common for all
carbon samples and is related to the removal of water [2,25]. Peaks
at about 700 C and 900 C could correspond to the evolution of

It was found that the modication of activated carbons with

urea followed by their consecutive heat treatment, especially at a
high temperature (950 C), has a positive effect on the removal of
NO2 . In dry air tests the positively-charged nitrogen centers are
likely to be involved in an electron transfer mechanism of NO2
chemisorption and its further oxidation to NO3 by the superoxide
ions. The adsorbed NO2 is also readily reduced to NO, which is
retained on the surface for quite a long time in the presence of
active nitrogen or other carbon active sites.
The NO2 adsorption on the carbon surface is further enhanced
by the presence of moisture. The complex shapes of breakthrough
curves in a moist air are related to the various processes. An initial increase in the concentration of NO2 is due to its physisorption/desorption. A further decrease in the concentration of NO2 is
due to the moisture enhanced oxidation of NO2 to NO3 and the
retention of NO
3 on the positively-charged nitrogen centers or
other carbon active sites. A nal increase in the concentration of
NO2 is related again to the physisorption/desorption of NO2 , which
happens when carbon/nitrogen active centers, involved in the reactions with HNO3 , are completely oxidized, and all the pores with
these centers are lled with the products of NO2 adsorption. The

S. Bashkova, T.J. Bandosz / Journal of Colloid and Interface Science 333 (2009) 97103

oxidation of carbon surface is clearly observed from the pK a distributions. As a result of the oxidation, the carbon/nitrogen active
centers are no longer available for the adsorption of NO, which results in its early release from the carbon surface.
The variety of products was found on the surface of carbons

tested in a moist air. The FTIR spectra showed NO

3 and NO2 being the major adsorption species, accompanied by some amounts
of the nitrate complexes (RONO2 ). The comparison was done between the amounts of NO2 adsorbed from breakthrough tests and
the weight loss of carbons after the adsorption of NO2 . A good balance was only found for B and BU450 carbons run in a dry air.
Acknowledgment
This work was supported by ARO Grant W911NF-05-1-0537.
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