Accepted Manuscript

Comprehensive Study of Ultra-Microporous Nitrogen-Doped Activated Carbon

for CO2 Capture

Govind Sethia, Abdelhamid Sayari

PII: S0008-6223(15)00414-5
DOI: http://dx.doi.org/10.1016/j.carbon.2015.05.017
Reference: CARBON 9911

To appear in: Carbon

Received Date: 9 February 2015

Accepted Date: 6 May 2015

Please cite this article as: Sethia, G., Sayari, A., Comprehensive Study of Ultra-Microporous Nitrogen-Doped
Activated Carbon for CO2 Capture, Carbon (2015), doi: http://dx.doi.org/10.1016/j.carbon.2015.05.017

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 Comprehensive Study of Ultra-Microporous Nitrogen-Doped Activated

Carbon for CO2 Capture

Govind Sethiaa,b and Abdelhamid Sayari*,a

a
Department of Chemistry, Centre for Catalysis Research and Innovation (CCRI), University of

Ottawa, Ottawa, Ontario, K1N 6N5, Canada.

b
Present address: Department of Advanced Analytical Sciences, Reliance Technology Group,

Reliance Industries Limited, Reliance Corporate Park, Thane-Belapur Road, Navi Mumbai,

400701, India

* Corresponding author. E-mail: [email protected] (Abdelhamid Sayari)

1
Abstract:

A series of strictly microporous nitrogen-doped activated carbons were used to delineate the role

of nitrogen and micropores in CO2 adsorption. A wide range of activation conditions, including

the KOH to carbon weight ratio (1 - 2), temperature (550 - 700 °C) and time (1 - 2 h) were

explored to generate activated carbons with adjustable pore sizes and nitrogen contents. The

materials were characterized using X-ray diffraction, elemental analysis, X-ray photoelectron

spectroscopy and Ar, N2, H2 adsorption/desorption at -196 °C. CO2 uptake, heat of adsorption,

and CO2/N2 selectivity were determined from the adsorption/desorption isotherms measured at

different temperatures. The optimized materials exhibited unusually high nitrogen content (22.3

wt%) and high surface area (1317 m2/g), in addition to large pore volume (0.27 cm3/g)

comprised of ultramicropores less than 0.7 nm in diameter. This material showed an

extraordinary CO2 uptake of 23.7 wt% (5.39 mmol/g) at 25 °C and 1 bar, one of the highest

uptakes reported so far for any activated carbon. Its CO2/N2 selectivity at 25 °C was 237 and 62

at 0.01 and 1 bar, respectively. The results led to the conclusion that both nitrogen content and

ultra-micropores played important roles for CO2 adsorption, the latter being predominant.

1. Introduction

Climate change associated with increasing emissions of greenhouse gases (GHGs) is one of the

greatest threats to humanity. Among the GHGs, anthropogenic CO2 contributes more than 60%

to global warming because of the staggering amounts released into the atmosphere [1]. It is

therefore essential to develop carbon capture and storage (CCS) technologies to deal with the

global demand of CO2 reduction. To date, most of the commercial CO2 capture facilities use

2
chemical absorption processes with monoethanolamine (MEA) and other amine-based solvents

which suffer from several drawbacks, including high energy requirements, equipment corrosion,

and solvent degradation [2]. Integrated in coal fired power plants, amine-based CCS decreases

the net energy output by about 28%, with most of the cost being associated with the CO2 capture

[3,4]. Compared to amine absorption, adsorption-based separation technologies represent a

promising alternative with several advantages, such as lower energy requirements and milder

operating conditions. Therefore, in recent years extensive research effort was directed towards

the design and synthesis of high performance porous sorbents for CO 2 capture. Many solid

material based on metal organic frameworks (MOFs) [5], coordination organic polymers (COPs)

[6], zeolites [7], clays [8], carbons [9], and amine containing porous materials [10-14] have been

proposed for CO2 adsorption. However, they are still far from large-scale applications due to

economic and/or technical challenges. To a large extent the success of adsorption as a mean to

recover large amounts of nearly pure CO2 rests on the development of efficient and low-cost

adsorbents with high capacity, selectivity and stability.

Among the many proposed materials, the development of carbons with tuned porosity is

of significant importance in CO2 capture [15-29]. In particular, porous nitrogen-doped carbons

are among the most promising materials, due to their high and adjustable porosity, high

adsorption capacity and selectivity, easy synthesis, hydrophobicity and low cost [9]. Moreover,

such materials hold the greatest potential for commercial use due to their high chemical and

structural stability even under relatively severe conditions such as exposure to dry CO2, SO2, air

or steam at 130 °C [9]. Other materials such as zeolites, MOFs and amine-supported silica may

exhibit significant loss in performance when exposed to dry CO2 [14,30,31], SO2 [11,32-34], air

[12,13,35-39], or steam [40].

3
 Recently, a number of microporous carbon materials with high CO 2 adsorption capacity

have been reported [18,24-26,35,41-49]. For example, Nandi et al. [46] reported a CO2 uptake of

5.14 mmol/g (25 °C and 1 atm) for a nitrogen-doped activated carbon having ultra-micropores

(0.72-0.88 nm), prepared by physical activation of mesoporous polyacrylonitrile monoliths using

CO2.

Out of several properties (surface area, pore volume, pore diameter, N-content, and H-

content) the two properties reported to be crucial for CO 2 capture over carbons are pore diameter

and N-content. Enhancement of CO2 adsorption capacity and selectivity over N-containing

carbons takes place via acid-base interaction, quadrupolar interaction, and hydrogen bonding

interactions [25,50]. In nitrogen-doped activated carbon materials, nitrogen occurs in the forms

of pyridinic, amine/imine, pyrrolic, quaternary, and oxidized nitrogen and contributes towards

the high CO2 uptake, along with the microporosity and surface area of the adsorbent

[17,19,23,25,27,41,42]. The above-mentioned N-species contribute differently in CO2

adsorption, with pyrrolic nitrogen being the most active [27]. Occurrence of nitrogen increases

the basicity of material by providing electron donor groups for the adsorption of acidic CO 2.

However, the one-to-one acid-base interaction does not fully explain the high increase in CO 2

capture compared to the often small nitrogen content. This was explained by the involvement of

hydrogen-bonding interactions between the surrounding C−H groups and CO2 molecules, which

results in greater CO2 uptake of N-doped carbons [25].

Among the wide range of pore sizes in carbon materials, several researchers stressed the

importance of small micropores (< 1 nm) for CO2 adsorption [43,51]. Presser et al. [52], and

Wickramaratne et al. [24] showed that CO2 capture at room temperature depends on micropores

with diameters smaller than 0.8 nm. Zhang et al. [26] drew a more general conclusion as they

4
found that the CO2 adsorption capacity on carbon materials is associated with pores below a

temperature-dependent size. This critical pore size increased with decreasing adsorption

temperature; the micropores with diameters smaller than 0.54, 0.7 and 0.8 nm determine the CO2

adsorption capacity at 75, 25 and 0 °C, respectively. Sevilla et al. [22] also investigated the CO2

adsorption over microporous carbons with and without nitrogen, and concluded that high CO2

capture by carbon materials is entirely due to the volume of micropores smaller than 0.8 nm

without any contribution of nitrogen content. Notice however that the maximum N-content was

somewhat low (3.2 wt%). On the contrary, Liu et al. [19] found only ca. 4% decrease in the CO2

capture for ca. 64% decrease in micropore volume for N-doped carbons, indicating that nitrogen

plays also a key role in CO2 adsorption. Detailed XPS, FT-IR, and isosteric heat of adsorption

measurements showed the occurrence of both physical and chemical adsorption mechanisms and

indicated that microporosity is not the only factor associated with CO2 capture [19]. The single

and dual site Langmuir model fitting for adsorption of N2 and CO2, respectively on N-doped

carbon reported by Bermudez et al. [53] further supports the role of basic N-sites for high CO2

capture. n n - n a . [54] reported that the pore structure has a determining

effect on CO2 adsorption at 0 °C, while surface chemistry plays an important role at higher

temperatures. This brief literature survey shows that the extent and exact role of chemical and

textural properties for CO2 adsorption is still a matter of debate and needs more detailed

investigations.

