Journal of Colloid and Interface Science 333 (2009) 97–103

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Journal of Colloid and Interface Science
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The effects of urea modification 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-modified and heat-treated wood-based activated carbons was studied. From
the obtained results it was found that these modifications, 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 significant 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 fires
and explosives combines nitrogen and oxygen from air. Thus, military personnel could easily be exposed to high concentrations of
NO2 in battlefield situations. Civilians could also be exposed as a
result of terrorist bombings or if trapped in a fire. 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 [2–15]. Although, a selective catalytic reduction (SCR) process has been
widely applied in the denitrification of flue 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 modification 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 modification 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 modified with urea and heat-treated at two
different temperatures, 450 ◦ C and 950 ◦ C. These kinds of modifications introduce nitrogen into the carbon matrix. Thus, it is believed
that amides, protonated amides, aromatic amines and pyridine-Noxides dominate at low temperature (400–700 ◦ 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-modified 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.

The tests were conducted until the concentrations of NO2 and NO reached the electrochemical sensors’ upper limit values of 20 ppm and 200 ppm.1% of NO2 was passed through the column of adsorbent. pK a ) f (pK a ) dpK a . Automatic titrator (Metrohm. ∞ Q (pH) = −∞ q(pH. Heat treatment (at 10 ◦ C/min) to 950 ◦ C was also applied to the initial BAX-1500 carbon and the product was designated “B950”. 1A suggests the higher NO2 adsorption on the nitrogen-containing carbons than on the carbons without modifications. and then measuring the pH of this suspension. 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). BU450. Evaluation of NO2 sorption capacity Evaluation of NO2 sorption capacity was conducted in a laboratory-scale. This behavior of BU950 could be explained by the high amount of quaternary nitrogen groups (29%) found by XPS for this carbon sample [21]. Methods 2. Characterization of carbon surface chemistry The surface chemical properties were evaluated using potentiometric titration procedure [20]. The experiments were conducted at room temperature and atmospheric pressure with a total gas flow rate of 0. suggesting a slow release of NO2 species weakly adsorbed in the carbon pore system. Carbon samples (1–2 mm particle size) were loaded into the glass column. mesopore volume (V mes ). 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. In the desorption runs (when NO2 gas was turned off).19) with hydrochloric acid (0. representing the total amount of deprotonated sites.2. The breakthrough of NO2 and the concentration of NO were monitored using multiple gas monitor with electrochemical sensors (RAE Systems. The trend in NO2 breakthrough curves in Fig. 370 mm long by 9 mm diameter. containing 50 ml of 0.16]. The Fourier transform infrared spectroscopy (FTIR) procedure was carried out on a spectrometer (Thermo Electron Corporation. (1) where q(pH. Although an immediate emission of NO was found for the carbons run in a dry air.1 M) until its pH reached about 10. T. to NO3 . Materials A wood-based activated carbon BAX-1500 (MeadWestvaco Corporation) was used in this study. The spectrum was collected 96 times and corrected for the background noise.2. − O–N=N–O− [23]. The latter species are likely to be formed inside the narrow micropores. MultiRAE Plus PGM-50/5P). 