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Accepted Article
Title: Effect of Heat Treatment on the Nitrogen Content and Its Role
on the CO2 Adsorption Capacity of Highly Ordered Mesoporous
Carbon Nitride

Authors: Kripal S. Lakhi, Dae-Hwan Park, Stalin Joseph, Siddulu N.

Talapaneni, Ugo Ravon, Khalid Al-Bahily, and Ajayan Vinu

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To be cited as: Chem. Asian J. 10.1002/asia.201601707

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Effect of Heat Treatment on the Nitrogen Content and Its Role on

the CO2 Adsorption Capacity of Highly Ordered Mesoporous
Carbon Nitride
Kripal S. Lakhi,[a] Dae-Hwan Park,*[a] Stalin Joseph,[a] Siddulu. N. Talapaneni,[a] Ugo Ravon,[b] Khalid
Al-Bahily,[b] and Ajayan Vinu*[a]
Abstract: Mesoporous carbon nitrides (MCN) with rod shaped the current rate, it would become extremely difficult to contain
morphology and tunable nitrogen contents have been synthesized the increase in global temperature below 2 °C. Consequently,
via calcination free method using ethanol-washed mesoporous SBA- the global warming and climate change threat posed by CO 2
15 as templates at different carbonization temperatures. Carbon pollution has resulted in massive research activities being
tetrachloride (CTC) and ethylenediamine (EDA) were used as the pursued aggressively in academia, government institutions and
sources of carbon and nitrogen respectively. The resulting MCN industry alike.[4]
materials were characterized with low and high angle power XRD,
A number of advanced and cost effective technologies are
N2 adsorption, HR-SEM, HR-TEM, CHN elemental analysis, XPS
being developed for capture, storage, and utilization of
and. XANES techniques. It is observed that the carbonization
atmospheric CO2. Concurrently, technologies are also being
temperature plays a critical role in controlling not only the crystallinity
developed to convert the captured CO2 into value added
but also the nitrogen content and the textural parameters of the
chemicals.[5] However, from an economic standpoint, the CO2
samples including specific surface area and specific pore volume.
capture and its subsequent conversion into value added
Nitrogen content of MCN decreases with the concomitant increase of
products continue to pose a challenge to the scientific
specific surface area and specific pore volume as well as the
community around the globe. Industrially, aqueous amine
crystallinity of the samples as the carbonization temperature is
scrubbing processes are the most commonly used methods to
increased. The results also reveal that the structural order of the
capture CO2 from flue gases.[6] However, the amine based
materials is retained even after the heat treatment at temperature
processes inherently suffer from a number of drawbacks
upto 900 °C with a significant reduction of the N content but the
including a high regeneration cost, expensive and toxic
structure is partially damaged at 1000 °C. It is also found that the
chemicals and corrosion of equipment. [6,7] Membrane separation
CO2 adsorption capacity of these materials is not only dependent on
processes are also used for CO2 capture but their high cost
the textural parameters but also on the nitrogen content. The MCN
makes the overall process economically untenable and therefore
prepared at 900 °C, which has optimum BET surface area and
unappealing.[7] In contrast, inorganic solid materials based
nitrogen content, registers the CO2 adsorption capacity of 20.1
adsorbents for CO2 capture present an attractive proposition
mmol/g at 273K and 30 bar, which is much higher than that of
both from economic and application viewpoints. Solid adsorption
mesoporous silica, MCN-1, activated carbon and multi-walled carbon
based methods are particularly attractive since the process is
nanotubes.
devoid of solvents which has a direct bearing on the energy
requirement for the regeneration step. [8]

Introduction Among the solid based adsorbents, porous materials were

found to be excellent candidates for CO2 adsorption because of
Carbon dioxide (CO2) has been recognized as the potent cause their inherent properties such as high surface area, pore
behind global climate change.[1] Among the greenhouse gases volume,[7] and the presence of free surface functional groups
present in the atmosphere, the quantity of CO2 is the largest and which can be used to tune the structural, textural properties and
rapidly increasing due to continuous anthropogenic emissions facilitate easy chemical modification. [8] Several porous materials
from sources such as fossil fuel combustion in the transport such as activated carbons, porous carbons, zeolites,
industry, power generation plants and other associated human mesoporous silica, metal-organic frameworks have been
activities.[2] According to an estimate, global CO2 emissions investigated as potential solid adsorbents for CO2.[9-11] However,
reached a massive 34 billion tones in 2011, the highest ever each of these materials has their own advantages and
recorded.[3] It is believed that if the CO2 emissions continue at disadvantages. For example, zeolites offer large surface areas
and have specific sites suitable for adsorption but the small
pore system poses diffusional problems. [7] On the other hand,
[a] K.S. Lakhi, Dr. D.-H. Park, Prof. A.Vinu metal-organic frameworks suffer from low physicochemical
Future Industries Institute, Division of Information Technology, stability even though they exhibit a high specific surface area. [11]
Engineering and Environment, Mawson Lakes Campus, University
of South Australia, Adelaide 5095, Australia Porous carbon materials present as an ideal adsorbent for
E-mail: [email protected]
E-mail: [email protected]
CO2 because of their high surface area, low cost and easy
[b] Dr. U. Ravon, Dr. K. Al-Bahily regeneration and high chemical and thermal stability, tunable
bSABIC Corporate Research and Development Center at KAUST, porosity and easy to control morphology. [2,12] However, the
Saudi Basic Industries Corporation, Thuwal 23955, Saudi Arabia adsorption capacity of carbon materials is low due to the
Supporting information for this article is given via a link at the end of weaker adsorbent-adsorbate interaction which is ascribed to
the document. hydrophobic nature and lack of surface charges. [2,13] It has been