Considering the importance of both material composition (C, H and N content) and

textural properties (surface area, pore size and pore volume) as well as the often contradictory

statements regarding the impact of such properties on CO2 uptake, we successfully optimized the

carbon activation procedure and developed strictly microporous activated carbons with high

5
nitrogen content and large volume of pores smaller than 0.8 nm for ultra-high CO2 uptake. The

effects of nitrogen and ultra-micropores were discussed in light of the experimental data

obtained.

2. Experimental

2.1 Materials Synthesis

2.1.1 Materials

Trimethylsilyl imidazole and chloroacetonitrile were obtained from Alfa Aesar, HCl (38 wt%)

and ammonia (28 wt%) were purchased from Sigma-Aldrich. Carbon dioxide (99.99%), nitrogen

(99.9993%), hydrogen (99.999%), argon (99.999%) and helium (99.999%) were supplied by

Linde Canada.

2.1.2 Synthesis of carbon precursor

The nitrogen rich (30.9 wt%) carbon precursor (CP) was synthesized by using a reported

procedure [27]. A mixture of trimethylsilyl imidazole (4.6 g, 0.033 mol) and chloroacetonitrile

(4.9 g, 0.033 mol) was stirred at room temperature for 24 h under inert atmosphere to form 1,3

bis(cynomethyl imidazolium) chloride a white solid material. The solid was washed with diethyl

ether (3 × 30 mL) and dried under vacuum for 24 h.

2.1.3 Preparation of activated carbon

A two-step method was applied in the preparation of N-doped activated carbons. The first step

was a carbonization process. The white solid was placed in an alumina boat, transferred into a

tubular furnace and then heated under N2 flow (100 cm3/min) at a rate of 10 °C/min, with a

holding time of 2 h at the final temperature. The material obtained after carbonization at 400 and

6
600 °C were denoted as CP-400 and CP-600, respectively. The second step was an activation

process to generate porosity in the synthesized material. The non-porous CP-400 material (vide

infra) was mixed with KOH (KOH/CP-400 weight ratio of 1, 1.25, 1.5, 1.75 and 2) and ground

in an agate mortar. The resulting powder was then heated under N2 flow (100 cm3/min) up to a

temperature in the range of 550-700 °C (heating rate: 3 °C/ min−1, holding time at the final

temperature: 1-2 h). The activated samples were then thoroughly washed several times with HCl

(10 wt%) to remove any inorganic impurities, then with NH4OH (3 wt%) to neutralize the acid

sites generated during acid wash, and finally washed several times with hot distilled water until

the sample was completely free from chlorides and the pH was neutral. The presence of chlorides

in washings was tested with AgNO3. The obtained samples were dried in an oven at 80 °C

overnight. The activated carbons thus synthesized were denoted as NAC-x-y, where NAC stands

for nitrogen-doped activated carbon, x is the KOH/CP-400 weight ratio and y is the activation

temperature (in °C).

2.2 Characterization

The textural properties of the synthesized materials were determined by nitrogen adsorption and

desorption at -196 °C using a Micromeritics ASAP 2020 apparatus. The surface area was

calculated by using the BET method applied to nitrogen adsorption data in the relative pressure

(P/Po) range of 0.05-0.20. The total pore volume was determined from the amount of nitrogen

adsorbed at P/Po = 0.97. The pore size distribution (PSD) was determined by density functional

theory (DFT) model with slit pore geometry using the nitrogen adsorption data. The total

micropore volume was also determined by applying the Dubinin-Astakhov equation to the CO2

adsorption isotherm measured at 0 °C. X-ray diffraction (XRD) measurements were carried out

on a P i ips X’p r MPD s s m in 2θ rang of 10-70° using CuKα1 (λ = 1.54056 Å)

7
radiation. The amount of carbon, nitrogen and hydrogen in the samples was determined by

elemental analysis using a Vario EL III instrument. The nature and content of nitrogen species

and oxygen in the material were determined by X-ray photoelectron spectroscopy (XPS)

recorded on a Kratos Axis Ultra spectrometer. Carbon C1s peak with binding energy of 284.6 eV

was used as reference. The XPS N1s signals were deconvoluted into characteristic peaks

belonging to pyridine, PhNH2 (or –C=NH), pyrrole, quaternary nitrogen and pyridine N-oxide

using the CasaXPS software.

2.3 CO2 and N2 adsorption isotherms measurements

CO2 and N2 adsorption isotherms were measured using a static volumetric system (ASAP 2020).

The presence of water in the materials significantly affects the adsorption isotherms of other
-1
species; therefore, the samples were activated in situ by heating to 300 °C, at a rate of 5 °C min

under vacuum (510-3 mm Hg) overnight using the degassing system of ASAP 2020. The

adsorption temperature was maintained ( 0.1 °C) by circulating water from a constant

temperature water bath (VWR, 04FA60). The adsorbate gas was injected into the set up at

volumes required to achieve a targeted set of pressures ranging from 0.001 to 760 mmHg. Three

pressure transducers with a range of 1, 10 and 1000 mmHg were used for the pressure

measurements. A minimum equilibrium interval of 30 seconds with a maximum relative

tolerance of 5% of the targeted pressure and an absolute tolerance of 5 mmHg were used to

determine the equilibrium for each measurement point. The adsorption capacity, as weight of gas

adsorbed per gram of adsorbent, the selectivity and the isosteric heat of adsorption were

determined from the adsorption isotherms measured at 0, 15 and 25 °C.

8
2.4 Heat of adsorption and adsorption selectivity

The heat of adsorption of CO2 over NAC materials is a measure of the surface affinity toward

CO2, and reflects the strength of interaction. It was calculated using the adsorption data collected

at 0, 15 and 25 °C and the Clausius-Clapeyron equation [5].

 lnp 
H ads
o
 R 
 (1 / T ) 

where, Hoads is the heat of adsorption, R is the ideal gas constant,  is the CO2 surface coverage

at a pressure p and temperature T. A plot of lnp versus 1/T gives a straight line with a slope of

H ads
o
.

Pure component adsorption selectivity was determined using the ideal adsorbed solution theory

(IAST). The adsorption isotherms data were fitted in Langmuir and dual-site Langmuir model

equations. The fitting and IAST data were calculated using OriginPro v8.5. All the fitting

corresponded to adjusted R2 values exceeding 0.999.

The single-site Langmuir model is defined as:

qmaxbp
q
1  bp

The dual-site Langmuir model is defined as:

qmaxbA p qmaxbB p
q  qa  qb  
1  bA p 1  bB p

where, q is the molar loading of adsorbate, qmax is the saturation loading, b is the Langmuir

constant, and A and B represent two different adsorption sites.

