Chemical Engineering Journal 414 (2021) 128763

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Chemical Engineering Journal

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Improved CO2 adsorption properties through amine functionalization of

multi-walled carbon nanotubes
Mirtha A.O. Lourenço a, *, Marco Fontana a, Pravin Jagdale a, b, Candido Fabrizio Pirri a, b,
Sergio Bocchini a, *
a
Center for Sustainable Future Technologies, CSFT@PoliTo, Istituto Italiano di Tecnologia, Via Livorno, 60, 10144 Torino, Italy
b
Department of Applied Science and Technology, Politecnico di Torino, Corso Duca degli Abruzzi, 24, 10129 Torino, Italy

A R T I C L E I N F O A B S T R A C T

Keywords: Multi-walled carbon nanotubes (MWCNT) with different functionalities (standard–; OH–; and COOH– func­
Multi-walled carbon nanotubes tionalized) are chemically modified with N1-(3-trimethoxysilylpropyl)diethylenetriamine (DETASi) aiming to
Amine modification enhance their CO2 adsorption/separation properties. The grafting of the DETASi groups to the surface of the
Surface modification
MWCNT samples is studied by X-ray photoelectron spectroscopy (XPS), operando thermogravimetric analysis -
CO2 adsorption
infrared spectroscopy (TGA-IR), –196 ◦ C N2-sorption isotherms, and scanning electron microscopy (SEM). A
Gas separation
comprehensive overview of the reaction mechanism and samples structure/composition is provided. It was found
that the aforementioned functionalities highly influence the physical–chemical and the textural properties of the
DETASi modified-MWCNT materials, impacting in the DETASi functionalization degree and its distribution on
the sample. Amount (by TGA-IR) and homogeneity (by SEM) of the organosilicon group in the functionalized
samples increases with the increase of the functionalities in the parent MWCNT materials. Standard-MWCNT and
OH– functionalized MWCNT showed to be unable to adsorb CO2, while COOH– modified MWCNT adsorbed just
0.1% at 1 bar and 30 ◦ C. At the same adsorption conditions, DETASi modification of the MWCNT materials
enhanced the CO2 adsorption capacity, with the maximum CO2 uptake (2.11%) for COOH-MWCNT function­
alized with DETASi. The selectivity for CO2/N2 separation was also improved after DETASi grafting reaction,
with the highest value (1.89%) observed for the standard-MWCNT material modified with DETASi. In general,
the increase of the DETASi amount and of the microporosity in the functionalized MWCNT sorbents is accom­
panied by an improvement of the CO2 adsorption-separation properties. The water vapor adsorption indicated
that the standard-MWCNT sample modified with DETASi is resistant to the presence of water and its presence
(water vapor of ~3.2 kPa) can improve the CO2 uptake.

1. Introduction implementation of the adsorption technology at the industrial level in­

The urgent need to lower global emissions and mitigate the climate
impact has generated new strategies towards global decarbonization.
The replacement of fossil fuels by renewable energy sources to reduce
CO2 emissions is the most widespread strategy, alongside the application
of new technologies for CO2 capture, storage and its economical valo­
rization, applying the concepts of circular economy. In this field,
different methodologies have been proposed to uptake this gas: ab­
sorption, adsorption, cryogenic distillation and membrane separation
technologies. [1-3] For instance, lower operation costs and adsorbent
reusability are benefits that can be accomplished using the adsorption
technology when compared to the other technologies. However, the
volves the presence of an adsorbent with high CO2 adsorption capacity,
high selectivity and reusability features. [3-7]
To finely tune the features of an adsorbent (polarity, pore size and
spacing) for a certain gas the characteristics of the molecules to be
adsorbed, such as molecular -size or -weight and polarity, should be
considered. [3,8] CO2 is a small molecule, and the use of multiwalled
carbon nanotubes (MWCNT) as adsorbents of gas molecules with small
size received some attention in recent years due to the intrinsic char­
acteristics of this class of materials. [9] For instance, MWCNT are hy­
drophobic, not being affected by the presence of water which is an
advantage for CO2 uptake comparatively with other materials like
mesoporous silicas [10,11], they are light in weight, high in surface

* Corresponding authors.
E-mail addresses: mirtha.lourenco@iit.it (M.A.O. Lourenço), sergio.bocchini@iit.it (S. Bocchini).