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.98 S.3. The equilibrated carbon suspension was then acidified (pH  3. These species are also highly reactive and could easily oxidize the carbon surface and facilitate the formation of N2 by the existing N–N bond [15]. The nitrogen-modified carbons were designated “BU450” and “BU950”. 2. and BU950 carbons are presented in Fig. which proves the reduction of NO2 to NO by the carbon matrix [3. The solution to this equation was obtained using the SAIEUS numerical procedure [20] and gave the spectrum of acidity constants for the sample. 2. Among the investigated carbon samples.8]. Downward gas and air flow rates were controlled by flow meters (Cole Palmer). For BU950. . Emmet and Teller (BET) model [18]. The experimental data was transformed into a protonbinding isotherm. and equilibrated overnight. Experimental 2. The lack of physically adsorbed NO2 during the first 30 min of the adsorption run could be attributed to its immediate reduction to NO [3]. Bashkova. A dry air (“DA”) or moist air (≈70%) (“MA”) with 0.2. formed from the adsorption of O2 on the positively charged nitrogen centers [15.1.1 g) was placed in a thermostatted (at 298 K) container. 2.01 M solution of sodium nitrate. The extra π -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.4. An almost immediate release of NO was noticed for all the carbons. The samples were ground and mixed with potassium bromide. fixed-bed reactor system. 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. where they are directly affected by the adsorption filed of the pore walls on both sides. Nicolet 380) using a smart diffuse reflectance mode. 3. micropore volume (V mic ). and volume of pores less than 1 nm (V <1 nm ) were calculated using the density functional theory approach (DFT) [19]. The treated carbon samples were washed with water to remove urea decomposition products and dried. The specific surface area (S BET ) was calculated from the isotherm data using the Brunauer.2. indicating a strong retention of NO2 on the surface. Carbon sample (0. The suspension was titrated with a standardized NaOH (0.1. The surface chemistry of the carbons was also analyzed by thermo-gravimetric analysis (TGA) using TA Instruments thermal analyzer (SDT 2960) with a nitrogen flow rate of 100 cm3 /min and a heating rate of 10 ◦ C/min. f (pK a ).J.01 N). The carbon was modified to introduce nitrogen into its structure.45 L/min. 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 donor–acceptor properties in a carbon matrix [22]. respectively. pK a ) is a fraction of the deprotonated sites having a certain pK a at a certain pH. Bandosz / Journal of Colloid and Interface Science 333 (2009) 97–103 2. The pH of the adsorbent surface was obtained by mixing a sample of a carbon (0. Results and discussion The outlet concentration curves of NO2 and NO for B. A 5 g sample was impregnated with urea by stirring it with a saturated aqueous solution of urea (30 ml) for 5 h. Total pore volume (V tot ). but stabilized later.2. the time spent to reach the concentration of 200 ppm was considerably longer in a dry air than in a moist air. 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. NO2 was released from the carbon surface only after about 30 min of adsorption.4 g) with distilled water (20 ml). The samples were outgassed at 120 ◦ C to a constant vacuum (10−4 Torr) immediately prior to the isotherm measurements. the outlet NO2 concentration decreased fast in the beginning. 1. This likely indicates the participation of quaternary nitrogen in the process of NO2 adsorption. stirring the suspension overnight to equilibrate. The surface chemistry was assessed assuming that the population of surface sites is described by continuous pK a distribution. such that the volume of the carbon bed was about 2 cm3 (measured in a graduated cylinder). BU950 exhibited the best performance for retention of NO. B950. Q . The initial sample was designated “B”. DMS Titrino 716) was first set to collect the equilibrium pH of the sample. During the titration the suspension was continuously stirred and purged with nitrogen gas.