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suggested in a number of reports that incorporation of basic Results and Discussion
functionalities such as nitrogen or free –NH or –NH2 groups
could enhance the CO2 adsorption capacity of the carbon based X-ray diffraction
adsorbents as nitrogen atoms can interact through their lone
pairs with the mildly acidic CO2 molecule.[2,14-15] It has been Figure 1 shows the low angle powder XRD patterns for the
reported that incorporation of nitrogen atom in the carbon matrix E-MCN-1-T samples (E = ethanol extraction, T = 600 to 1000 °C).
is a complex process as it is normally done either by post As can be seen in the XRD plots, all the E-MCN-1-T samples
treatment with ammonia at high temperature or by organic exhibit a high intense peak at low angle together with a few high
functionalization of carbon materials with a suitable amine. [2,16-18] order peaks with varying intensities. The sharp and prominent
However, these methods of incorporation of nitrogen atoms in peak is indexed as (100) reflection plane while the low order
the carbon matrix are expensive and time consuming and there peak is indexed as (110) reflection plan. Further, it can be seen
is very little control over the basic functions that are introduced. [2] that the effect of changing the carbonization temperature from
600 °C through 1000 °C on the structure of the MCN is clearly
The above problems associated with incorporation of reflected in the XRD patterns. As the carbonization temperature
nitrogen or basic sites in the carbon matrix can be overcome in is varied from 600 to 1000 °C, a significant difference in the
mesoporous carbon nitride (MCN) materials. The MCN intensity of the peaks is observed. For example, the peak
represents a class of highly versatile material which has inherent intensity increases on increasing the temperature from 600 to
basic functionalities because of the presence of large number of 700 °C and then shows a clear decreasing trend as the
free –NH and –NH2 on the surface besides tunable pore temperature is further increased up to 1000 °C . Interestingly, the
structure, morphology and textural properties 19. MCN are multi- peak is shifted towards higher angle as the carbonization
faceted materials which find applications in basic catalysis, [20] temperature is increased, revealing a reduction in the structural
enzyme like catalysis,[21] gas sensing,[22] CO2 capture,[23,24] water order of the sample. It should be mentioned that the (100)
splitting,[25] energy storage,[26] and environment applications.[27] reflection of the sample treated at 1000 °C became quite broad
In our previous report,[28] the synthesis of MCN with controlled and shifted significantly to higher angle, revealing a partial
morphology was successfully achieved by synthesizing the silica destruction of the mesostructural order of this sample due to the
template under “static” condition and then using it as a template contraction of the CN framework structure. The contraction or
to prepare MCN with rod shaped morphology which showed partial structural collapse is understandable as the
enhanced CO2 capacity compared to MCN with irregular decomposition of the nitrogen from the carbon matrix makes a
morphology. However, the low temperature carbonization is huge strain in the structure, leaving a disturbance in the
needed to preserve a high content of nitrogen in the carbon structural order of the materials. This is also confirmed by a
matrix due to the poor thermodynamic stability of nitrogen in the significant reduction in the intensity of the main peak of the
carbon matrix but is also the reason for the amorphous CN wall sample heat treated at 1000 °C and the unit cell size which
structure together with low specific surface area in MCN. By decreases from 11.6 nm to 10.7 nm.
tuning the carbonization temperature, the nitrogen content,
crystallinity and specific surface area and specific pore volume
could be optimized. However, no reports are available on the
effects of carbonization temperature on the structural and
textural properties, morphology control, nitrogen contents, and
basic property of MCN with controlled morphology for CO2
capture.

In this work, we report on the synthesis of MCN with

tunable nitrogen content, crystallinity and textural parameters by
varying the carbonization temperature. Uncalcined and ethanol
washed mesoporous silica washed has been used as templates
for the fabrication of MCN in order to reduce the energy
intensive process of fabrication of MCN. The nitrogen content
and graphitic nature of the MCN is tuned by varying the
carbonization temperature from 600 to 1000 °C. The MCN
materials exhibited uniform rod shaped morphology and are
evaluated as adsorbents for CO2 at different temperatures and
pressure upto 30 bar. The surface interaction between the
adsorbents with different nitrogen content and specific surface
area and the CO2 molecules is studied. The effect of varying the Figure 1. Low angle XRD patterns of E-MCN-1-T samples (T is the
carbonization temperature).
carbonization temperature on the textural properties, and
nitrogen content and their role on controlling the adsorption In order to understand the crystal structure of the sample
capacity for CO2 are also discussed. It is found that the optimum as a function of calcination temperature, the samples were
amount of the nitrogen content and specific surface area analyzed by wide angle XRD measurements (Figure 1S). As can
together with a high crystallinity is required to achieve a be seen in Figure 1S, the XRD patterns of MCN samples show
maximum CO2 adsorption capacity. one broad peak in the range 24-25 °C. This peak is assigned to
(002) plane and is characteristic of interplanar stacking peaks of
aromatic system.[28] The d spacing calculated from (002) plane is