The IAST selectivities for the CO2:N2 (0.15:0.85) gas mixture were calculated using the

following equation:

9
 q1 / q2
S
p1 / p2

where, S is the selectivity, q1 and q2 represent the amount adsorbed of components 1 and 2, and

p1 and p2 represent the partial pressure of components 1 and 2, respectively.

3. Result and Discussion

3.1 X-ray photoelectron spectroscopy

According to previous studies, CO2 adsorption capacity of activated carbon materials is strongly

dependent on the pore size and surface chemical properties, especially the N-containing

functional groups [17,19,25-27]. Therefore, the surface properties of the current activated

carbons were investigated using XPS and the resulting spectra are presented in Fig. 1. The N1s

signal was deconvoluted into 3 to 5 components. The corresponding binding energies of ca. 398,

399, 400, 401 and 403 eV were attributed to pyridine, Ar–NH2 (or –C=NH), pyrrole, quaternary

nitrogen and pyridine N-oxide respectively (Table 1) [17,19,25-27,41]. To study the relationship

between surface chemistry, preparation conditions and CO2 capture of the activated carbons, the

relative amount of each type of surface nitrogen was calculated using the deconvoluted N1s XPS

spectra (Fig. 1) and are given in Table 1. Three peaks for non-activated carbon and four to five

peaks were observed for materials activated with KOH at different temperatures. The XPS

spectra clearly show that significant chemical changes occurred during the activation stage. The

N-profile was different for materials prepared under different conditions; the activated samples

showed the presence of Ar–NH2 (or –C=NH), and pyridine N-oxide species which were absent

in non-activated CP-400. Materials activated at 550 and 600 °C showed similar nitrogen profiles

and contents. However, the sample prepared at higher temperature (700 °C) exhibited different

nitrogen profile and lower content. NAC-1.5-700 showed the presence of pyridine N-oxide

10
which was not observed in any of the CP-400 (non-activated), NAC-1.5-550 and NAC-1.5-600

materials. Similarly, Gu et al. [41] found that the percentage of quaternary-N and pyridine N-

oxide moieties increased with increasing carbonization temperature. It was also observed that

during high temperature activation, the pyridinic nitrogen content decreased gradually both in

absolute and in relative terms. The overall content decreased by 80% from 15.0 wt% for CP-400

to 3.0 wt%, whereas the relative content decreased only by half, from 50.5 to 25.2% (Table 1).

This indicates that in addition to the selective removal of nitrogen during high temperature

activation, pyridinic nitrogen was converted to other species, particularly PhNH 2 (or –C=NH),

and pyridine N-oxide. Parallel to the evolution of nitrogen species the oxygen content increased

after KOH activation providing evidence for the insertion of oxygen atoms in the carbon material

[19]. The insertion of oxygen is consistent with the d002 spacing observed in the XRD

measurements.

11
Fig. 1 XPS N1s spectra for (a) CP-400 (b) NAC-1.5-550, (c) NAC-1.5-600, (d) NAC-1.5-700.

Table 1 Surface composition of the NAC materials

Pyridinea PhNH2/- Pyrrolea Quaternary- Pyridine N- Total

Oxygena
Samples C=NHa Na Oxidea Nitrogen
α β Α β α Β Α β α β b
(wt%) (wt%)

CP-400 15.0 50.5 --- --- 10.3 34.6 4.4 14.9 ---- 29.7 6.8
NAC-1.5- 550 9.5 37.8 2.7 10.5 9.7 38.3 3.4 13.4 ---- 25.2 10.1
NAC-1.5- 600 8.0 35.9 2.7 12.1 8.6 38.6 2.8 13.3 ---- 22.3 9.2
NAC-1.5- 700 3.0 25.4 1.9 15.8 3.8 32 1.4 11.7 1.8 15.1 11.9 8.3
Binding
398-398.7 399 399.7-400.9 400.7-401.9 402.8-403.9
Energy (eV)
a
determined from XPS measurements, and b determined from CHN analysis
α: wt% of the total material, and β: relative % of total nitrogen

12
3.2. Effect of KOH/CP-400 ratio on the properties of activated carbons

3.2.1 Textural properties of activated carbons

The nitrogen sorption isotherms and corresponding PSDs of activated carbons prepared with

KOH/CP-400 ratios in the range of 1 to 2 at 600 °C are displayed in Fig. S1 and 2, respectively.

The sharp uptake at low relative pressure (P/P0 < 0.1) indicates the microporous nature of all the

samples. The changes in the shape of the PSD with increasing KOH/CP-400 ratio indicate

changes in the pore structure of the activated carbons. Indeed, Fig. 2 indicates that the porosity of

the samples activated at 600 °C with KOH/CP-400 = (1, 1.5, and 2) was comprised mostly of

mi ropor s (≤ 2 nm). As the KOH/CP-400 ratio increased, the PSD shifted to larger pores. The

porosity of the materials prepared with KOH/CP-400 = 1, and 1.5 consisted mostly of ultra-

micropores around 0.54 and 0.59 nm in diameter, whereas the material prepared with KOH/CP-

400 = 2 contained mostly wider micropores centered around 0.73 nm (Fig. 2).

The textural properties of the activated carbons are listed in Table S2. It can be seen that

the BET surface area and the pore volume increased significantly from 796 to 1317 m2/g and

0.39 to 0.64 cm3/g, respectively when the KOH/CP-400 ratio increased from 1.0 to 1.5. As

shown in Fig. 2, the enhancement of pore volume and by inference the surface area, is due

mostly to the formation of slightly larger micropores (0.59 vs 0.54 nm). The decrease in surface

area (517 m2/g) and pore volume (0.25 cm3/g) with further increase in KOH/CP-400 ratio to 2.0

was attributed to the formation of larger pores with broad size distribution. The PSDs showed a

gradual increase in micropore size going from mild to severe activation condition. Fig. 3 clearly

shows that the textural properties of activated carbons strongly depend on the relative amount of

KOH used. Therefore, the KOH/CP-400 ratio must be carefully optimized to prepare materials

with high surface area, pore volume and narrow micropore diameters.

13
Fig. 2 DFT pore size distributions for NAC materials prepared with different KOH/CP-400

ratios.

Fig. 3 Correlation between surface area, pore volume and KOH/CP-400 ratios.

14
3.2.2 Chemical composition of activated carbons

The chemical composition of the activated carbons as determined by the CHN analysis is

presented in Table S3. It is observed that the nitrogen content decreased whereas the carbon

content increased with increasing carbonization temperature from 400 to 600 °C, indicating the

selective removal of nitrogen during the thermal treatment. The nitrogen content decreased from

27.3 % for the non-activated CP-600 to 21.5-23.5 % for the materials activated with KOH

(KOH/CP-400 = 1 to 2) at 600 °C. Interestingly, materials prepared with different KOH/CP-400

ratios (1, 1.5, 1.75 and 2) at fixed temperature of 600 °C showed comparable compositions

(Table S3, Fig. 4), indicating that neither nitrogen nor carbon was removed preferentially during

activation at constant temperature regardless of the KOH/CP-400 ratio. However, as mentioned

earlier, the selective removal of nitrogen is highly dependent on the activation temperature.

Fig. 4 Correlation between elemental composition, elemental ratio, and KOH/CP-400 ratio.