and the positive effect of active carbon centers on B950 in the adsorption of NO2 from a moist air. 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 filling of the pores with the products of NO2 adsorption. and BU950 of: (A) NO2 in dry air. 1. (4) –C(O) + HNO2 → –C–O–NO + OH− . B950. The outlet concentration curves of NO2 in a moist air have rather complex shapes (Fig. along with the large amount of NO formed (from the oxidation of carbon and the decomposition of HNO2 intermediate [2. (B) NO in dry air.S. Bandosz / Journal of Colloid and Interface Science 333 (2009) 97–103 99 Fig. (3) –C(O) + HNO3 → –C–O–NO2 + OH− . The formation of –NO3 is enhanced by the presence of water. the outlet concentration of NO for all the carbons run in a moist air reached its maximum of 200 ppm within the first 8 min of adsorption (Fig. (5) where –C∗ is the carbon active site. are lower for the modified carbons than for the initial B carbon. BU450.J. Furthermore. In fact. The pH values along with NO2 breakthrough capacities of the activated carbons before and after the adsorption of NO2 are sum- . Therefore. Bashkova. The outlet concentrations as a function of time for B. (C) NO2 in moist air and (D) NO in moist air. T. It is also interesting that the outlet concentrations of NO2 .7]). fitting the N 1s core level spectra to BAX carbon oxidized with HNO3 [21].7]. On the other hand. The nitric acid will then dissociate to form NO− 3. 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. 1C). A decrease in the outlet concentration of NO2 after about 100–150 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.6. the nitrogen-containing groups will likely be oxidized by HNO2 /HNO3 intermediates and will no longer be available for the adsorption of NO. at the point where they decrease after the initial increase. resulted in a fast release of NO. which enhance the overall carbon oxidation rate [6. As to BAX carbon. The process of NO2 adsorption/reduction is more complex in a moist air. both NO2 and NO3 species were found by XPS. Besides. its stabilization in concentration of NO2 could likely be explained by the oxidation of carbon surface by HNO2 / HNO3 intermediates and the formation of –O–NO2 and –O–NO complexes. it was found by Mochida and coworkers [5] that the air of high humidity (80%) reduces the adsorption of NO. Water has a catalytic effect on the oxidation of carbon. This proves the positive effect of quaternary nitrogen on BU450 and BU950. it is likely that the presence of moisture. 1D). –C∗ + HNO3 → –C(O) + HNO2 . 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. In fact.

which were found to increase the adsorption of NO on the activated carbons and activated carbon fibers [23].2/2. From these data.28].04 0.53 marized in Table 1. the heterogeneity of B carbon heated at 450 ◦ C is higher than the heterogeneity of its high-temperature-treated counterpart.28].51 0.0/1.0/2.80 0. after the adsorption of NO2 from a moist air.9 7.100 S. However.0/1.52 BU450 BU450DA BU450MA 1835 1653 1389 1. NO2 .19 0. It is apparent from Fig. When moisture is present in the system.73 0.23 0.81 0. The structural parameters of activated carbons in terms of the surface area.4 with the lower values received in a moist air.53 B950 B950DA B950MA 1591 1528 1364 0.9 7.50 0. The heat treatment at 950◦ significantly reduced the above-mentioned bands. Bandosz / Journal of Colloid and Interface Science 333 (2009) 97–103 Table 1 NO2 breakthrough capacities and surface pH values for the carbon samples. Nevertheless. After the adsorption of NO2 . NH ) could be found in a pK a range of 9 to 10 [26]. In fact. the intensities of the peaks increased.13 0. This interesting behavior is most likely the result of oxidation of the carbon surface by HNO2 /HNO3 . and NO2 adsorption on B carbon are seen in the FTIR spectra (Fig.J. ketoester.27.41 0.49 0. and micropore volume of the carbons decreased after the heat treatment and urea modification. This is likely due to the fact. Sample pHin a /pHE b NO2 breakthrough capacity (mg/g) BDA B950DA BMA B950MA BU450DA BU450MA BU950DA BU950MA 6. These low pH values are likely the result of oxidation of the carbon surface by HNO3 and the formation of acidic nitrogen oxides. the active sites are likely to be covered by water [5] and/or oxidized by the products of NO2 adsorption.27. thermal modifications.9 7. In fact.2/1. On the contrary.28]. the intensities of these peaks decreased.41 0.19 0.0/2.25]. after the heat treatment of this carbon. More so. Analyzing the performance of these carbons for the adsorption of NO2 in a dry air. The reaction of oxygen-containing groups with urea followed by the heat treatment at 450 ◦ C decreased the band at 1714 cm−1 but increased the band at 1600 cm−1 . The effects of urea impregnation. On the other hand.52 0.39 0. However.44 0.13 0. 