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around 0.34-0.35 nm for the samples which is similar to the successful replication of mesoporosity from the silica template to
value obtained for nonporous carbon nitrides and indicates that the MCN samples. It is interesting to note that the amount of
the wall structure of these samples is composed of carbon and nitrogen adsorbed increases with increasing the carbonization
nitrogen that are arranged in turbostratic form. [29,30] It should be temperature. From the shape of the isotherm, it is clear that the
noted that the intensity of higher order peaks increases with pore structure is maintained till the carbonization temperature of
increasing the carbonization temperature, revealing a change in 900 °C. However, the structure of the sample is completely
the crystallinity of the samples at different temperature. The retained. The capillary condensation step of the isotherms
intensity of the higher order graphic peak is much higher for E- changes significantly when the carbonization temperature is
MCN-1-1000 than that of other samples, suggesting a high increased to 1000 °C. This suggests a slow degradation of
crystallinity in the sample. mesostructure of the sample. This is also supported by the data
obtained from XRD.
Table 1 shows the textural properties i.e., pore volume,
N2 adsorption-desorption
pore diameter, and surface areas of the samples. Since all the
samples were prepared with the same silica E-SBA-15 template
and filled with same quantity of precursors, one would expect
the pore diameter of the MCN to be nearly same or show a
progressive increase trend. Interestingly, the pore diameters of
all the samples are nearly same and lie in the range of 4.4-4.9
nm with the samples carbonized at 1000 °C having the highest
pore diameter of 4.9 nm. This could be attributed to the removal
of a few layers of CN framework due to the decomposition of
nitrogen from the CN matrix due to the low thermodynamic
stability of nitrogen in carbon matrix. The pore volumes also
show an increasing trend as the carbonization temperature is
increased from 600 to 1000 °C which is due to the change in the
pore diameter of the materials.

Table 1. Textural properties and CO2 adsorption capacities of SEW-MCN-1-

130-T samples.

PD[a]
[b]
ao d PV BET S.A CO2
Sample
(nm) (nm) (cm3/g) (nm) (m2/g) (mmol/g)

E-MCN-1-600 11.6 10.1 0.72 4.4 655 15.4

E-MCN-1-700 10.8 9.4 0.88 4.2 705 17.4

E-MCN-1-800 10.7 9.32 0.91 4.4 735 17.2

E-MCN-1-900 10.9 9.48 0.92 4.5 738 20.1

E-MCN-1-1000 11.3 9.84 1.00 4.9 780 18.4

[a] Pore diameter calculated using the adsorption branch.

[b] CO2 adsorption isotherms recorded using pure and dry CO2 at 0 oC/30 bar.

Figure 3 shows the variation of pore volume and BET

Figure 2 (a,b). N2 adsorption-desorption isotherms of E-MCN-1-T samples. specific surface areas of the samples with carbonization
temperature. As anticipated, all the samples show increasing
trend with increase in carbonization temperature from 600 to
The mesoporous nature of MCN treated at different 1000 °C. The increase in the specific surface area of the
temperatures was investigated using N2 sorption experiments. samples with increasing carbonization temperature is mainly
The N2 adsorption and desorption isotherms for the MCN ascribed to the formation of the micropores which are originated
samples is shown in Figure 2(a,b) while the BJH pore-size from the decomposition of the nitrogen from the CN matrix at a
distributions obtained using the adsorption branch are shown in high temperature. However, this effect is more significant when
Figure 2S. As can be seen in Figure 2, all the MCN samples the carbonization temperature is 1000 °C as the nitrogen content
also show type IV nature which as per the IUPAC convention of the sample is significantly low. This explains clearly the
corresponds to mesoporous materials. Further all samples reason for the increase of the pore diameter and the specific
exhibit H1 type hysteresis loop which is further suggestive of surface area of the sample treated at a high temperature.
presence of mesoporous structure in the MCN samples and a