https://doi.org/10.1016/j.cej.2021.128763
Received 29 October 2020; Received in revised form 18 January 2021; Accepted 25 January 2021
Available online 6 February 2021
1385-8947/© 2021 Elsevier B.V. All rights reserved.
M.A.O. Lourenço et al.
area, thermally and chemically stable and easy to be modified. [12] A
few examples of MWCNT and modified-MWCNT adsorbents reported in
the literature were suggested to be used for CO2 [13-16], H2 [17], CH4
[18] and NH3 [19] adsorption and biogas gases separation (CO2, CH4
and N2 gases) [20]. Typically, modifications of MWCNT are incorpo­
rated by post-synthesis functionalization of the graphitic structure of
these materials. Zgrzebnicki et al. [14] studied the oxidation impact of
MWCNT on the CO2 adsorption at 0 ◦ C and up to atmospheric pressure.
The authors observed an enhancement of the CO2 adsorption capacity of
the MWCNT with the increase of the oxidation degree (acidic groups).
Zgrzebnicki et al. [14] attributed this CO2 adsorption behavior to the
increase of the pore volume of sub-micropores with the oxidation de­
gree. Yang et al. [10] modified the oxidized MWCNT (named MWCNTs-
o) with N-(2-aminoethyl)-3-aminopropyltrimethoxysilane (AEAPS)
through grafting reaction and employed the materials in the CO2
adsorption. The results showed that the obtained adsorbent (named
MWCNTs-o_AEAPS) has high capacity, high thermal stability, elevated
tolerance to humidity and reduced regeneration cost which are good
indicators for direct CO2 capture in confined space. Su et al. [16]
modified MWCNT prepared by chemical vapor deposition (CVD) with 3-
aminopropyl-triethoxysilane (APTES), polyethylenimine (PEI), and N-
[3-(trimethoxysilyl)propyl]ethylenediamine (AEAPS). The authors [16]
tested the MWCNT and amine-modified MWCNT in the CO2 adsorption
at different temperatures (20–100 ◦ C) and different relative pressures
(10, 15 and 50%). The introduction of amino groups improved the CO2
adsorption capacity of the MWCNT, being this enhancement more sig­
nificant for the MWCNT modified with APTES (named CNT-APTES).
Moreover, the CO2 adsorption capacities via MWCNT and APTES-
MWCNT decreased with temperature showing the exothermic nature
of adsorption process and increased with water content in air (0–7%).
[16] The mechanism of CO2 adsorption on both materials was attributed
to physical forces, making the regeneration of these adsorbents feasible
at low temperature, thus the energy requirement in desorption process
can be reduced. [16] Omidfar et al. [15] also investigated the CO2
adsorption of MWCNT and single-walled carbon nanotube (SWCNT)
with different pore diameters, by using a mixture of CO2/Ar at a tem­
perature of 70 ◦ C and atmospheric pressure. The authors observed that
MWCNT materials with the largest diameter have the highest CO2 up­
take. Then the authors [15] modified the MWCNT with urea (named
MWCNT-U) improving significantly the CO2 uptake capacity of the
MWCNT. These findings indicate considerable potential of functional­
ized MWCNT in comparison with other silica and carbon adsorbents.
To the best of our knowledge, we describe for the first time the
modification of three different commercial MWCNT (standard MWCNT,
OH functionalized MWCNT and COOH functionalized MWCNT) with
N1-(3-trimethoxysilylpropyl)diethylenetriamine (DETASi) towards CO2
adsorption-separation, in a comprehensive study. MWCNT with
different functional groups are used to understand its influence on the
grafting reaction of the amino-alkyl-silyl reagent. X-ray photoelectron
spectroscopy (XPS) and operando thermogravimetric analysis infrared
spectroscopy (TGA-IR) techniques are used to determine the chemical
characteristics of the samples. The combination of both techniques is
also used to understand the DETASi functionalization mechanism on the
surface of the different pristine MWCNT. Pure CO2 adsorption isotherms
are studied in all materials, at 30 ◦ C up to the atmospheric pressure, to
assess their potential for CO2 uptake. The results are correlated with the
physicochemical characterization (specific surface area, pore volume,
pore diameter, accessibility, and nitrogen content) to fully understand
its relationship with the CO2 adsorption. The selectivity for CO2 over N2
(in a mixture of CO2/N2 of 20%) is determined for all materials. Finally,
the sensitivity to the presence of water and reusability are studied for the
best performing sample, which are important factors for application in
the capture and separation of CO2 under real operation conditions.
2
Chemical Engineering Journal 414 (2021) 128763
2. Experimental details
2.1. Chemicals
Commercial standard MWCNT (herein named CNT-SD), commercial
OH functionalized MWCNT (herein named CNT-OH) and commercial
COOH functionalized MWCNT (herein named CNT-COOH) were ob­
tained from Cheap Tubes. All the MWCNTs have identical diameters
(30–50 nm), lengths (13–20 µm) and purity (>95 wt%). Ethanol (EtOH,
PA) and N1-(3-trimethoxysilylpropyl)diethylenetriamine (DETASi,
>95%) were obtained from Sigma-Aldrich. All chemicals are used as
received without further purification. Toluene (≥99.7%, Sigma-Aldrich)
is dried for 24 h before use, adding activated molecular sieves (4 Å,
Sigma-Aldrich, activated at 350 ◦ C during 4 h).
2.2. Amine modification of MWCNT
Commercial MWCNT (100 mg) with different functionalities (SD,
–OH and –COOH functionalized MWCNT) are dried under vacuum at
80 ◦ C overnight. Then, the carbon nanomaterials are dispersed in 10 mL
of dried toluene through sonication (5 min at 37 kHz) followed by
dropwise addition of DETASi (37 µL) under inert conditions. The
resultant suspension is stirred under reflux conditions for 16 h. Finally,
the suspension is filtered off and the amine-functionalized materials
(named CNT-SD_DETASi, CNT-OH_DETASi and CNT-COOH_DETASi) are
washed three consecutive times with dried toluene (50 mL each time) to
remove the unreacted DETASi species, followed by distilled water (three
consecutive cycles, 50 mL each cycle) and finally with ethanol (50 mL).
The samples are left to dry overnight by evaporation inside a partial
open Petri dish (6 cm) at room temperature under a normal atmosphere.
2.3. Materials characterization
–196 ◦ C Nitrogen adsorption/desorption isotherms are acquired
using a BET (Micromeritics, USA). The MWCNT and the amine modified-
MWCNT materials are degassed at 120 ◦ C for 2 h.
The morphology of the MWCNT and the amine modified-MWCNT
materials is observed by means of Field Emission Scanning Electron
Microscopy (FESEM) with a Zeiss Supra 40 microscope (Zeiss, Oberko­
chen, Germany) equipped with an Energy Dispersive X-ray (EDX)
spectrometer (Oxford Instruments, Abingdon-on-Thames, UK) for
elemental analysis.
Operando TGA-IR is performed on a Thermogravimetric Analyzer
(TGA) NETZSCH TG209 F1Libra instrument coupled to a Fourier
transform infrared (FTIR) Bruker Tensor II spectrophotometer equipped
with DTGS detector and a Bruker heated gas chamber analysis accessory.
Approximately 3 mg of sample in alumina pans are heated from 30 to
1000 ◦ C (20 ◦ C⋅min− 1) under air (20 mL⋅min− 1), nitrogen flow is used as
protection gas (20 mL⋅min− 1). The FTIR analysis is collected in the
absorbance mode in the range 650–4400 cm− 1. The gas development
kinetics are followed at the maximum of adsorption for the different
molecules: carbon monoxide (CO) 2179 cm− 1 [21]; carbon dioxide
(CO2) 2349 cm− 1 [22]; water (H2O) 3735 cm− 1 [23]; ammonia (NH3)
965 cm− 1 [24]; dinitrogen oxide (N2O) 2252 cm− 1 [25].
XPS analysis is performed with a PHI 5000 Versaprobe spectrometer
(Physical Electronics, Chanhassen, US), equipped with monochromatic
Al K-alpha X-ray source (1486.6 eV). A charge compensation system,
based on an electron gun and Ar+ ion gun, is used to neutralize surface
charging. Survey and high resolution (HR) spectra are acquired using
pass energy (PE) values of 187.85 and 23.50 eV, respectively. The
calibration of the binding energy (BE) scale is achieved by fixing the C–C
sp2 component of the C1s region of the photoelectron spectrum to 284.5
eV. Casa XPS dedicated software is used to analyze the spectra. The
Shirley background function [26] is subtracted from HR spectra to
remove the background signal. Concerning the peak fitting procedure,
two types of lineshapes provided in Casa XPS are exploited: Gaussian/
M.A.O. Lourenço et al. Chemical Engineering Journal 414 (2021) 128763

Lorentzian GL(30) for every component besides the C–C sp2 component are performed under pure N2 (flow rate = 40 mL⋅min− 1) at atmospheric
in the C1s region, which utilized a Lorentzian-based asymmetric line­ pressure with increasing temperature until 100 ◦ C (heating rate =
shape LF(0.6, 1, 255, 350, 6). For semi-quantitative analysis, relative 40 ◦ C⋅min− 1).
sensitivity factors (RSF) provided by the manufacturer of the spec­
trometer are used. The reported uncertainties on semi-quantitative data 3. Results and discussion
are calculated with Monte Carlo routines implemented in Casa XPS.
rmalr 3.1. Characterization of materials