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.27. The pH values of the carbons after the adsorption of NO2 were between 1.58 0.3 6.15 0.28].81 0. The broad band from about 1300 cm−1 to about 1000 cm−1 is probably due to C–O–C lactone structures.41 0.35 0.4 7.74 0. More so. Furthermore. 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 [5.6 7. some contribution from the supermicropores.12 0. the retention of NO significantly increased.19 0.38 0. The band at 1250 cm−1 is possibly due to C–N stretching vibrations incorporated into the carbon structure [16. two carbons were chosen for comparison. Thus.43 0. and was assigned to the asymmetric .2 7. having both carboxylic groups (pK a < 8) and phenolic groups (pK a > 8) on its surface [26]. no longer be involved in the adsorption of NO. and therefore.35 0. pore volumes.73 0. especially for B and BU450.41 0. 3).19 0. that prior to the nitrogen adsorption. the urea treatment introduced nitrogen-containing functionalities to the carbon sur+ face. The band at about 1600 cm−1 is likely the combination of C=C stretching vibration of the aromatic ring structures (1590 cm−1 ) and conjugated systems such as diketone. 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.28]. 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. HNO2 and HNO3 were likely desorbed from the surface.0/1. 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.50 0.39 0. one major absorption band at 1385 cm−1 was found for all the carbons. which could be related to the abundance of nitrogencontaining functionalities on the former one. where the number of peaks for each sample is related to the degree of its surface heterogeneity. NO3 .49 0. B carbon is quite heterogeneous. pore volume distribution and relative microporosity (V mic / V tot ) are presented in Table 2. quinone (1550–1680 cm−1 ) and carboxylate structures (1380 cm−1 ) [16. some decrease in the capacity of NO2 upon the heat treatment was found.41 0.8 35 23 71 93 45 135 66 140 a b pH of the initial carbons (before the NO2 adsorption). and mean pore width of activated carbons examined.84 0. Putting aside a role of nitrogen and a possible contribution of a mineral matter (the ash content of BAX is about 3%).40 0.77 0. The peak at 1714 cm−1 corresponds to the carboxyl C=O stretching of non-aromatic carboxylic acid or lactone structures [16. after the adsorption of NO2 .6 and 2. which now could be associated with the pyridinic or amide structures [16. is also possible. stretching C–O vibrations of phenol structures and ethers and bending O–H modes of phenol structures [16. no significant changes were noticed.40 0.28].87 0. This behavior is similar to the urea-modified carbons and is likely related to the oxidation of NO2 to NO3 and the retention of the latter species on carbon active centers. Such band was also reported by Shirahama and coworkers in the case of NO2 adsorption on the activated carbon fibers.42 0. with the highest capacity found for BU950. pH of the exhausted carbons (after the NO2 adsorption).42 0. 2 in terms of the pK a distributions.46 0.93 0.51 BU950 BU950DA BU950MA 1533 1477 1402 0. it is seen that the surface area. some increase in the volume of supermicropores (V <1 nm ) [24] was noticed for the high temperature treated carbons. total pore volume. 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 . However. the carbon samples were heated in the oven at 100 ◦ C and then outgassed at 120 ◦ C to a constant vacuum (10−4 Torr).44 0. 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.39 0.15 0.38 0. The band at 1600 cm−1 for B950 could now be assigned to the quinone and/or ion-radical structures [16. some decrease in the volumes of total pores and an increase in the relative microporosity after the adsorption of NO2 .19 0.27. 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]. especially in a moist air. Table 2 Surface area. this process is enhanced when the active centers are located inside the pores and will proceed until all of the pores are filled with the products of NO2 adsorption. a moist air has a positive effect on NO2 breakthrough capacity of B950. The surface chemistry of the carbons is presented in Fig. Obviously.44 0. during which the water and weakly adsorbed NO.35 0.49 0.75 0. Bashkova. some of which (NH+ 2 . could be due to the oxidation of carbons and formation of the new surface groups mainly within the mesopores.18 0.40 0.15 0. T.0/1. B and B950.