15
3.2.3 CO2 adsorption properties of activated carbons

Fig. 5 shows CO2 and N2 adsorption isotherms at 25 °C and up to 1 bar pressure. On increasing

the carbonization temperature from 400 to 600 °C, the CO2 adsorption capacity increased

significantly; e.g. from 2.9 to 8.0 wt% at 1 bar. However, changes in surface area (18 vs. 11

m2/g) and pore volume as determined from N2 adsorption at -196 °C (0.02 vs. 0.01 cm3/g) were

rather modest. The sizable increase in CO2 adsorption capacity with increasing carbonization

temperature may be due to changes in the N-profile and/or the formation of ultra-micropores, not

accessible to nitrogen molecules at -196 °C. To explore the latter possibility, adsorption

isotherms of gas molecules with different kinetic diameters were measured in the presence of

CP-400 and CP-600 at -196 °C and up to 200 mbar (Fig. 6). Ar, N2, CO2 and H2 with kinetic

diameters of 0.384, 0.364, 0.33, and 0.29 nm, respectively, were used as probe molecules

[7,8,51,55].

CP-400 and CP-600 showed very low (< 5 cm3/g) adsorption for nitrogen and argon,

indicating that no pores with diameter larger than 0.364 nm occurred in such materials. However,

the materials showed different behaviors towards hydrogen adsorption. While almost no

hydrogen (< 5 cm3/g), adsorbed on CP-400 at 200 mbar, CP-600 exhibited significant adsorption

(70.3 cm3/g). The difference in hydrogen uptake clearly indicates the presence of ultra-

micropores accessible to hydrogen (> 0.289 nm) but not to argon and nitrogen (> 0.364 nm). It is

thus inferred that CP-600 is endowed with ultra-micropores that are large enough to

accommodate CO2 (0.33 nm), but not N2 or Ar, whereas CP-400 is essentially non-porous.

16
Fig. 5 CO2 and N2 adsorption isotherms at 25 °C for CP-400, CP-600 and NAC-1.5-600.

Fig. 6 N2, H2 and Ar adsorption isotherms at -196 °C for CP-400 and CP-600.

17
 The CO2 adsorption capacities at 0 and 25 °C and 1 bar for the materials prepared under

different carbonization and activation conditions are given in Table 2. The CO2 uptake for the

materials activated under mild condition (KOH/CP-400 = 1, 1.25, and 1.5) increased with

increasing KOH/CP-400 ratios. However, the adsorption capacity decreased on further increase

in KOH/CP-400 ratio. Fig. S2 shows the CO2 adsorption isotherms of the carbon samples

activated under different conditions (KOH/CP-400 = 1 - 2). The material prepared under

optimum activation condition (KOH/CP-400 = 1.5) showed the highest adsorption capacity of

23.7 wt% (5.39 mmol/g) reported for any N-doped activated carbon at 25 °C and 1 bar (Table

S1). This is because this optimized material exhibits both key features which are crucial for high

CO2 adsorption, namely the occurrence of ultra-micropores below 0.7 nm; in this case, narrowly

distributed around 0.59 nm (Fig. 2 and Table 3), in addition to unusually high nitrogen content of

22.3 wt% (Fig. 2 and table 4). Further comparison with literature data is shown in Table S1.

Table 2 CO2 and N2 adsorption capacity, and heat of adsorption for materials activated at 600 °C

with different KOH/CP-400 ratios

CO2 ads. capacitya (wt%) N2 ads. capacitya (wt%) CO2 ΔHads

Samples
0 °C 25 °C 25 °C (kJ/mole)b
CP-400 2.8 2.9 0.32 45.3
CP-600 9.8 8.0 0.80 43.9
NAC-1-600 18.4 14.1 0.85 42.3
NAC-1.25-600 20.8 16.0 1.11 42.8
NAC-1.5-600 31.7 23.7 1.37 42.4
NAC-1.75-600 18.3 12.3 1.30 37.7
NAC-2-600 15.6 10.9 1.18 38.6
a
at 1 bar, b at 0.1 cm3/g

18
3.3 Effect of activation temperature on textural properties of activated carbons

3.3.1 Textural properties of activated carbons

The nitrogen adsorption isotherms at -196 °C and the corresponding PSDs for carbons activated

at different temperatures (550 - 700) using the same KOH/CP-400 ratio of 1.5, are shown in Fig.

S3 and 7, respectively. The sharp uptake at low relative pressure (P/P0 < 0.01) shows the strictly

microporous nature of all the samples, except NAC-1.5-700, which exhibited a wide range of

micropores and mesopores. The changes in the shape of the PSD with increasing activation time

and temperature reflect changes in the pore structure of activated carbons. In particular, as shown

in Fig. 7 the PSD widened and shifted towards larger pores as the activation time and

temperature increased.

The porosity of carbons prepared at 550 and 600 °C consisted mostly of two groups of

ultra-micropores with diameters around of 0.56 and 0.59 nm, respectively (Fig. 7). The porosity

of the material prepared at 650 °C consisted mostly of micropores around 0.63 and 1.09 nm in

size. The porosity increased with temperature as NAC-1.5-700 exhibited significantly higher

surface area (2386 m2/g) and pore volume (1.16 cm3/g) with broader PSD. Table 3 shows that

although the surface area and total pore volume increased significantly with increasing activation

temperature, the DFT pore volume of pores below 0.73 nm in diameter actually decreased after

activation between 600 and 700 °C, in favor of larger pores. It is also observed that not only the

temperature, but the duration of activation also significantly affects the porosity of the materials.

The PSD of the material prepared at 600 °C with longer activation time (2 h) showed a broader

micropore distribution around 0.77 and 0.93 nm. Most of such micropores were formed by the

widening of ultra-micropores (diameter 0.59 nm) which formed during the first hour of

activation.

19
 Table 3 shows detailed analysis of the porosity of N-doped carbon materials prepared at

different temperatures with KOH/CP-400 = 1.5. The cumulative micropore volume up to

different sizes from 0.59 to 2 nm was calculated by the DFT method using N 2 adsorption data at

-196 °C. Moreover, the total volume of micropores up to 1.5 nm diameter, was also calculated

based on CO2 uptake at 0 °C using the Dubinin-Astakhov equation. As indicated in Table 3,

there is strong agreement between the two methods. NAC-1.5-550 exhibited a surface area and

total pore volume of 526 m2/g and 0.26 cm3/g, respectively. Increasing the temperature to 600 °C

(NAC-1.5-600) was accompanied by a sharp increase in surface area (1312 m2/g) and pore

volume (0.64 cm3/g) due to increased porosity, particularly in the ultra micropore region.

However, the decrease in surface area (728 m2/g) and pore volume (0.35 cm3/g) for carbon

prepared at 600 °C and longer activation time (2 h) was due to enlargement of micropores,

leading to broader PSD.

Fig. 7 DFT pore size distribution for NAC materials prepared at different temperatures with

KOH/CP-400 ratio of 1.5.