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even at higher carbonization temperature of 1000 °C. It may be
mentioned that although the rod shaped morphology is retained
at higher carbonization temperature, the size of the particles is
significantly affected by the high temperature carbonization. For
example, the size of the SEW-MCN-1-600 particles is much
larger than that of SEW-MCN-1-700/800/900/1000 (Figure 4).
This is also confirmed in the high resolution scanning
electron microscope images of the sample, which show a large
array of mesopores. However, the pore structure in the particles
is partially destroyed as the carbonization temperature is
increased to 1000 °C (Figure 4B). The reduction in the size of
the particles at higher carbonization temperature is attributed to
the breaking of CN bonding in the wall structure of the MCN
which leads to the breakage of large particles. This reason is
also supported by the fact that the particles become thinner as
the carbonization temperature is increased. The surface texture
of the particles prepared at higher carbonization temperature
shows the presence of a large number of micropores which are
Figure 3. Variation of pore volume (PV) and BET surface area with probably generated due to liberation of N from CN matric
carbonization temperature.. because of the higher carbonization temperature and eventually
contribute to the large specific surface and pore volumes.
The mesoporosity in the E-MCN-1-T samples was also
SEM and TEM images investigated using HR-TEM. Figure 5 shows the HR-TEM
images of all the samples. From the images, it can be clearly
seen that all the samples except E-MCN-1-1000 exhibit parallel
Figure 4 (A and B) shows the SEM images of the E-MCN- mesoporous channels confirming the presence of mesosporosity.
1-T samples. From the SEM images, it is clear that each of the The TEM images are similar to those of the parent silica
samples has uniform rod shaped morphology. The morphology template (Figure 4S) suggesting successful replication of
is similar to the rod shaped morphology exhibited by SBA-15 mesoporosity from the template to the MCN materials. The TEM
prepared under static condition.[23] This means that morphology results further confirm the mesoporous nature of E-MCN-1-T
of the template is successfully replicated into the MCN. Further, materials as deduced from N2 adsorption experiments. These
it is also interesting that the particle morphology is conserved results reveal that the samples possess excellent thermal

Figure 4. SEM images of E-MCN-1-T samples (low resolution (top) and high resolution (bottom)).

Figure 5. HR-TEM images of E-MCN-1-T samples.

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stability. However, the mesostructure of E-MCN-1-1000 is temperature. It should also be noted that the peak width of the G
somewhat affected when the carbonization temperature is band is much narrower for the samples treated at high
increased to 1000 °C. This is confirmed by the fact that only carbonization temperature. From this result it can be concluded
small areas of the images contain hexagonally ordered that the pore wall is composed of a large number of sp2-
mesopores while the disordered ordered pores are seen in other hybridized C species. This further supports the fact that the
areas of the samples. These results are in perfect agreement disorder in the sp2-hybridized carbon in the CN matrix can be
with the data obtained from the nitrogen adsorption and XRD controlled with a simple adjustment of the carbonization
measurement that reveal the collapse of the mesostructure at temperature.
carbonization temperature higher than 1000 °C.
With increasing the carbonization temperature, N atoms X-ray photoelectron spectroscopy (XPS)
are partially removed from the CN matrix which weakens the CN
walls of the mesostructure. High energy generated at high
carbonization temperature is found to be more than enough to
break the CN walls of mesostructure that ultimately destroys the
mesostructure and decreases the particle size. These results
reveal that the optimum carbonization temperature is critical to
preserve not only the mesostructure but also maintain the CN
framework with high nitrogen content together with a high
specific surface area and large pore volume. Based on the
surface properties and mesostructural details, it may be
concluded that the carbonization temperature of 900 °C is the
best condition to preserve both the structural order and excellent
textural parameters.

Raman spectroscopy

E-MCN-1-600
E-MCN-1-700
E-MCN-1-800
E-MCN-1-900
Intensity (a.u.)

E-MCN-1-1000

Figure 7. High resolution N1s scan at (a) 600 °C, (b) 700 °C, (c) 800 °C, (d)
900 °C, (e) 1000 °C, and (f) variation of surface atomic carbon and nitrogen
with carbonization temperature (600 to 1000 oC).

500 1000 1500 2000 2500

-1
Raman Shift (cm ) Table 2. Elemental analysis from XPS and CNS analyser.

Figure 6. Raman spectra of E-MCN-1-T samples.

XPS CNS analysis

(surface atomic composition) (Bulk composition)
The effect of the carbonization temperature on the
Sample
graphitic nature MCN was also analyzed by Raman
spectroscopy and the results are shown in Figure 6. The Raman C N O C N
(%) (%) (%) (%) (%)
spectra of all the samples show two distinct and intense bands
at 1371 cm-1 and1575 cm-1, which are attributed to the D E-MCN-1-600 80.7 16.2 2.7 64.6 17.8
(disordered) and G (graphitic) bands of the sp2-hybridized based
carbon.[30] Normally, the relative intensity of D and G band in the E-MCN-1-700 82.4 14.3 3.0 66.4 14.1
Raman spectrum gives the information about the quantity of the
E-MCN-1-800 86.2 10.3 3.4 71.7 10.6
structural defects in the CN wall structure of MCN. It is
interesting to note that the ID/IG ratio of E-MCN-1-600 is 0.85 E-MCN-1-900 89.3 6.3 4.4 71.0 6.2
while it is increased to 0.94 when the carbonization temperature
is increased to 900 °C. This reveals that the graphitic nature of E-MCN-1-1000 92.3 4.0 3.0 75 4.3