2.4. CO2 adsorption tests The chemical modification of the different commercial MWCNT with
DETASi groups is assessed by XPS and operando TGA-IR techniques.
2.4.1. Dynamic vapor sorption The analysis of XPS survey spectra (Fig. S1, in the SM) confirms the
Pure CO2 adsorption isotherms are performed using a Surface Mea­ expected chemical composition of the starting materials (C and O
surement System, Dynamic Vapor Sorption (DVS) Instrument. All ma­ chemical elements) without any sort of contamination above the
terials are previously activated under a vacuum of 10− 4 hPa at 120 ◦ C for detection limit (~0.1 at%). All the functionalized samples present peaks
30 min before starting each measurement. The CO2 gas is used as pro­ corresponding to N and Si, giving a first indication of the successful
vided by Rivoira (Italy), with a purity of 99.99%. The isotherm tem­ functionalization of the external surface of the MWCNT. The most
perature is kept at 30 ◦ C with increasing pressure (P/P0 = 5% each step) interesting regions of the photoelectron spectrum (C1s, O1s, N1s, Si2p)
up to 0.9 bar in semi-static conditions (max flow rate = 50 mL⋅min− 1); are selected for high-resolution (HR) acquisitions, in order to obtain
each step was kept up to equilibrium (criterion dm/dt = 0.001%⋅min− 1). semi-quantitative information based on peak areas (Table 1) and
The reversing procedure (pressure decrease) is studied in the same chemical information from the deconvolution into different chemically-
conditions. The CO2 adsorption isotherms are fitted using the Virial shifted components.
model. The fitting parameters are used to determine the Henry’s con­ Concerning the starting commercial materials, the semi-quantitative
stant of adsorption (K, in mmol⋅g− 1⋅kPa− 1) for each adsorbent by getting analysis confirms that the oxidized MWCNT samples (CNT-OH, CNT-
the slope of the isotherm in the limit of zero coverage. The Henry con­ COOH) have a significantly higher oxygen content with respect to the
stant measures the affinity of the CO2 gas for the solid surface. standard sample (CNT-SD), as expected. It should be noticed that CNT-
After the isothermal measurement, the reusability of the most SD sample also presents C–OH (2.3%) and C=O (1.2%) species (cf.
promising sample is tested by 10 consecutive CO2 adsorp­ Table S1 in the SM). After the chemical modification process, Si and N
tion–desorption cycles. Each cycle combines a CO2 adsorption mea­ are present at the external surface, with a Si at% in the 2.4–2.9 at%
surement at 0.2 bar and 30 ◦ C (with a flow rate = 50 mL⋅min− 1 and an range. Therefore, the degree of oxidation of the starting material seems
equilibrium criterion = 0.02%⋅min− 1) and a desorption measurement at to not play a significant role in the final loading of the molecule at the
80 ◦ C under vacuum of 10− 4 hPa (dm/dt = 0.02%⋅min− 1). surface. Further insight into the functionalization mechanism is ob­
The water vapor adsorption isotherm is performed at 30 ◦ C using the tained by a careful analysis of the chemical shift of the different com­
same equipment. The water vapor is taken from the vapor in equilibrium ponents in HR spectra, combined with semi-quantitative results.
in a flask filled with ultrapure water (Milli-Q). The pressure is increased Specifically, the aim of this analysis is to highlight the possible mecha­
up to 0.04 bar (~2.76 kPa, by introducing a water vapor pressure of nisms by which the chemical functionalization of the MWCNT takes
~1.06 kPa each step, with a max target vapor flow = 15 sccm and an place (see Fig. 1 for an overview of the possible mechanisms considering
equilibrium criterion dm/dt = 0.001%⋅min− 1). The reversing procedure the synthesis conditions used). In particular, two main kinds of mech­
(pressure decrease) is also performed in the same conditions. anisms are expected, based on previous studies on the functionalization
H2O/CO2 adsorption isotherms are studied at 30 ◦ C using the same of CNT and other nanostructured materials with similar molecules
DVS apparatus in continuous gas flow. In this case, the water vapor [10,11,27,28]:
generated is mixed with a second stream of pure CO2 before be inserted
in the balance. The partial pressure of the gases is controlled by 1. physisorption of the nitrogen-containing groups interacting with the
changing the flow rates of these two streams and thus the ratio of the OH groups at the surface (via hydrogen bond)
total pressure. The Three cycles are performed to study different ratios of 2. chemisorption via the silane group with possible Si–O–Si bridges
H2O/CO2 and total pressures (1st cycle = ~2.76 kPa, 2nd cycle = ~1.70 between the different molecules
kPa , and 3rd cycle = ~0.74 kPa). The equilibrium criterion used is of
dm/dt = 0.001%⋅min− 1 and the desorption procedure is done in the Considering the chemical properties of the MWCNT materials/
same conditions as the adsorption measurement. DETASi group, the reaction conditions used in this study and the
chemistry reactivity fundamentals, [10,16,29,30] the mechanism
2.4.2. Thermal gravimetric analysis
The CO2 adsorption performance of the modified- and non-modified-
Table 1
MWCNTs is evaluated using a TGA (NETZSCH TG 209F1 Libra). The CO2 semi-quantitative results obtained by the analysis of XPS high-resolution ac­
adsorption isotherm for all samples is performed at 35 ◦ C, at environ­ quisitions. Uncertainties are reported in brackets and they refer to the last digit.
mental pressure (~1 bar). A schematic representation of the method is
Sample C (at%) O (at N (at Si(at N(at%)/Si(at
presented in Scheme S1 (Supplementary material, SM). The samples %) %) %) %)
(~10 mg) are activated through 3 consecutive cycles of vacuum and
CNT-SD 98.0 2.0 (3) < 0.1 < 0.1 /
pure N2, followed by heating the samples until 120 ◦ C (heating rate = (3)
40 ◦ C⋅min− 1) under vacuum for 30 min, to desorb water and other gases CNT-SD_DETASi 82.3 8.2 (2) 6.6 (2) 2.9 (1) 2.3 (1)
on the surface. After cooling at 35 ◦ C (cooling rate = 2 ◦ C⋅min− 1), the (2)
modified- and non-modified- MWCNT are exposed to pure N2 (flow rate CNT-OH 94.4 5.6 (1) < 0.1 < 0.1 /
(1)
= 40 mL⋅min− 1) at atmospheric pressure during 30 min, until weight
CNT-OH_DETASi 84.2 8.5 (2) 4.8 (2) 2.5 (1) 1.9 (1)
stabilization. Then the N2 gas is swept with a mixture of CO2/N2 (20 vol (3)
% of CO2, total flowrate = 40 mL⋅min− 1) for 120 min. Both CO2 and N2 CNT-COOH 92.9 7.1 (2) < 0.1 < 0.1 /
flow rates are kept constant. The weight difference between the initial (2)
and final moment of the CO2 adsorption indicates the CO2 amount CNT- 83.6 7.9 (1) 6.1 (2) 2.4 (1) 2.5 (1)
COOH_DETASi (2)
adsorbed by the materials. Finally, the CO2 desorption measurements

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 M.A.O. Lourenço et al. Chemical Engineering Journal 414 (2021) 128763

Fig. 1. a-d) Schematic representation of possible DETASi grafting mechanisms at the surface of MWCNTs through silanization reaction. Possible side reactions: e)
physisorption via hydrogen-interactions between –OH groups from the MWCNT and the –NH and –NH2 groups from the DETASi, f) amide formation and g) NH2-
silicon polymerization. MWCNT are represented by the black rectangles.

related to the formation of a covalent bond between the carbon atom of Fig. 2 shows both the N1s and Si2p core-level peaks for the func­
the MWCNT and the Si or N atoms of the DETASi groups (CMWCNT–Si tionalized samples, which are expected to be sensitive to the chemical
DETASi and CMWCNT–NDETASi bonds) is not possible. Thus, it is excluded environment of the atoms involved. First of all, it is very interesting to
from Fig. 1. notice that for all the samples considered the N1s and Si2p region show

Fig. 2. XPS high-resolution spectra of the N1s (a) and Si2p (b) regions for the functionalized samples CNT-SD_DETASi, CNT-OH_DETASi and CNT-COOH_DETASi,
labeled ‘SD’, ‘OH’, ‘COOH’ in the figure.