20
 Table 3 Textural properties of N-doped carbon materials prepared at different temperatures with

KOH/CP-400 = 1.5

BET DFT D-A total

Total pore Cumulative DFT pore volume (cm3/g)
surface pore micropore
Samples volumeb
area sizea volumec
(cm3/g)
(m2/g) (nm) (cm3/g) 0.59 nm 0.73 nm 1 nm 2 nm
NAC-1.5-550 526 0.54 0.26 0.14 0.12 0.12 0.13 0.16

NAC-1.5-600 1317 0.59 0.64 0.37 0.27 0.27 0.32 0.43

NAC-1.5-650 1342 0.63 0.65 0.39 0.0 0.21 0.29 0.50

NAC-1.5-700 2386 0.74 1.16 0.59 0.0 0.18 0.23 0.69

NAC-1.5-600 (2h) 728 0.99 0.35 NA 0.0 0.07 0.27` 0.28

a
Maxima of the PSDs calculated by DFT

b
Total pore volume from N2 adsorption at -196 °C

c
Dubinin-Astakhov (D-A) total volume of micropores with diameter less than 1.5 nm, calculated from
CO2 adsorption data at 0 °C

3.3.2 Chemical composition of activated carbons

The chemical composition of materials prepared at different temperatures with KOH/CP-400

ratio of 1.5 is presented in Table 4. As can be seen, there is a decrease in the nitrogen content

from 29.7 wt% for non-activated CP-400 to 25.2 wt% after activation under mild conditions (550

°C and KOH/CP = 1.5). Materials prepared at 600, 650, and 700 °C showed significant decrease

in nitrogen and hydrogen contents. This selective removal of nitrogen and hydrogen at increasing

activation temperature is consistent with Wang et al. [56-58] findings. Nonetheless, to the best of

our knowledge, the optimum material, namely NAC-1.5-600 exhibited the highest nitrogen

21
content (22.3 wt%) ever reported for any nitrogen containing activated carbon for CO2 capture

(Table S1) [59,60]. The retention of high N-content even under severe activation condition may

be attributed to enhanced stability due to the graphitic nature of materials.

Table 4 Chemical composition of N-doped activated carbons prepared at different temperatures

and KOH/CP-400 = 1.5

Chemical composition (wt%)

Samples N/Ca H/Ca
N C H Other

CP-400 29.7 56.9 2.8 10.6 0.522 0.049

NAC-1.5-550 25.2 60.3 2.9 11.6 0.419 0.048
NAC-1.5-600 22.3 56.8 2.6 18.3 0.393 0.047
NAC-1.5-650 18.0 64.5 2.2 15.3 0.279 0.035
NAC-1.5-700 11.9 70.7 1.4 16.0 0.168 0.020
a
weight ratios

3.3.3 CO2 adsorption properties of activated carbons

Table 5 summarizes the CO2 adsorption capacities at 0 and 25 °C of materials prepared at

different temperatures with a KOH/CP ratio of 1.5. CP-400, NAC-1.5-550, NAC-1.5-600, NAC-

1.5-650, and NAC-1.5-700 showed CO2 adsorption capacity of 2.9, 14.0, 23.7, 18.4, and 14.8 wt

%, respectively at 25 °C and 1 bar, whereas the nitrogen content decreases steadily in the same

order (Table 4). The high uptake for NAC-1.5-600 is associated with the formation of a large

number of ultra-micropores (≤ 0.59 nm), whose cumulative volume as calculated by DFT

increased from 0.12 to 0.27 cm3/g (Table 3). The decrease in CO2 uptake for NAC-1.5-650 and

NAC-1.5-700 is predominantly due to the lack of ultra-mi ropor s (≤ 0.59 nm), broader PSD,

and possibly the abrupt decrease in nitrogen content from 22.3 (NAC-1.5-600) to 11.9 wt%
22
(NAC-1.5-700). This is direct evidence that CO2 uptake is strongly dependent on the occurrence

of ultra-micropores and much less on the nitrogen content.

The material prepared under optimized activation condition (NAC-1.5-600) showed the

highest adsorption capacity because of optimized pore size distribution, large pore volume and

high nitrogen content. The regeneration of NAC-1.5-600 was investigated by repeated

adsorption-desorption cycles carried out at 25 °C (Fig. S4). The material was degassed at 200 °C

under high vacuum prior to measurements of each isotherm. There was no significant change in

the CO2 uptake after 4 adsorption-desorption cycles, indicating that the material can be

regenerated over multiple cycles without any decrease in CO 2 uptake.

Fig. 8 and 9 show the CO2 adsorption isotherms of carbon samples activated under

different conditions (KOH/CP-400 = 1.5, and temperature = 550-700 °C) at 25 and 0 °C,

respectively. The adsorption isotherms indicate that the CO2 adsorption capacity at 1 bar for

NAC-1.5-700 was higher than NAC-1.5-550. However, NAC-1.5-550 showed higher adsorption

capacity in the low pressure region. NAC-1.5-550 showed cumulative pore volume of 0.12 cm3/g

of ultra-micropores having diameters below 0.59 nm, while NAC-1.5-700 does not exhibits any

ultra-micropores (Table 3). CO2 adsorption in the ultra-mi ropor s (≤ 0.7 nm) o urs via

pore filling mechanism at 25 °C [26]. It may thus be inferred that the presence of ultra-

micropores in NAC-1.5-550 is responsible for the higher CO2 uptake in the low pressure region.

Moreover, NAC-1.5-550 and NAC-1.5-700 have nitrogen contents of 25.2 and 11.9 wt%

respectively, the large amount of basic nitrogen containing groups is also responsible for the

initial high CO2 uptake in the low pressure region.

23
 Interestingly, the adsorption isotherms (Fig. 8 and 9) indicate that NAC-1.5-700 exhibits

lower CO2 uptake than NAC-1.5-550 up to 850 mbar at 25 °C and up to 500 mbar at 0 °C. This

behavior is due to the different CO2 adsorption mechanisms at different temperatures in the

micropores. NAC-1.5-700 has cumulative pore volume of 0.18 cm3/g from the micropores

having diameter 0.73 nm (Table 3 and Fig. 7), where CO2 adsorption occurs via the pore filling

mechanism at 0 °C but not at 25 °C. This is in line with Zhang et al. [26] findings that critical

pore size for high CO2 uptake by pore filling mechanism in activated carbons increases with

decreasing adsorption temperature and micropores having diameters less than 0.7 and 0.8 nm are

responsible for the high CO2 uptake at 25 and 0 °C, respectively. The CO2 adsorption behavior

of NAC-1.5-550 and NAC-1.5-700 also indicates the role of ultra-micropores in the CO2 capture.

Table 5 CO2 and N2 adsorption capacity, selectivity and heat of adsorption for carbons activated

at different temperatures with KOH/CP-400 ratio of 1.5

CO2 Ads. capacitya N2 Ads. capacitya

CO2/N2 Selectivity CO2 ΔHads
Samples (wt%) (wt%)
(kJ/mole)
0 °C 25 °C 25 °C 0.01 (bar) 1 (bar)
CP-400 2.8 2.9 0.32 62 33 45.3
CP-600 9.8 8.0 0.80 419 54 43.9
NAC-1.5-550 16.5 14.0 0.91 365 56 44.3
NAC-1.5-600 31.7 23.7 1.37 237 62 42.4
NAC-1.5-650 24.6 18.4 1.2 219 57 33.1
NAC-1.5-700 21.5 14.8 1.1 85 49 30.1
NAC-1.5-600 (2h) NA 15.2 1.0 NA NA NA
a
at 1 bar, b at 0.1 cm3/g

24
Fig. 8 CO2 adsorption isotherms at 25 °C for materials prepared at different temperatures with
KOH/CP-400 ratio of 1.5.

Fig. 9 CO2 adsorption isotherms at 0 °C for materials prepared at different temperatures with
KOH/CP-400 = 1.5.