the CN wall structure can be improved with the carbonization

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The surface composition, and the nature and co-ordination the CN bonds. This is in agreement with the fact that the sample
of C and N in the samples were analyzed by XPS technique. at 600 °C has the highest N atomic % while the sample at
Figure 3S (supporting information) shows the survey spectrum 1000 °C has the lowest N content. Further, the two curves in
for all these materials. In addition to the expected elements Figure 7f intersect at carbonization temperature between 800-
namely C, N and O, the survey spectrum also shows the 900 °C suggesting that the optimum temperature is somewhere
presence of trace quantities of F. The fluorine could be attributed close to 850 °C and the corresponding C and N atomic
to the HF used for dissolving silica whereas the oxygen mainly percentages are the optimum values of C and N for these
comes from the adsorption of atmospheric CO2 or moisture or samples. From the survey spectra, it is clear that changing the
from the ethanol used in the washing procedure. The elemental carbonization temperature has a direct bearing on the quantity of
surface composition for different samples is shown in Table 2. N content which in turn affects the chemistry of N in the samples.
Figure 7f and show the variation of C and N surface atomic In other words, the environment and chemistry of N in the
composition with carbonization temperature. From the Figure 7f, samples changes drastically with changing carbonization
it is clear that there is a progressive increase in the C atomic % temperature and the same was investigated through high
with a concomitant reduction in the quantity of N as the resolution N1s spectra of these samples. These results are
carbonization temperature is increased. This is an expected further reinforced by the bulk C and N composition obtained
result since the thermodynamic stability of N in the carbon matrix from CNS analysis as shown in Table 2.
is a function of carbonization temperature. At higher The curve-fitted N1s spectra are displayed in Figure 7 (a-
temperatures, N tends to escape from the system by breaking e). All spectra were calibrated using the graphitic C1s at

Figure 8. (A) C K-edge and (B) N K-edge NEXAFS spectra of (a) E-MCN-1-600 (b) E-MCN-1-700, (c) E-MCN-1-800, (d) E-MCN-1-900, and (e) E-MCN-1-1000
(inset: proposed molecular structure). Intensity ratio of the π* to σ* peak at the (A) C K-edge and (B) N K-edge as a function of carbonization temperature.

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284.4eV. The four N components present are consistent with the morphology and therefore qualify as an excellent adsorbents for
following N species: ~398 eV which is attributed to the sp 2 N CO2 uptake. Figure 9 shows the CO2 adsorption isotherms for
atoms bonded to C atoms in aromatic rings while ~399.2 eV the E-MCN-1-T samples at 0 oC and up to 30 bar pressure.
corresponds to N atoms in an amide (O=C-NH2) group; the peak From the isotherms, it is clear that the amount of CO 2 adsorbed
at ~400.5 eV is related with the N atoms trigonally bonded to increases with increasing the carbonization temperature upto
three C atoms whereas the peak at 401.5 eV is ascribed to the 900 °C but decreases at 1000 °C. The sample carbonized at 900
quaternary N+ (N three fold sp2 bonded in a salt).[31,32] There has o
C records the highest CO2 adsorption capacity of 20.1 mmol/g
been a reduction in the pyridine N species (~399.2 eV) with a compared to other samples. This is the highest ever value
corresponding increase in the N trigonally bonded to three C reported so far for the MCN based samples at the adsorption
atoms (~400.5 eV) as the carbonization temperature is condition of 0 oC and up to 30 bar pressure. Table 1 shows the
increased from 600 to 1000 oC. This is because of the low CO2 adsorption capacities of different samples carbonized at
thermodynamics stability of nitrogen in the carbon matrix. different temperature. The highest CO2 adsorption capacity of E-
MCN-1-900 sample is attributed to its optimum surface area and
Near edge X-ray absorption fine structure (NEXAFS) nitrogen content.
A comparison of the textural properties (Table 1) and
Synchrotron-based near-edge X-ray absorption fine nitrogen content of the samples (Table 2) and the corresponding
structure (NEXAFS) was analyzed to further probe bonding CO2 adsorption capacities suggests that it is not the highest
nature and structural changes of E-MCN-1-T samples at surface area or the highest nitrogen content alone that dictates
different carbonization temperatures. All NEXAFS spectra were the overall CO2 adsorption capacity of a material. Instead there
normalized at the maximum intensity for comparison purposes. appears to be a synergy in the contribution from surface area
In the carbon K-edge region (Figure 8A), three main features are and nitrogen content and a sample with optimum surface area
identified along with structural defects in the E-MCN-1-T and nitrogen content together with a high crystallinity records the
materials: i) π*C=C (C1) at 286.2 eV and ii) π*C–N–C (C2) at 288.0 highest CO2 adsorption. This observation is also supported and
eV due to the transitions from the 1s orbital to different π* levels,
further reinforced by the conclusions drawn from Figure 7 based
and iii) broader resonance over the range 292-300 eV on the XPS analysis. The effect of temperature on the CO 2
corresponding to the σ*C–C transition (C3). In the nitrogen K- adsorption was investigated by recording the adsorption
edge NEXAFS spectra (Fig. 8B), three typical π* resonance isotherms for each sample at three different temperature 0, 10
peaks observed at 399.3, 400.5, and 402.3 eV corresponding to
and 25 oC and pressure up to 30 bar.
nitrogen atoms with two carbon neighbours in a pyridine-like
configuration (π*C–N–C (N1)), sp2/sp3 CNH bonding configuration
(π*C–N–H (N2)), and sp3 N–3C bridging among three structural
units (π*N–3C (N3)).[33,34] The intensity ratio of π*/σ* peaks at the
C and N K-edge as a function of carbonization temperature is
shown in Figure 8C and 8D. At high carbonization temperature
of 1000 °C, the significant decrease of π*/σ* ratio in both C and
N K-edges is the sign of the deformation of sp2 graphite-like
MCN structure. Both the sp2 cluster size and distribution of sp2
domain in the MCN matrix was changed with sp3 bonding
configurations in amorphous carbon network accompanying with
tiny peaks around 289.2 (1s→π*C-H) and 290.6 eV (1s→π*C=O) in
CN bonds. As compared with an intensity ratio of π*(N3)/σ*(N4),
decreased intensities of π*(N1)/σ*(N4) and π*(N2)/σ*(N4) reveal
deformation of pyridine-like structure and partial breaking of N–
3C bridgings, which is in good agreement with the XPS results.