and B950 carbons before and after the adsorption of NO2 from dry and moist air. Bashkova. Bandosz / Journal of Colloid and Interface Science 333 (2009) 97–103 Fig. Fig. BU950. 101 . B950 and BU950 carbons before and after the adsorption of NO2 from dry and moist air. The pK a distributions of B. BU450. 3.J. 2. T.S. The FTIR spectra of B. BU450.

2 41.2 40. Bandosz / Journal of Colloid and Interface Science 333 (2009) 97–103 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. T. –C(ONO2 ) complexes. However.102 S. Interestingly enough.29]. The . 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. and B950 carbons before and after the adsorption of NO2 from dry and moist air. Summary Fig. The NO2 adsorption on the carbon surface is further enhanced by the presence of moisture. BU450. ether.4 5 . O2 and HNO3 . A final increase in the concentration of NO2 is related again to the physisorption/desorption of NO2 .6 7. Bashkova.0 13. After the adsorption of NO2 from a dry air the first peak on the DTG curves in Fig. formed by the oxidation of carbon surface with HNO3 .J. stretching vibration of NO3 [4]. 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. The appearance of two other bands at 1350 cm−1 and 1540 cm−1 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]. The DTG curve of the initial B carbon reveals three peaks at 80 ◦ C. are completely oxidized. 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.3 13. The high temperature peak of B950 could be attributed to the release of C=O groups of the conjugated ketone or quinone structures [28]. 700 ◦ C and 900 ◦ C. 4) obtained from the thermal analysis runs in nitrogen. An initial increase in the concentration of NO2 is due to its physisorption/desorption.5 14.0 3 . the good balance was observed only for B and BU450 after the adsorption of NO2 from a dry air (Table 3). which happens when carbon/nitrogen active centers. pyridone or pyridinic nitrogen as a molecular nitrogen or HCN [17. which is retained on the surface for quite a long time in the presence of active nitrogen or other carbon active sites. both of the latter peaks were also identified by FTIR on BAX carbon oxidized with HNO3 [21]. 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. The first peak (at about 80 ◦ C) is common for all carbon samples and is related to the removal of water [2. The same peak may also represent the removal of HNO3 for the adsorption of NO2 from a moist air. 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 DTG curves in N2 of B.8 3 .3 4. The surface chemistry of activated carbons studied was also analyzed based on the differential thermogravimetric (DTG) curves (Fig.1 9. The complex shapes of breakthrough curves in a moist air are related to the various processes.25]. 4 represents the removal of water and physically adsorbed NO2 and NO [2]. Peaks at about 700 ◦ C and 900 ◦ C could correspond to the evolution of It was found that the modification of activated carbons with urea followed by their consecutive heat treatment. The appearance of another band at 830 cm−1 along with an increase in the intensities of the bands at 1640 and 1260 cm−1 are commonly attributed to organic nitrates (R–O–NO2 ) [10. The adsorbed NO2 is also readily reduced to NO. It is clear that in such cases a variety of products is present on the surface of carbons as a result of NO2 adsorption.0 45. an appearance of the new peaks in a 200–500 ◦ C temperature range for the carbons run in a moist air may correspond to the decomposition of carboxylic groups. and quinone functional groups [28]. H2 O.30]. BU950. has a positive effect on the removal of NO2 . and all the pores with these centers are filled with the products of NO2 adsorption. Furthermore.5 6. Sample %NO2 breakthrough %Weight loss (30–200 ◦ C) TA BDA B950DA BU450DA BU950DA BMA B950MA BU450MA BU950MA 3. carboxylic anhydrides and/or lactone groups [28]. carbonyl.0 CO attributed to the decomposition of phenol.5 2. 4. 4. The most likely species to be present on the surface are –NO3 .0 45. involved in the reactions with HNO3 . For these carbons it is likely that NO2 is weakly adsorbed on the surface and is desorbed as NO2 upon heating. especially at a high temperature (950 ◦ C).

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