25
3.4 Adsorption selectivity of carbon dioxide versus nitrogen

The N2 adsorption isotherms for all carbon materials were also measured at 25 °C and up to 1 bar

pressure. Representative data were included in Fig. 5. Regardless of the material, the adsorption

capacity for N2 was much smaller than for CO2 at any pressure. CO2 and N2 adsorption data at 1

bar are provided in Tables 2 and 5. The N2 and CO2 adsorption isotherms were used to calculate

the selectivity of all materials for CO2 versus N2 at different pressures. Fig. 10 shows CO2:N2

(0.15:0.85) selectivity in the range of 0 - 1 bar pressure at 25 °C for the materials prepared at

550, 600, 650, and 700 °C with KOH/CP-400 = 1.5 as calculated using the ideal adsorbed

solution theory (IAST). The pure component CO2 and N2 adsorption isotherms were fitted with

single-site Langmuir model and dual site Langmuir model, respectively and the obtained

saturation loading and Langmuir constant were used to calculate CO 2/N2 selectivity. The CO2/N2

selectivity at 0.01 and 1 bar pressure and 25 °C is given in Table 5. The higher selectivity in the

low pressure region is consistent with literature data [61].

The model fitting suggest different adsorption mechanisms for CO2 and N2 adsorption

and surface heterogeneity of activated carbon. Contrary to dual site Langmuir model, the single

site model provided an excellent fit to the N2 adsorption isotherms, indicating the occurrence of a

single adsorption site for N2 adsorption. It is thus inferred that the basic N-sites are not involved

in the adsorption of neutral N2. However, well fitted dual site Langmuir model with CO 2

adsorption isotherms suggest the involvement of different sites for CO2 adsorption and possible

role of N-sites for high CO2 uptake and CO2/N2 selectivity.

The materials activated in the range of 550 - 700 °C exhibited CO2/N2 adsorption

selectivity higher than CP-400. However, non-activated CP-600 showed a selectivity of 419 at

26
0.01 bar, higher than activated carbon samples. The high adsorption selectivity for CP-600 at

0.01 bar is due to the presence of ultra-micropores (Fig. 6 and Table S2) which, as mentioned

earlier are accessible to carbon dioxide but not to nitrogen adsorption. The selectivity decreased

with increasing activation temperature and NAC-1.5-550 showed the highest selectivity of 365 at

0.01 bar and 25 °C among activated carbon samples. This trend is attributed to the enlargement

of pore diameters [62] and decreasing nitrogen content, which significantly affects the CO2

capture in the low pressure region. However, at 1 bar, NAC-1.5-600 showed maximum

selectivity of 62, higher than NAC-1.5-550 (Table 5). This was attributed to the significantly

higher surface area and micropore volume. NAC-1.5-700 exhibited the lowest selectivity of 85

and 49 at 0.01 and 1 bar, respectively, because of its broad pore size distribution and low

nitrogen content.

CO2 has smaller kinetic diameter (0.33 vs. 0.364 nm) and higher quadrupole moment

(4.30 × 10-26 vs. 1.52 × 10-26 esu*cm2) than nitrogen, which results in stronger adsorbate-

adsorbent interactions, leading to high adsorption in the low pressure region via the micropore

filling mechanism [61]. Additionally, the high CO 2 uptake observed in the low pressure region is

due to strong interactions of CO2 with pyridinic, amine/imine, and pyrrolic sites of activated

carbon materials [63]. Adsorption occurs at more favorable sites first, followed by less favorable

sites at increasing pressure.

27
Fig. 10 CO2 vs. N2 selectivity as predicted by the IAST method for CO2:N2 = 0.15:0.85 gas

mixture at 25 °C for materials prepared at different temperatures with KOH/CP-400 = 1.5.

3.5 Heat of adsorption

The heat of CO2 adsorption for all the samples was determined from the adsorption isotherms

generated at 0, 15 and 25 °C. The initial heat of adsorption at 0.1 cm3/g for materials prepared

with different KOH/CP-400 ratios and different activation temperatures is given in Tables 2 and

5, respectively. The heat of adsorption for all materials was high because of the strong attractive

electrostatic interactions between acidic CO2 and basic N-containing sites. Activated carbon

samples showed decreasing heat of adsorption with increasing coverage (Fig. S5 and S6). This

was attributed to the preferential adsorption of CO2 on basic nitrogen sites and ultra-micropore

28
filling followed by adsorption in pores with larger diameters. This behavior clearly shows the

surface heterogeneity of activated carbons and the role of surface chemistry on the CO2 capture.

The heat of adsorption for CP-400 decreased rapidly with increasing coverage. CP-400 is

a non-activated, non-porous material and the observed heat of adsorption is mainly associated

with CO2 interaction with surface nitrogen functionalities. When these active sites are occupied

the heat of adsorption decreases suddenly. Material carbonized at higher temperature CP-600

showed lower nitrogen content along with the development of very fine ultra-micropres. Despite

the presence of ultra-micropores as shown in Fig. 6, the heat of adsorption was low because of

very slow CO2 adsorption due to diffusional limitations. CP-600 has ultra-micropores (0.29 –

0.364 nm) restricting the adsorption to a single layer of CO2 molecules, which probably lie flat to

the micropore walls and results in lower heat of adsorption [64]. Moreover, due to single layer

adsorption CO2-CO2 interactions are unlikely to occur in CP-600.

Fig. S5 also shows that the heat of adsorption for activated carbons at high CO2 loading is

significantly higher than non-activated CP-400 and CP-600. The lower heat of adsorption for

ultra-microporous CP-600 (pore diameter 0.29 – 0.364 nm) than activated carbons (pore

diam r ≤ 0.7 nm) shows the importance of optimized pore size for high CO2 uptake via volume

filling mechanism. This observation provides evidence for the dominating role of ultra-

micropores over nitrogen content for CO2 adsorption at high loading.

The high heat of CO2 adsorption for NAC materials (Fig S5 and S6) was attributed not

only to the strong electrostatic interactions but also to the non-electrostatic interactions which

occur inside the micropores. Beyond a pore size that is large enough to accommodate more than

one layer of CO2 molecules (0.5 nm) [64], the smaller the pores the stronger the interactions.

29
 The heat of adsorption for activated carbons decreased with increasing activation

temperature (Fig. S6) due to the increase in the pore size and decrease in nitrogen content.

However, the decreasing heat of adsorption for samples prepared with different KOH/CP-400

ratios (Table 2), having similar N/C ratios (Table S3) again shows the dominating role of pore

size over nitrogen content in CO2 capture and heat of adsorption.

4. Conclusion

Activated carbons with tunable porosity and nitrogen content were prepared by optimizing the

KOH/CP-400 ratio and the activation temperature and time. To a large extent, the textural

properties and composition of materials depend more strongly on activation temperature and

time than KOH/CP-400 ratio. The NAC-1.5-600 exhibited the highest nitrogen content (22.3

wt%) ever reported for any nitrogen-doped activated carbon, and a very high CO2 adsorption

capacity of 23.7 wt% at 25 °C and 1 bar. The material also exhibited high CO2/N2 (0.15:0.85)

room temperature selectivity of 237 and 62 at 0.01 and 1 bar, respectively, The remarkable CO2

uptake and CO2/N2 selectivity is attributed to the occurrence of ultra-micropores around 0.59 nm

in diameter, large micropore volume and high nitrogen content. The single-site and dual-site

Langmuir model fittings indicate different adsorption mechanisms for CO2 and N2 adsorption.