High pressure CO2 adsorption

Figure 9. CO2 adsorption isotherms of E-MCN-1-T samples at 273K and 30
The CO2 adsorption capacity of the MCN materials with bar.
different nitrogen content was evaluated at different analysis
temperatures of 0, 10 and 25 °C and pressure range of 0-30 bar.
A large number of reports have indicated that a combination of
The adsorption capacities of the samples E-MCN-1-T (T =
high surface area and high nitrogen density are some of the 600 TO 1000 OC) at three different analysis temperature (0,10
necessary attributes of good CO2 adsorbents.[2,23-24] As and 25 oC) are shown in supporting information Figure 5S(a-e)
discussed earlier, MCN have large number of free –NH and – and the corresponding values are shown in Table 1S.It is clear
NH2 groups which can act to anchor the slightly acidic molecule
from the adsorption capacities that the adsorption temperature is
such as CO2. Previous reports have indicated how regular increased from 0 to 25 °C, the adsorption quantity decreases
morphology of the adsorbents facilitates easy access to the drastically. This suggests that the adsorption process is
active sites and enhances inter- particle diffusion besides exothermic in nature and is favored at lower adsorption
affecting the textural properties of the adsorbent material.[23]
temperatures. Mathematically, the CO2 adsorption isotherms
In the present study, E-MCN-1-T samples demonstrate represent strictly monotonic increasing functions of pressure
reasonably high surface area [655-781] m2/g, surface nitrogen which means as the pressure is increased; the quantity of CO2
content varying from [16.17-2.43] % and uniform rod shaped adsorbed also increases. Based on the above discussion, it can