4
­
M.A.O. Lourenço et al.
very similar characteristics: they are mainly constituted by one single
dominating contribution. This means that, regardless of the degree of
oxidation of the starting material, after the functionalization, the N and
Si atoms are in similar chemical environments in the different samples
(at least from the point of view of chemical shift).
Specifically, the N1s region is determined by a single peak with a
binding energy in the 399.9–400.1 eV range with FWHM ~ 2.4, which is
attributed to –NH, –NH2 groups. [31] The absence of a contribution at
binding energies higher than 401 eV, reported in the literature as
hydrogen-bonded NH2 species on titania and silica substrates
[27,32,33], is an indication that the main grafting mechanism is not
physisorption. This indicates that the unreacted DETASi species are
successfully removed by the washing procedure with dried toluene.
Based on the N1s region, the presence of amides (NHC=O, mechanism f)
in Fig. 1) in principle cannot be ruled out, since they manifest them­
selves as a contribution in the 400.3–400.7 eV binding energy range,
according to the literature [31,34]. However, based on the analysis of
the C1s region (see Fig. S2 and Table S1 in the SM for a detailed
description), this option has to be excluded for samples CNT-SD_DETASi
and CNT-COOH_DETASi, since the C=O component in the C1s region is
negligible (Table S1, SM). The main candidate for the grafting mecha­
nism is therefore the silane group present in the starting DETASi
Fig. 3. TGA analysis under air atmosphere (40 mL⋅min− 1, 10 ◦ C⋅min− 1) of a) CNT-SD b) CNT-SD_DETASi c) CNT-OH d) CNT-OH_DETASi e) CNT-COOH f)
CNT-COOH_DETASi.
5
Chemical Engineering Journal 414 (2021) 128763
molecule. Again, it is worth noting that the Si2p region is rather similar
between the functionalized samples, with a main contribution located in
the 102.9–103.1 eV binding energy range with FWHM ~ 1.8 eV. Ac­
cording to the existing literature [34,35], this contribution is compatible
with Si grafted to the surface through bonds with oxygen atoms at the
surface. Moreover, it must be stressed that Si–O–Si bridges between
molecules are also compatible with the measured binding energy and
that the dominant contribution to the O1s region (see Fig. S3 in the SM)
is also pointing to this kind of chemical environment [34,36] for Si
atoms. This mechanism, (d) in Fig. 1), is also corroborated by semi-
quantitative analysis for sample CNT-SD_DETASi, since the O at% in
the starting material (2 at%) is comparable with Si loading in the
functionalized sample (2.9 at%), meaning that all the oxygen groups at
the external surface of the nanotubes are used for grafting the molecule.
Regarding the other samples, a combination of mechanisms a), b), c)
(Fig. 1) is not impossible, but the main contribution is expected to be the
same as sample CNT-SD_DETASi, since the Si2p and O1s regions are
actually comparable. Additionally, mechanism c) is unlikely to occur on
all MWCNT studied, as it is necessary to have three hydroxyl species in
the vicinities to react with the DETASi group. However, it is interesting
to notice that although the –OH and –COOH functionalized commercial
samples provide more oxygen-containing groups at the surface when
M.A.O. Lourenço et al.
comparing with the CNT-SD sample, the final loading with the DETASi
molecule is similar in all samples.
Fig. 3 shows the thermal degradation in air of all samples up to
1000 ◦ C. The TGA of CNT-SD (Fig. 3a) shows a single weight loss step
with a maximum degradation at about 725 ◦ C and a residue of about 3.6
wt% at 800 ◦ C (Fig. 3a and Fig. S4 in the SM).
IR analyses of the developed gasses shows the complete conversion
of the nanotubes into CO2 (FT-IR 725 ◦ C) by oxidation. Only a small
amount of carbon monoxide is produced at a lower temperature
(maximum around 715 ◦ C) when the process oxidation rate is lower
(Fig. S4 and Table S2, SM).
Once functionalized, the CNT-SD shows several weight losses, the
first with a maximum weight loss at about 73 ◦ C, the second at about
370 ◦ C, and the last step that reaches a maximum degradation rate at
766 ◦ C (Fig. 4). From FT-IR analysis the first weight loss shows the
presence of the bands related to H2O and CO2 mainly adsorbed gases on
the functionalized material. The second weight loss at 370 ◦ C shows the
presence of CO2, H2O, NH3, and N2O (Fig. 4 and Table S2 in the SM) that
can be attributed to the degradation of the functional material through
the oxidation of hydrogen to water and the formation of ammonia and
dinitrogen oxide from the degradation of –NH and –NH2 functionalities.
Fig. 4. TGA-IR data of CNT-SD_DETASi material. a) TGA and first derivative; b) maximum adsorption peak vs temperature for CO2 (blue lozenges); CO (grey tri­
angles), H2O (green squares) and NH3 (red circles); c) IR spectra of developed gases at a) 73 ◦ C b) 370 ◦ C c) 766 ◦ C.
6
Chemical Engineering Journal 414 (2021) 128763
[37] The last weight loss at 766 ◦ C is mainly due to the degradation of
MWCNT with the production of CO2. The shift at higher temperature of
the degradation of MWCNT is probably due to the presence of SiO2
formed from the degradation of the organic modifier that decreases the
diffusion of oxygen and thus delays the oxidation process. [38]
The TGA-IR analysis of CNT-OH (Fig. S5, SM), similarly to CNT-SD,
shows a single loss of weight step with a maximum degradation at about
718 ◦ C and a residue of about 4.5 wt at 800 ◦ C. The gases developed are
mainly CO and CO2 being water developed in too low amount to be
distinguished from the IR background noises. As observed for the CNT-
SD sample, once the CNT-OH is functionalized several degradation steps
are present (Fig. S6 and Table S2 in the SM). The first step, with a
maximum degradation at about 85 ◦ C, is mainly due to the presence of
H2O and CO2 adsorbed while the second step, at about 369 ◦ C, can be
attributed to the degradation of the alkyl amine functionalities of the
CNT-OH_DETASi material. [39] A third step at 548 ◦ C is also due to
functional materials degradation probably from a carbonized char
formed at lower temperature. [40] Finally, the last degradation step at
776 ◦ C is mainly due to the degradation of MWCNT with the production
of CO2. [39]
The TGA-IR of CNT-COOH (Fig. S7 and Table S2, SM) shows some
M.A.O. Lourenço et al.
peculiarities: there is a continuous loss of weight in the range of
100–500 ◦ C (about 2.5 wt% loss) with the development of CO2 and a
small quantity of H2O thus it can be supposed that there is the formation
of CO2 from decarboxylation of the carboxylic groups. [41] The main
degradation step has a maximum at about 712 ◦ C, the thermal degra­
dation happens in a wide temperature range demonstrating a large
number of different structures and probably a large number of defects on
the CNT-COOH surface which is in agreement with XPS analysis (see
Table S1 in the SM). Finally, the CNT-COOH_DETASi material shows a
behavior similar to the CNT-COOH sample with a continuous loss of
weight in the range of 100–500 ◦ C (Fig. S8 and Table S2, SM). However,
it is split into two well-defined steps, the first one at 100 ◦ C that is mainly
due to the volatilization of small molecules such as adsorbed water and
CO2, and the second one at 361 ◦ C from the degradation CNT-
COOH_DETASi alkyl amine functionalities. The last degradation step is
due as usual to the oxidation of the MWCNT main chains with the
development of CO2.
Fig. 3 also shows that the residue amount of the degradation of the
DETASi functionalized MWCNT samples at 800 ◦ C augmented in the
order CNT-SD_DETASi (5.2%) < CNT-OH_DETASi (8.8%) < CNT-
COOH_DETASi (9.6%). The increase of the residue in the functionalized
samples comparing with the parent MWCNT materials is related to the
formation of silica from the organosilylated precursor and the amount
can be associated with the quantity of DETASi groups incorporated in
the functionalized samples. Thus, the incorporation of the DETASi
groups is highly dependent on both type and amount of functionalities
present in the parent MWCNT materials: CNT-SD < CNT-OH < CNT-
COOH. This result is against the one observed by XPS. However, it
should be noticed that XPS is a superficial technique. For instance, in the
case of heterogeneous dispersion of the DETASi functionalities on the
modified-MWCNT materials, a good correlation between the quantity of
DETASi incorporated and the amount of OH or COOH groups present in
the parent MWCNT materials can be absent using XPS.
The physical and textural properties of the MWCNT-based materials
are studied –196 ◦ C N2 adsorption–desorption isotherms and FESEM.