The nitrogen-doped ultra-microporous carbons exhibited high heat of adsorption because of

strong electrostatic and non-electrostatic interactions. The heat of adsorption decreased with

increasing CO2 loading as the adsorption occur at more favorable nitrogen-containing sites and

ultra-micropores first, followed by larger pores. The decreased heat of adsorption for materials

prepared at higher activation temperature is due to the decreased strength of non-electrostatic

interactions inside the larger pores. At high CO2 loading, the heat of adsorption is significantly

higher for activated carbons than the non-activated narrow ultra-microporous CP-600, indicating

30
the importance of optimized pore size for high CO2 uptake. This detailed study showed that both

nitrogen content and micropore sizes are important for high CO2 uptake with the ultra-micropore

effect being predominant.

Acknowledgments

The financial support of the Natural Sciences and Engineering Council of Canada (NSERC) is

acknowledged. A.S. thanks the Federal Government for the Canada Research Chair in

Nanostructured Materials for Catalysis and Separation (2001−2015).

Appendix A. Supplementary data

Supplementary data associated with this article can be found, in the online version, at

http://dx.doi.org.

References

[1] Sayari A, Belmabkhout Y, Serna-Guerrero R. Flue gas treatment via CO2 adsorption.

Chem Eng J 2011;171(3):760-74.

[2] Markewitz P, Kuckshinrichs W, Leitner W, Linssen J, Zapp P, Bongartz R, et al.

Worldwide innovations in the development of carbon capture technologies and the

utilization of CO2. Energy Environ Sci 2012;5(6):7281-305.

[3] Freeman B. Assessment of post-combustion capture technology developments. Electric

Power Research Institute, California, USA, 1012796, 2012.

[4] Ebner AD, Ritter JA. State-of-the-art adsorption and membrane separation processes for

carbon dioxide production from carbon dioxide emitting industries. Sep Sci Technol

2009;44(6):1273-421.

31
[5] Munusamy K, Sethia G, Patil DV, Somayajulu Rallapalli PB, Somani RS, Bajaj HC.

Sorption of carbon dioxide, methane, nitrogen and carbon monoxide on MIL-101(Cr):

Volumetric measurements and dynamic adsorption studies. Chem Eng J 2012;195–

196:359-68.

[6] Patel HA, Je SH, Park J, Jung Y, Coskun A, Yavuz CT. Directing the structural features

of N2-phobic nanoporous covalent organic polymers for CO2 capture and separation.

Chem Eur J 2014;20(3):772-80.

[7] Jiang Q, Rentschler J, Sethia G, Weinman S, Perrone R, Liu K. Synthesis of T-type

zeolite nanoparticles for the separation of CO2/N2 and CO2/CH4 by adsorption process.

Chem Eng J 2013;230:380-8.

[8] Pawar RR, Patel HA, Sethia G, Bajaj HC. Selective adsorption of carbon dioxide over

nitrogen on calcined synthetic hectorites with tailor-made porosity. Appl Clay Sci

2009;46(1):109-13.

[9] Sethia G, Sayari A. Nitrogen-doped carbons: Remarkably stable materials for CO2

capture. energy Fuels 2014;28(4):2727-31.

[10] Belmabkhout Y, De Weireld G, Sayari A. Amine-bearing mesoporous silica for CO2 and

H2S removal from natural gas and biogas. Langmuir 2009;25(23):13275-8.

[11] Belmabkhout Y, Sayari A. Isothermal versus non-iso rma adsorp ion−d sorp ion

cycling of triamine-grafted pore-expanded MCM-41 mesoporous silica for CO2 capture

from flue gas. Energy Fuels 2010;24(9):5273-80.

[12] Heydari-Gorji A, Belmabkhout Y, Sayari A. Degradation of amine-supported CO2

adsorbents in the presence of oxygen-containing gases. Microporous Mesoporous Mater

2011;145(1–3):146-9.

32
[13] Heydari-Gorji A, Sayari A. Thermal, oxidative, and CO2-induced degradation of

supported polyethylenimine adsorbents. Ind Eng Chem Res 2012;51(19):6887-94.

[14] Sayari A, Belmabkhout Y. Stabilization of amine-containing CO2 adsorbents: Dramatic

effect of water vapor. J Am Chem Soc 2010;132(18):6312-4.

[15] Bates ED, Mayton RD, Ntai I, Davis JH. CO2 capture by a task-specific ionic liquid. J

Am Chem Soc 2002;124(6):926-7.

[16] Drage TC, Snape CE, Stevens LA, Wood J, Wang J, Cooper AI, et al. Materials

challenges for the development of solid sorbents for post-combustion carbon capture. J

Mater Chem 2012;22(7):2815-23.

[17] Hao G-P, Li W-C, Qian D, Lu A-H. Rapid synthesis of nitrogen-doped porous carbon

monolith for CO2 Capture. Adv Mater 2010;22(7):853-7.

[18] Li P-Z, Zhao Y. Nitrogen-rich porous adsorbents for co 2 capture and storage. Chem

Asian J 2013;8(8):1680-91.

[19] Liu Z, Du Z, Song H, Wang C, Subhan F, Xing W, et al. The fabrication of porous N-

doped carbon from widely available urea formaldehyde resin for carbon dioxide

adsorption. J Colloid Interf Sci 2014;416:124-32.

[20] Pevida C, Plaza MG, Arias B, Fermoso J, Rubiera F, Pis JJ. Surface modification of

activated carbons for CO2 capture. Appl Surf Sci 2008;254(22):7165-72.

[21] Plaza MG, Pevida C, Arenillas A, Rubiera F, Pis JJ. CO2 capture by adsorption with

nitrogen enriched carbons. Fuel 2007;86(14):2204-12.

[22] Sevilla M, Parra JB, Fuertes AB. Assessment of the role of micropore size and N-doping

in co2 capture by porous carbons. ACS Appl Mater Interf 2013;5(13):6360-8.

33
[23] Sevilla M, Valle-Vigón P, Fuertes AB. N-Doped polypyrrole-based porous carbons for

CO2 capture. Adv Funct Mater 2011;21(14):2781-7.

[24] Wickramaratne NP, Jaroniec M. Importance of small micropores in CO 2 capture by

phenolic resin-based activated carbon spheres. J Mater Chem A 2013;1(1):112-6.

[25] Xing W, Liu C, Zhou Z, Zhang L, Zhou J, Zhuo S, et al. Superior CO 2 uptake of N-doped

activated carbon through hydrogen-bonding interaction. Energy Environ Sci

2012;5(6):7323-7.

[26] Zhang Z, Zhou J, Xing W, Xue Q, Yan Z, Zhuo S, et al. Critical role of small micropores

in high CO2 uptake. Phys Chem Chem Phys 2013;15(7):2523-9.

[27] Zhu X, Hillesheim PC, Mahurin SM, Wang C, Tian C, Brown S, et al. Efficient CO 2

capture by porous, nitrogen-doped carbonaceous adsorbents derived from task-specific

ionic liquids. ChemSusChem 2012;5(10):1912-7.

[28] Wang Q, Luo J, Zhong Z, Borgna A. CO2 capture by solid adsorbents and their

applications: current status and new trends. Energy Environ Sci 2011;4(1):42-55.

[29] Wang J, Huang L, Yang R, Zhang Z, Wu J, Gao Y, et al. Recent advances in solid

sorbents for CO2 capture and new development trends. Energy Environ Sci 2014;7:3478-

518.

[30] a ari A B mabk ou Y Da’na E. CO2 Deactivation of supported amines: does the

nature of amine matter? Langmuir 2012;28(9):4241-7.