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be concluded that CO2 adsorption by E-MCN-1-T samples are This implies that CO2 adsorption on E-MCN-1-900 is
strongly affected by temperature and pressure conditions and predominantly physical in nature and therefore highly reversible.
low temperatures and higher pressures favor higher adsorption. The materials can be regenerated by heating it to 250 °C for
For the purpose of comparison, Table 2S shows the CO2 about 6 hr under vacuum and the regenerated materials shows
adsorption capacities of different materials at different the same amount of adsorption capacity at the same adsorption
temperature and pressure conditions.[35-38] condition, revealing the structural stability of the MCN
In general, the total amount of adsorbed CO2 molecules nanostructures carbonized at high temperature.
depends mainly on the surface area, porosity, and pore volume
of the mesoporous materials. The abundant presence of
nitrogen surface groups of MCN materials is also responsible for
the enhancement of CO2 uptake, but the correlation and effect of
the different nitrogen functional groups on the CO 2 capture has
not been systematically clarified in previous works. As discussed,
the total amount of CO2 uptake is higher for the MCN sample
carbonized at 900 °C than for those synthesized at other
temperatures, indicating that the types of quaternary nitrogen
were relatively more and contributed to the improvement of CO2
capture than pyridinic and pyrrolic functionalities at each
adsorption temperature. As noted in the XPS analysis, with
increasing carbonization temperature, the pyridinic nitrogen
decreases while quaternary N species increases. As expected
from the existence of strong specific attractions via charge-
induced chemisorption and dipole-induced dipole interaction, it
was demonstrated that incorporation of basic functionalities,
especially quaternary structure inside the MCN matrix, can
improve the adsorption capacity of CO2 with a soft acidic Figure 10. Variation of Isosteric heat of adsorption with CO2 loading for E-
character at relatively low pressure and high temperature. MCN-1-T samples.
Furthermore, the strength of adsorbate-adsorbent
interaction was investigated by calculating the isosteric heat of
adsorption from the Clausius-Clapeyron equation using three Conclusions
isotherms recorded at 0, 10 and 25 °C for each sample as
shown in Figure 10 and values indicated in Table 3S. It appears In summary, mesoporous carbon nitride with tunable
that among the samples studied in this work, the sample crystallinity, nitrogen content and textural parameters were
carbonized at 600 °C which has the highest surface nitrogen prepared from uncalcined silica template by tuning the
content (Table 1S) and lowest surface area and pore volume carbonization temperature from 600 to 1000 °C. It was found
shows the highest isosteric heat of adsorption at lower CO 2 that the specific surface area and the specific pore volume of the
loading whereas the sample which recorded the highest overall MCN increased with the concomitant decrease of nitrogen
CO2 adsorption shows the lowest isosteric heat of adsorption at content as the carbonization temperature was increased from
lower CO2 loading. These results are in agreement with the 600 to 1000 °C. The structural order of the sample was partially
reports in the literature.[2] The values of isosteric heat of destroyed when the carbonization temperature was increased
adsorption obtained in this study are comparable to the above 900 °C. XPS and XANES results reveal that coordination
theoretically predicated values for Li-Ferrierite.[39] It is believed of N with the carbon matrix in MCN was significantly affected by
that the overall CO2 adsorption is largely dictated by the porosity the increase of carbonization temperature from 600 to 1000 oC.
of the material (such as surface area, pore volume) whereas the We also demonstrated the effect of carbonization temperature
surface nitrogen functions are mainly responsible for higher on the CO2 adsorption capacity of the materials. We have shown
isosteric heat of adsorption at lower CO2 loading. Thus, it is clear that MCN can be prepared from ethanol washed silica as a
from this study that there is a synergistic play between the template which is less energetically demanding than the
textural properties and nitrogen density and that CO 2 adsorption calcination route. It has been found that the sample prepared at
capacity is strongly influenced by textural parameters whereas 900 °C registered the highest adsorption capacity of 20.1
nitrogen density dictates the strength of interaction between mmol/g which is the highest ever value reported so far for the
adsorbate and adsorbent. From these results, it is clear that MCN nanostructures. Although the heat of adsorption of
optimized carbonization temperature which has the potential to samples with the higher nitrogen content was higher, the amount
control the nitrogen, crystallinity and textural properties of the of CO2 adsorption capacity was lower than that of sample with
materials is the key factor in dictating the final performance of lower nitrogen content but higher surface area. It can be
the MCN nanostructures. The materials are recycled and re- concluded that the samples with the optimum nitrogen content
used several times and no visible loss of adsorption capacity is and the high specific surface area and pore volume are the best
observed. The CO2 adsorption-desorption isotherm for E-MCN- adsorbents for the CO2 adsorption. It is believed that this work
1-900 sample is shown in Figure 6S (supporting information). would provide a platform for making new adsorbent materials for
From figure 6S, it is clear that the CO2 adsorption on E-MCN-1- the specific adsorption of CO2 molecules and would open new
900 is completely reversible as the adsorption and desorption avenues for development of other cost effective and versatile
arms almost completely overlap over the entire pressure range. adsorbents for CO2 capture.