Table 2 shows the textural features of the modified- and non-
modified-MWCNT and Fig. S9 shows the N2 sorption isotherms of
MWCNT based materials. All samples (Fig. S9, SM) display a typical
Type IV isotherm (IUPAC classification) [42], with a clear hysteresis at
high P/P0 (type H3 hysteresis), indicating the presence of both meso-
and macro-porosity for all materials. The commercial samples present a
specific surface area (SBET) between 103–121 m2⋅g− 1 and a pore volume
(Vt) between 0.54 and 0.63 cm3⋅g− 1. The DETASi functionalization of
the MWCNT samples promotes a decrease in both SBET and Vt, being
more noticeable for the CNT-COOH based material.
Fig. S10 in the SM shows the pore size distribution (PSD) curves of
the modified- and non-modified- CNT, calculated via the non-local
density functional theory (NLDFT) method, confirming the pore size
viewpoint. It is possible to observe that all commercial MWCNT mate­
rials present similar PSD curves in the mesoporous size range and the
functionalization of the CNT samples with DETASi groups leads with a
decrease in the pore size of the materials corroborating the
Table 2
Textural properties of MWCNT based materials.
Sample SBET (m2⋅g− 1) Vt (cm3⋅g− 1)a dP (nm)b Curve type
CNT-SD 112 0.58 2.6–66 IVa
CNT-SD_DETASi 88 0.37 1.9–63
CNT-OH 103 0.54 2.5–66
CNT-OH_DETASi 83 0.34 1.9–63
CNT-COOH 121 0.63 1.3–63
CNT-COOH_DETASi 74 0.35 1.9–63
a
The total volume (Vt) is determined from N2 uptake at P/P0 = 0.98, using the
Barrett, Joyner, and Halenda (BJH) method.
b
Pore width range obtained from the non-local density functional theory
(NLDFT) method.
7
Chemical Engineering Journal 414 (2021) 128763
functionalization of MWCNT also into the pores. From the DETASi
functionalized samples, CNT-SD_DETASi material has higher pore vol­
ume in both the micropore and smaller mesopore ranges (1.5–6 nm),
followed by CNT-COOH_DETASi and CNT-OH_DETASi samples
(Fig. S10, SM).
FESEM images of the modified- and non-modified- MWCNT are
displayed in Fig. 5. It can be confirmed that most MWCNT presents pore
sizes between 30 and 50 nm. It is possible to observe that the func­
tionalization with DETASi can occur in three different forms: i) forma­
tion of DETASi nanoparticles attached to the MWCNT wall; ii) surface
coverage of MWCNT by DETASi and iii) pore blocking (functionalization
of DETASi starts at the beginning of the MWCNT pores leading to pore
blocking). The latter form of functionalization is very common to occur
in MWCNT with smaller pores. In the case of CNT-SD it is possible to
observe DETASi nanoparticles with 100–540 nm of dimension attached
to the lateral part of the CNT-SD wall, due to the homo-condensation
reaction, being this functionalization form the predominant one in this
sample (mechanism d) in Fig. 1).
At the submicrometer scale, EDX elemental mapping (figures S11
and S12 provided in the SM) confirms the good uniformity of the
functionalization with DETASi.
At the nanometer scale, FESEM images also show that the DETASi
surface modification of the CNT-OH and CNT-COOH materials is more
homogenous because of the presence of OH groups at the surface of the
MWCNT allows a better distribution of the DETASi functionalities. This
behavior is explained by the grafting reaction through hydrolysis and
condensation of the methoxysilyl groups of DETASi precursor to the OH
groups of both CNT-OH and CNT-COOH materials.
This result explains the high quantity of DETASi functionalities
observed by XPS in the CNT-SD_DETASi sample comparing with the one
obtained for CNT-OH_DETASi and CNT-COOH_DETASi materials.
3.2. CO2 adsorption
3.2.1. Pure CO2 adsorption measurements
All non-modified and modified MWCNT samples are tested in the
pure CO2 adsorption up to 0.9 bar (89 kPa) at 30 ◦ C and the results are
presented in Fig. 6.
Fig. 6 shows that both commercial CNT-SD (Fig. 6a) and CNT-OH
(Fig. 6b) materials are unable to adsorb CO2, due to the absence of
functional groups into the MWCNT surface. From the commercial
MWCNT materials, CNT-COOH sample shows the best CO2 adsorption
results, adsorbing 0.1% of CO2 per gram of material (Fig. 6c). This small
increase can be associated with the presence of the carboxylic acid
groups that are able to interact with the CO2 molecules. [14] The
functionalization of the samples with DETASi leads to an important
improvement in the CO2 adsorption capacity, with the highest value for
CNT-COOH_DETASi sample (2.11%, Fig. 6f) and decreases in the order
CNT-COOH_DETASi > CNT-SD_DETASi > CNT-OH_DETASi as can be
clearly noticed in Fig. S13 in the SM. As the SBET is very similar for all
DETASi functionalized samples (in the range of 103–121 m⋅g− 1), the
results indicate that the amount of N content in the materials has a high
influence on the adsorption of CO2. Also, the micro-porosity can play an
important role in the CO2 adsorption behavior of the MWCNT samples.
[43] The combination of both micro-porosity and high N content
together with a good distribution of the DETASi functionalization on the
material leads to increased adsorption capacity, which appears to occur
in the case of the CNT-COOH_DETASi adsorbent, that presents high pore
volume in the smaller pores-size range and high N content (6.1% from
XPS analysis). Despite, in general, the CNT-OH_DETASi sample has a
higher amount of DETASi groups than the CNT-SD_DETASi material
(observed by TGA-IR), in the latter case its distribution occurs more at
the surface of the MWCNT (observed by FESEM and corroborated by
XPS). Thus, the DETASi groups in the CNT-SD_DETASi sorbent are more
available to interact with the CO2 molecules. This feature together with
the highest pore volume in the 1.5–6 nm pore size range appear to highly
M.A.O. Lourenço et al.
Fig. 5. FESEM images of a) CNT-SD, b) CNT-SD_DETASi, c) CNT-OH, d) CNT-OH_DETASi, e) CNT-COOH, and f) CNT-COOH_DETASi.
influence the CO2 adsorption.
Table 3 presents the calculated Henry’s constants (KH) of CO2
adsorption in the commercial- and DETASi modified- MWCNT-based
adsorbents.
Fig. S14 in the SM shows the pure CO2 adsorption equilibrium iso­
therms fitted by the Virial isotherm model. The Henry constants for the
CO2 adsorption in CNT-SD and CNT-OH adsorbents could not be
determined due to the negligible amounts of adsorbed CO2 in these
materials. The modification of the samples with the DETASi function­
ality provided an enhancement of the adsorption capacity of all com­
mercial MWCNT materials as can be understood from the increase of the
Henry’s constant. This increase is better noticed in the CNT-
COOH_DETASi adsorbent, which presents the highest KH from the
overall samples.
The possibility of using adsorbent materials for applications at the
industrial level on the CO2 adsorption-separation process can be eval­
uated only if the sorbent can be easily regenerated with minimum loss of
capacity after each regeneration cycle. [5] Overall results indicate that
the desorption of CO2 is slower than its up-take for all samples, resulting
in hysteresis. This finding can be associated with the existence of small
micropores (<1 nm) that are able to strongly retain the CO2 molecules
[43,44] or to the formation of carbamate ion species. [3,45,46] How­
ever, Fig. 6 also shows that it is possible to regenerate these materials
8
Chemical Engineering Journal 414 (2021) 128763
just by applying vacuum, a feature that is more pronounced on the CNT-
SD_DETASi material (Fig. 6d).
3.2.2. CO2 adsorption behavior in the presence of N2
The CO2 selectivity over N2 was measured at 35 ◦ C on the pristine-
and DETASi modified- MWCNT materials and the weight increase is
displayed in Fig. 7. As it can be observed, no weight difference was
detected on CNT-SD, CNT-OH and CNT-COOH samples when the CO2
gas (20 vol%) is introduced in the system, showing no selectivity for CO2
over N2 by these materials. Unlike the pristine carbons, DETASi modi­
fication of the MWCNT samples leads to an increase of the adsorbed
weight when the CO2 gas is added.
CNT-SD_DETASi has the highest CO2 adsorption capacity over N2,
with 1.89% of weight increase (0.43 mmol⋅g− 1), followed by CNT-
COOH_DETASi (1.46%, 0.33 mmol⋅g− 1) and CNT-OH_DETASi (0.74%,
0.17 mmol⋅g− 1). As both SBET and Vt are similar in all alkyl amine
modified CNT sorbents, this behavior can be correlated with both the
amount of DETASi groups at the surface of MWCNT and pore volume in
the 1.5–6 nm range, which is highest on the sample CNT-SD_DETASi and
lowest in the CNT-OH_DETASi material (from XPS analysis and PSD
curves, respectively).
The CO2 desorption process is also studied by exchanging the
mixture of CO2 and N2 gases for pure N2 flux while the temperature is
M.A.O. Lourenço et al. Chemical Engineering Journal 414 (2021) 128763