[31] Sayari A, Heydari-Gorji A, Yang Y. CO2-Induced degradation of amine-containing

adsorbents: Reaction products and pathways. J Am Chem Soc 2012;134(33):13834-42.

34
[32] Rezaei F, Jones CW. Stability of supported amine adsorbents to SO2 and NOx in

postcombustion CO2 capture. 1. Single-component adsorption. Ind Eng Chem Res

2013;52(34):12192-201.

[33] Hallenbeck AP, Kitchin JR. Effects of O2 and SO2 on the capture capacity of a primary-

amine based polymeric CO2 sorbent. Ind Eng Chem Res 2013;52(31):10788-94.

[34] Khatri RA, Chuang SSC, Soong Y, Gray M. Thermal and chemical stability of

regenerable solid amine sorbent for CO2 capture. Energy Fuels 2006;20(4):1514-20.

[35] Ahmadalinezhad A, Tailor R, Sayari A. Molecular-level insights into the oxidative

degradation of grafted amines. Chem Eur J 2013;19(32):10543-50.

[36] Bollini P, Choi S, Drese JH, Jones CW. Oxidative degradation of aminosilica adsorbents

relevant to postcombustion CO2 capture. Energy Fuels 2011;25(5):2416-25.

[37] Bali S, Chen TT, Chaikittisilp W, Jones CW. Oxidative stability of amino polymer–

alumina hybrid adsorbents for carbon dioxide capture. Energy Fuels 2013;27(3):1547-54.

[38] Gebald C, Wurzbacher JA, Tingaut P, Steinfeld A. Stability of amine-functionalized

cellulose during temperature-vacuum-swing cycling for CO2 capture from air. Environ

Sci Technol 2013;47(17):10063-70.

[39] Calleja G, Sanz R, Arencibia A, Sanz-Pérez ES. Influence of drying conditions on amine-

functionalized SBA-15 as adsorbent of CO2. Top Catal 2011;54(1-4):135-45.

[40] Li W, Bollini P, Didas SA, Choi S, Drese JH, Jones CW. Structural Changes of silica

mesocellular foam supported amine-functionalized CO2 adsorbents upon exposure to

steam. ACS Appl Mater Interf 2010;2(11):3363-72.

[41] Gu J-M, Kim W-S, Hwang Y-K, Huh S. Template-free synthesis of N-doped porous

carbons and their gas sorption properties. Carbon 2013;56:208-17.

35
[42] Wang L, Yang RT. Significantly Increased CO2 Adsorption performance of

nanostructured templated carbon by tuning surface area and nitrogen doping. J Phys

Chem C 2011;116(1):1099-106.

[43] Wickramaratne NP, Jaroniec M. Activated carbon spheres for CO2 adsorption. ACS Appl

Mater Interf 2013;5(5):1849-55.

[44] Sevilla M, Fuertes AB. Sustainable porous carbons with a superior performance for CO 2

capture. Energy Environ Sci 2011;4(5):1765-71.

[45] Deng S, Wei H, Chen T, Wang B, Huang J, Yu G. Superior CO2 adsorption on pine nut

shell-derived activated carbons and the effective micropores at different temperatures.

Chem Eng J 2014;253:46-54.

[46] Nandi M, Okada K, Dutta A, Bhaumik A, Maruyama J, Derks D, et al. Unprecedented

CO2 uptake over highly porous N-doped activated carbon monoliths prepared by physical

activation. Chem Commun 2012;48(83):10283-5.

[47] Srinivas G, Krungleviciute V, Guo ZX, Yildirim T. Exceptional CO 2 capture in a

hierarchically porous carbon with simultaneous high surface area and pore volume.

Energy Environ Sci 2014;7(1):335-42.

[48] Fan X, Zhang L, Zhang G, Shu Z, Shi J. Chitosan derived nitrogen-doped microporous

carbons for high performance CO2 capture. Carbon 2013;61:423-30.

[49] Zhu B, Qiu K, Shang C, Guo Z. Naturally derived porous carbon with selective metal-

and/or nitrogen-doping for efficient CO2 capture and oxygen reduction. J Mater Chem A,

2015;3:5212-22.

36
[50] Chaffee AL, Knowles GP, Liang Z, Zhang J, Xiao P, Webley PA. CO 2 capture by

adsorption: Materials and process development. Int J Greenh Gas Control 2007;1(1):11-8.

[51] Morris JR, Contescu CI, Chisholm MF, Cooper VR, Guo J, He L, et al. Modern

approaches to studying gas adsorption in nanoporous carbons. J Mater Chem A

2013;1(33):9341-50.

[52] Presser V, McDonough J, Yeon S-H, Gogotsi Y. Effect of pore size on carbon dioxide

sorption by carbide derived carbon. Energy Environ Sci 2011;4(8):3059-66.

[53] Bermúdez J, Dominguez P, Arenillas A, Cot J, Weber J, Luque R. CO 2 separation and

capture properties of porous carbonaceous materials from leather residues. Materials

2013;6(10):4641-53.

[54] Sánchez-Sánchez A, Suárez-García F, Martínez-Alonso A, Tascón JMD. Influence of

porous texture and surface chemistry on the CO2 adsorption capacity of porous carbons:

Acidic and basic site interactions. ACS Appl Mater Interf 2014;(6):21237-47.

[55] Peter SA, Moharir AS, Jasra RV. Selective adsorption of oxygen over argon in alkaline-

earth-metal cation-exchanged zeolite X. Ind Eng Chem Res 2010;49(16):7524-9.

[56] Wang J, Senkovska I, Oschatz M, Lohe MR, Borchardt L, Heerwig A, et al. Imine-linked

polymer-derived nitrogen-doped microporous carbons with excellent CO2 capture

properties. ACS Appl Mater Interf 2013;5(8):3160-7.

[57] Wang J, Liu Q. An efficient one-step condensation and activation strategy to synthesize

porous carbons with optimal micropore sizes for highly selective CO 2 adsorption.

Nanoscale 2014;6(8):4148-56.

[58] Wang J, Liu Q. An ordered mesoporous aluminosilicate oxynitride template to prepare N-

incorporated ordered mesoporous carbon. J Phys Chem C 2007;111(20):7266-72.

37
[59] Shen W, Fan W. Nitrogen-containing porous carbons: synthesis and application. J Mater

Chem A 2013;1(4):999-1013.

[60] Zhao Y, Zhao L, Yao KX, Yang Y, Zhang Q, Han Y. Novel porous carbon materials with

ultrahigh nitrogen contents for selective CO2 capture. J Mater Chem 2012;22(37):19726-

31.

[61] Liu Y, Wilcox J. Molecular simulation studies of CO2 adsorption by carbon model

compounds for carbon capture and sequestration applications. Environ Sci Technol

2013;47(1):95-101.

[62] Cracknell R, Nicholson D, Tennison S, Bromhead J. Adsorption and selectivity of carbon

dioxide with methane and nitrogen in slit-shaped carbonaceous micropores: Simulation

and experiment. Adsorption 1996;2(3):193-203.

[63] Rabbani MG, El-Kaderi HM. Synthesis and characterization of porous benzimidazole-

linked polymers and their performance in small gas storage and selective uptake. Chem

Mater 2012;24(8):1511-7.

[64] Ravikovitch PI, Vishnyakov A, Russo R, Neimark AV. Unified approach to pore size

characterization of microporous carbonaceous materials from N 2, Ar, and CO2 adsorption

isotherms. Langmuir 2000;16(5):2311-20.

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