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Experimental Section Pore size distribution was obtained from the adsorption branches of the
nitrogen isotherms using the BJH model. XPS data was acquired using a
Kratos Axis ULTRA X-ray Photoelectron Spectrometer incorporating a
Materials synthesis and reagents 165mm hemispherical electron energy analyser. The incident radiation
was Monochromatic Al Kα X-rays (1486.6eV) at 225W (15kV, 15ma).
Survey (wide) scans were taken at analyser pass energy of 160 eV and
The silica template E-SBA-15 (E is abbreviated as ethanol extraction) multiplex (narrow) high resolution scans at 20 eV. Survey scans were
was synthesized under static condition using a soft templating approach carried out over 1200-0 eV binding energy range with 1.0 eV steps and a
o
under strongly acidic conditions. After hydrothermal treatment at 130 C, dwell time of 100 ms. Narrow high-resolution scans were run with 0.05
the polymeric surfactant P-123 was removed by solvent extraction using eV steps and 250 ms dwell time. Base pressure in the analysis chamber
ethanol at room temperature. In a typical synthesis, 2g of non-ionic was 1.0x10-9 torr and during sample analysis 1.0x10-8 torr. Atomic
surfactant Pluronic P-123 which is a triblock copolymer (EO20 PO70 concentrations were calculated using the CasaXPS version 2.3.14
EO20), Avg. mwt ~5800, Sigma-Aldrich) was added to 15 g of water in a software and a Shirley baseline with Kratos library Relative Sensitivity
polypropylene (PP) bottle with a cap and the solution was stirred for 4 hr Factors (RSFs). Peak fitting of the high-resolution data was also carried
at room temperature followed by addition of 60 g of 2 M HCl and out using the CasaXPS software. When doing the curve fitting of XPS
o
simultaneously the temperature was raised to 40 C. Then, the mixture spectra, it was important to keep the FWHM (full-width half maximum) of
was stirred for 2 hr. After this, 4.5 g of TEOS (tetraethyl orthosilicate, all species in the one element to the same value +/- 0.2 eV. A Shirley
98% Sigma-Aldrich) was added and the mixture was stirred for just 20 background was used throughout. For the N1s spectra taken at analyser
min after which stirring was stopped completely and the sample was left pass energy of 20 eV, it was established that a FWHM of 1.3 eV was
undisturbed for the next 24 hr with the temperature in the water bath ideal. These restrictions not only gave good fits but also gave
maintained at 40 oC. The solution mixture was then transferred to a reasonable cross-correlation of the N1s species with the corresponding C
Teflon lined autoclave and kept in an oven at 130 oC for 48 hr. The 1s species. The synchrotron NEXAFS measurements were carried out
product was filtered in hot and washed three times with water. The on the soft X-ray spectroscopy beamline at the Australian Synchrotron.
o
filtered product was dried in an oven at 100 C for 6-8 hr and then Spectra have been recorded in partial electron yield and then raw data
washed twice with ethanol, each time stirred with ethanol for 3 hr at room were normalized to the photoelectron current of the photon beam.
temperature. Finally filtered sample is dried again in an oven overnight
before use. E-MCN-1-T samples were prepared by using a hard
templating approach involving a polymerization reaction between the High pressure CO2 adsorption
carbon source CCl4 and nitrogen source EDA inside the mesopores of
the ethanol washed silica template. In a typical synthesis, 0.5 g of E-
SBA-15 was mixed with 3 g of CCl4 and 1.35 g of EDA in a round bottom High pressure CO2 adsorption was carried out on a Quanta chrome Isorb
flask fitted with water cooled condenser. The mixture was refluxed at 90 HP1 equipped with temperature controlled circulator. The CO2 adsorption
o was carried out up to a pressure of 30 bar and different analysis
C for 6 hr under constant stirring. The temperature was increased in
o o
steps of 10 C from 60 to 90 C. After 6 hr, the unreacted CCl4 and EDA temperatures of 0, 10 and 25 oC were used. Prior to CO2 adsorption,
in the composite polymer was removed in rotavapor at 55 oC. The samples were degassed for 10 hr at 250 oC. The isosteric heat of
o adsorption was calculated using Clausius-Clapeyron equation. The
sample was then dried at 100 C for 6 hr and then crushed into powder
using a mortar and pestle. The crushed powder was then carbonized in a structural morphology of E-MCN-1-T samples was observed in JEOL FE
tubular furnace at 600 oC for 5 hr under nitrogen flow. The carbonized SEM 7001. The sample preparation for HR-SEM was involved sprinkling
sample was then treated with 5% HF and the sample was washed three of a small quantity of powder sample on the carbon tab. The stub is kept
times with excess ethanol and then kept for drying at 100 oC for 6 hr in a vacuum oven at 70 oC for 7 hr before insertion into the SEM. The
before characterization. Following the above procedure, a series of MCN samples were coated with 5 nm layer of Iridium using Baltek coater using
materials were prepared by changing the carbonization temperature from a nominal current of 15.5 mAps and coating time 60 sec. The HR-TEM
600 to 1000 oC. The samples were labelled as E-MCN-1-T (where T is images were taken using Tecnai F20 FEG TEM equipped with EDAX
the carbonization temperature). EDS and GIF (Gatan Image Filter). The preparation of the samples for
HR-TEM imaging involved dissolution of a very small quantity about 10-
15 mg of the sample in ethanol followed by sonication for 5-8 min. One
Physical and chemical characterization drop from micro pipette is dropped on the holey carbon film supported on
a copper grid and dried in open air before insertion in the TEM machine.
The samples were also studied using Raman spectroscopy technique.
o
The MCN materials E-MCN-1-T (T= 600-1000 C) were characterized Raman spectra were recorded on a Renishaw inVia Raman microscope
with low angle powder XRD. The powder X-ray diffraction measurements using the 514 nm argon green laser with dwell time of 30 sec,
were carried out on a Bruker Advance D8-IIIdiffractometer using Bragg- accumulation 1 and power consumption of 0.1 mW.
Brentano geometry. The measurements were collected using CuKα
radiation from a sealed tube source operating at 40 kV and 40 mA, a
fixed divergence slit of 0.1° and a Lynxeye multi-pixel detector. The scan Acknowledgements
rate used was 0.01 o/sec. Nitrogen adsorption and desorption isotherms
were measured at -196 oC on a Micromeritics ASAP 2420 surface area Prof. A. Vinu is grateful to UniSA for the startup grant and
and porosity analyser. All the samples were degassed for 10 hr at 250 oC Australian Research Council for Future Fellowship. We
under a vacuum (p < 1 x 10-5 pa) in the degas port of the adsorption acknowledge the support and opportunity provided by Australian
analyser. The specific surface area was calculated using the BET model. Synchroton for carrying out the NEXFAS experiements. The

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Entry for the Table of Contents

FULL PAPER
Temperature as an effective tool to Kripal S. Lakhi, Dae-Hwan Park,*
tune the nitrogen content and CO2 Stalin Joseph, Siddulu. N. Talapaneni,
adsorption capacity of mesoporous Ugo Ravon, Khalid Al-Bahily, and
carbon nitride. Ajayan Vinu*

Page No. – Page No.

Effect of Heat Treatment on the

Nitrogen Content and Its Role on the
CO2 Adsorption Capacity of Highly
Ordered Mesoporous Carbon Nitride

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