Fig. 6. Pure CO2 adsorption isotherms at 30 ◦ C of a) CNT-SD, b) CNT-OH, c) CNT-COOH, d) CNT-SD_DETASi, e) CNT-OH_DETASi, and f) CNT-COOH_DETASi
materials. Blue filled circles correspond to the CO2 adsorption process for and orange open circles are associated with the CO2 desorption process.

Table 3
Virial coefficients (C1 and C2) and Henry’s constants (KH) for the adsorption of
CO2 at 30 ◦ C on the prepared materials.a
Material KH (mol⋅kg− 1⋅kPa− 1) × C1 C2
10− 2 kg⋅mol− 1
(kg⋅mol− 1)2

CNT-SD – – –
CNT-SD_DETASi 19.5 26.50 –38.83
CNT-OH – – –
CNT-OH_DETASi 3.17 36.16 –93.67
CNT-COOH 0.08 44.62 –
CNT- 99.89 14.26 –6.95
COOH_DETASi
a
Obtained by nonlinear least-squares fitting of the virial equation to the
adsorption data.

increased up to 100 ◦ C. Fig. S15 (in the SM) shows the derivative of the
CO2 desorbed amount of all samples during the desorption process. The
DETASi functionalized MWCNT samples showed a maximum release of
the CO2 adsorbed molecules between 56 and 62 ◦ C and at 100 ◦ C most of
the adsorbed CO2 was released.
Fig. 7. CO2 adsorbed amounts (%) at 35 ◦ C and 1 bar of a mixture of CO2/N2
gases determined by TGA analysis.
3.2.3. CO2 adsorption behavior under humid conditions
The water vapor adsorption isotherm (Fig. 8a) and the H2O/CO2
just applying vacuum, confirming the presence of a physisorption pro­
adsorption under the presence of the different ratios of H2O/CO2
cess. In the case of adsorption under H2O/CO2 mixtures up to 0.04 bar
(Fig. 8b-d) are studied at 30 ◦ C for the most CO2/N2 selective sample,
(~3.8 kPa, Fig. 8b-d), CNT-SD_DETASi shows a preferential adsorption
CNT-SD_DETASi, in order to understand how a MWCNT with just
of CO2 when the pressure of the water vapor is superior to ~3.2 kPa (3rd
DETASi functional groups behaves under humid conditions. Fig. 8a
cycle, Fig. 8c-d), noticed by the increase of almost 2% of weight after
shows that CNT-SD_DETASi is able to adsorb approx. 4.5% of water (2.5
addition of CO2 gas.
mmol⋅g− 1) at 0.04 bar, which is much higher than the amount of the CO2
The CO2 adsorption is thus highly favorable in presence of water
adsorbed under the same conditions. However, this process is much
being the adsorption similar to the one obtained for the CNT-
slower than the adsorption of the CO2 and takes almost 22 h to reach the
COOH_DETASi sample in dry condition (~2.1%) but at much higher
maximum water up-take. The absorbed water results in capillary
pressure 89 kPa (Fig. 6f). This result is in agreement with the literature
condensation, and its release, by decreasing humidity, occurs more
and can be associated to the direct reaction between the secondary and
slowly than the adsorption process, resulting in hysteresis (Fig. 8a).[47]
primary amine groups present in the DETASi functionality with the CO2
As observed for CO2, the H2O desorption process can be performed by
and water molecules to form bicarbonate ions. [3,45,46] It should be

9
M.A.O. Lourenço et al. Chemical Engineering Journal 414 (2021) 128763

Fig. 8. Adsorption isotherms at 30 ◦ C on the CNT-SD_DETASi material. a) water vapor adsorption isotherm; b) H2O/CO2 adsorption isotherm vs total pressure; c)
H2O/CO2 adsorption isotherm vs water vapor partial pressure; and d) H2O/CO2 adsorption isotherm vs CO2 partial pressure. Filled symbols correspond to the increase
of pressure and empty symbols correspond to the decrease of pressure. Color scheme: 1st adsorption cycle – orange circles, 2nd cycle – blue triangles, 3rd cycle
purple squares.

noted that under humid conditions 1 mol of amine can react with 1 mol
of CO2 (equation (1)). [3,45,46] However, this behavior is absent at
lower amounts of water (1st and 2nd cycle, Fig. 8c-d), and maybe related
to the absence of enough water to form the bicarbonate ions. Instead, the
secondary and primary amines of the DETASi functionality may react
directly with the CO2 molecules to form carbamate ion species (like in
dry conditions), and thus 2 mol of amine are necessary to react with 1
mol of CO2 (equation (2)). [3,45,46]
(1)
(2)
3.2.4. Adsorbent regeneration capacity
The adsorbents regeneration capacity is an important feature for
long-time operation. Thus, the adsorption performance of the most se­
lective sample (CNT-SD_DETASi) is evaluated on a fast-cyclic adsorp­
tion/desorption study of 10 cycles, subsequently performed after the
adsorption isotherm. The adsorption measurements are made at 0.2 bar
(~20 kPa) and 30 ◦ C while the desorption process is carried out under
vacuum and 80 ◦ C. The results are presented in Fig. 9. It is possible to
observe that the CNT-SD_DETASi sorbent is stable after each adsorp­
tion–desorption cycle, having a good cycling performance without a
significant loss of adsorption capacity of CO2. Therefore, this sample has
the potential to retain a stable CO2 capture ability during multicycle
operations.
However, the CNT-SD_DETASi material has a CO2 adsorption ca­
pacity of 0.4 wt% in the first cycle, which is 40% less than for the virgin
sample at the same adsorption pressure and temperature (Fig. 6d). Due
to the good reversibility behavior observed in this sample during the
adsorption–desorption isotherms (cf. Fig. 6d), this loss of adsorption
capacity can be associated with the adsorption conditions established in
the cyclic reusability test. The equilibrium criterion of this test is of
0.02%⋅min− 1, which is twenty times faster than the equilibrium crite­
rion used in the adsorption–desorption isotherm measurement of the
virgin sample (0.001%⋅min− 1). Regarding the CNT-COOH_DETASi
sample, under the same cycling conditions, the first cycle shows a CO2
uptake of 0.7% (Fig. S16 in the SM). However, contrarily to observed for
the CNT-SD_DETASi sample, this material loses its ability to adsorb CO2
each cycle, demonstrating a loss of the regenerable capacity. This
behavior can be related to the formation of the ureic functional group

10
M.A.O. Lourenço et al. Chemical Engineering Journal 414 (2021) 128763

promising DETASi modified MWCNT (CNT-SD_DETASi and CNT-

Fig. 9. Cyclic regenerability of the CNT-SD_DETASi up to 10 repetitive
adsorption (30 ◦ C) - desorption (80 ◦ C) cycles at 0.2 bar.
[48], less reversible than carbamate and carbamic acid species
[3,45,46]. The former species are obtained by the reaction between the
primary and secondary amines of the DETASi groups and the CO2
molecules, catalyzed by the remaining unreacted COOH groups of the
sample.
3.3. Comparison with other materials
The capacities for the CO2 and N2 adsorption of the two most
COOH_DETASi) for the CO2/N2 separation are compared with other
types of materials in Table 4. The possibility to use these materials under
humid conditions is also demonstrated.
As it can be observed, all materials compiled in this Table are found
to adsorb CO2 in the temperature range 20–70 ◦ C. Additionally, the
modification of the carbon nanotubes with amine functionalities leads to
an increase in the CO2 uptake. However, the comparison of the different
materials in the CO2 adsorption-separation is difficult to perform. As can
be perceived in Table 4 both the functionalization and CO2 adsorption
conditions are completely distinct in the different reported studies. For
instance, the materials functionalized with APTES, Urea, DAP, and
AEAPS (first 5 entries in Table 4) used from 150 to 8 times more amount
of precursor per gram of carbon nanotubes than in this study. Addi­
tionally, the inserted nitrogen quantity is not evaluated on the different
materials reported in the literature (Table 4). Thus, a possible calcula­
tion of the CO2/N ratio to be used as a comparison factor is not possible.
Moreover, different gas mixtures (from Ar/CO2, N2/CO2, and pure CO2),
adsorption temperature, and pressure were used in the different re­
ported studies making a comparison with our materials a hard task to
accomplish. Furthermore, it seems that the pristine MWCNT used in the
other studies (first 4 entries, Table 4) are able to adsorb high amounts of
CO2 (from 0.23 to 1.22 mmol⋅g− 1) when compared with the carbon
nanotubes used in this study that are unable to adsorb CO2.
Having into consideration all the works listed in Table 4, a possible
comparison of the materials synthesized in this study may be possible
with the materials MWCNTs-o_AEAPS and MWCNT_Chitosan. For
instance, both MWCNTs-o_AEAPS [10] and MWCNT_Chitosan [50] are
prepared from MWCNT unable to adsorb CO2. In the case of MWCNTs-
o_AEAPS [10] the amount of precursor added is just 8 times superior to
the one used to prepare the CNT-SD_DETASi and CNT-COOH_DETASi
samples. Moreover, the same kind of gas mixture (N2/CO2) is used to
perform the CO2 adsorption measurements. However, the gas pressure

Table 4
Capacities of different carbon nanotubes adsorbents in the CO2 adsorption-separation.
Materials REF. Precursor amounta N content CO2 capacity Humid Tbads Gas Pcads Tdact
(mmol⋅g− 1) (%) (mmol⋅g− 1) conditions (◦ C) (bar) (◦ C)

CNT [16] – – ~0.64f n.d.g 20 (air/CO2) – m.i.h

CNT_APTESe [16] 213.7 m.i.h ~1.20f tested 15%
~0.98f n.d.g 40
SWCNT [15] – – 1.39 n.d.g 70 (Ar/CO2) 5% 120i
MWCNT (<8 nm)j [15] 1.22
MWCNT-U1l [15] 166.5 m.i.h 1.40
MWCNT-U4l [15] 1.46
MWCNT (8–15 nm)m [49] – – 0.91 40 Pure CO2 6 120
MWCNT-DAPn [49] 80.9 m.i.h 1.78
SWCNT (0.7–1.1 nm)p [13] – – 0.25 35 1.1 110q
MWCNT (6–9 nm)p [13] 0.23
MWCNT (<8 nm)p [13] 0.09
MWCNTs-o (8–15 nm)r – – 0.09 s n.d.g 25 (N2/CO2) 2% – m.i.h
[10]
MWCNTs-o_AEAPSt [10] 11.5 7.28u 0.64 s tested
MWCNT [50] – – 0.01 n.d.g 45 Pure CO2 1.1 110v
MWCNT_Chitosan [50] – n.d.g 0.07
This study
CNT-COOH_DETASi ~1.4 6.6u 0.33 n.d.g 35 (N2/CO2) 1.0 120
CNT-SD_DETASi 6.6u 0.43 20%
CNT-COOH_DETASi 6.6u 0.48 30 Pure CO2 0.9 120
CNT-SD_DETASi 6.1u 0.25 tested
a
Amount of the amine precursor added per gram of carbon nanotubes; bAdsorption temperature; cAdsorption pressure; dActivation temperature corresponds to the
degasification temperature. eAPTES is the abbreviation for 3-aminopropyl-triethoxysilane. fThe experiments were performed in an adsorption column under dynamic
conditions; dried air was mixed with pure CO2 (15%). gn.d. denotes non determined. hm.i. denotes missing information. iSamples were degassed at 120 ◦ C for 1 h under
Ar flow. jMWCNT with an outer diameter lower than 8 nm. lMWCNT with an outer diameter lower than 8 nm was modified with urea for 1 or 4 h (MWCNT-U1 or
MWCNT-U4, respectively). mMWCNT with an outer diameter between 8 and 15 nm. nOxidized MWCNT functionalized with 1,3-Diaminopropane (DAP). pThe values
under parentheses denotes the interval of the outer diameter of the carbon nanotubes. qSamples were activated at 110 ◦ C for 30 min under N2 flow. rMWCNT with an
outer diameter between 8 and 15 nm oxidized under O2/N2 gas mixtures at 500 ◦ C for 3 h. sThe experiments were performed in an adsorption column under dynamic
conditions; a cylinder with N2/CO2 gas mixture was used containing 2% of CO2. tMWCNT-o were grafted with N-(2-aminoethyl)-3-aminopropyltrimethoxysilane
(AEAPS). uDetermined by XPS. vSamples were degassed at 110 ◦ C for 30 min under vacuum.

11
M.A.O. Lourenço et al.
used in reference [10] is not presented, the percentage of CO2 used is
2%, and the temperature is 10 ◦ C lower than the one used in this study.
Despite the difference in the temperature and inserted N content, the
CO2 adsorption results of the CNT-SD_DETASi sample for a gas mixture
of N2/CO2 are slightly lower than the one reported for MWCNTs-
o_AEAPS. However, it should be highlighted the differences in the
CO2/N2 adsorption method between these two works. The CO2
adsorption study in the MWCNTs-o_AEAPS [10] is performed from the
direct introduction of the gas mixture (N2/CO2, 2%) in a column with
the material under vacuum while in this study, the pure N2 is first
introduced on the chamber until weight stabilization of the CNT-
SD_DETASi sample and then the gas is switched for N2/CO2 mixture
(20%), demonstrating a real selectivity of CNT-SD_DETASi towards CO2
over N2. Pure CO2 adsorption in both CNT-SD_DETASi and CNT-
COOH_DETASi materials can be compared with the MWCNT_Chitosan
material [50], despite both temperature and pressure used in this study
are 15 ◦ C and 0.2 bar lowest, respectively. CNT-SD_DETASi and CNT-
COOH_DETASi samples showed an adsorption capacity higher 3.6 and
6.9 times, respectively, than the one obtained for the MWCNT_Chitosan
material.
Under humid conditions, all MWCNT materials functionalized with
organosilylated precursors demonstrated, in general, an improvement in
the CO2 adsorption behavior (cf. references [10,16]), independently of
the synthesis/adsorption conditions used, showing the possibility to use
this family of materials in the presence of water.
4. Conclusions
Commercial MWCNT with different functional groups (non-modi­
fied, and with –OH and –COOH functionalities) are chemically func­
tionalized with the DETASi molecule, resulting in alkyl-amino modified
MWCNT materials with different chemical and textural properties. The
amount of DETASi groups attached to the MWCNT surface (observed by
XPS and TGA-IR) and its distribution on the sample (noticed by FESEM)
are the most significant differences observed when compared with the
unmodified materials. The surface area, pore volume and pore size are
also smaller after the modification, demonstrating the functionalization
of the MWCNT also inside of the pores. Additionally, XPS data showed
that independently of the functional groups of the pristine samples, the
DETASi functionalization seems to occur through the same mechanism.
Operando TGA-IR showed that the pure MWCNT (CNT-SD) just develop
CO2 and CO gases during the degradation process while the MWCNT
with –OH and –COOH functional groups at the surface also release water
with the increase of the temperature, confirming the functionalization of
the samples. After the modification of the MWCNT surface with DETASi
groups, also –CN and NH3 gaseous species are released. Operando TGA-
IR also revealed a correlation between the quantity of DETASi groups
incorporated and the amount and type of functionalities present in the
parent MWCNT materials. All materials are tested in the pure CO2 and in
the CO2/N2 adsorption (20% of CO2) at 30 ◦ C and 35 ◦ C, respectively.
The CO2 adsorption capacity and the selectivity for CO2/N2 separation
are enhanced for all DETASi modified MWCNT adsorbents. The highest
adsorption capacity and selectivity in the CO2/N2 separation is observed
for materials with the highest DETASi amount. CNT-COOH_DETASi
showed the highest Henry constant (99.89 × 10− 2 mol⋅kg− 1⋅kPa− 1)
followed by CNT-SD_DETASi material (19.5 × 10− 2 mol⋅kg− 1⋅kPa− 1),
while the best selectivity in the CO2/N2 separation is observed for the
CNT-SD_DETASi sorbent. The water vapor adsorption at 30 ◦ C on the
CNT-SD_DETASi showed that these DETASi modified-MWCNT materials
are resistant to the presence of water. In fact, the H2O/CO2 adsorption
isotherms indicated that the presence of water can enhance the CO2
uptake when the water vapor is ~3.2 kPa. In the case of CO2 adsorption
from exhaust gas containing water, we therefore have the advantage of
higher adsorption at lower pressure, but this could be offset by the need
for an additional water/CO2 separation step. Finally, the most selective
sample, CNT-SD_DETASi, is reused for 10 cycles without any loss of CO2
12
Chemical Engineering Journal 414 (2021) 128763
capacity, which indicates the possible surface regeneration of these
materials applying just vacuum, a crucial factor for its potential appli­
cation in cyclic separation processes at the industrial level.
Author contributions
The manuscript was written through the contributions of all authors.
All authors have given approval to the final version of the manuscript.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgements
Mr. Mauro Raimondo and Prof. Alberto Tagliaferro are acknowl­
edged for FESEM analyses.
Appendix A. Supplementary data
Materials characterization data from TGA-IR spectroscopy, –196 ◦ C
N2-sorption isotherms, and XPS, and further FESEM analysis and CO2
adsorption results. Supplementary data to this article can be found on­
line at https://doi.org/10.1016/j.cej.2021.128763.
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