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Structure design of a hyperbranched polyamine

Cite this: Green Chem., 2016, 18,
adsorbent for CO2 adsorption†
5859
Hui He,a Linzhou Zhuang,a Shuixia Chen,*a,b Hucheng Liua and Qihan Lia

Received 24th May 2016,
Accepted 11th August 2016
DOI: 10.1039/c6gc01416j
www.rsc.org/greenchem
An amino-terminated hyperbranched polymer (HBP-NH2) has been prepared through the Michael
addition reaction between amines and methyl acrylate (MA) at 0 °C, followed by self-condensation of the
addition reaction products at 100 °C and 140 °C. A novel CO2-“imprinted” hyperbranched polymeric
adsorbent (IHBPA) with a high amino density was conveniently prepared by using glutaraldehyde to cross-
link HBP-NH2 which had pre-adsorbed CO2. Through comparing the adsorption capacities of the IHBPA
with HBPA, which was prepared with a similar procedure to that of IHBPA but without CO2 pre-adsorp-
tion, it could be found that the pre-adsorbed CO2 on HBP-NH2 would occupy the reactive sites of amino
groups, and play the role of “imprinting” in the preparation of the adsorbent. The adsorption capacity of
the IHBPA could thus be improved. After reducing the imino groups of the IHBPA to alkyl amine by
NaBH4, the adsorption capacity of the reducing solid amine adsorbent (IHBPA-R) can be further
improved. The prepared solid amine adsorbents also showed promising regeneration performance, which
could maintain almost the same adsorption capacity for CO2 after 10 adsorption and desorption recycles.
The high CO2 adsorption capacity (7.65 mmol g−1) of IHBPA-R can be attributed to its high amino density,
terminal amine and hyper-branched structures.

1. Introduction demonstrated that graphene-based mesoporous silica

CO2 capture from exhaust gas streams is considered as a poss-
ible method to decrease anthropogenic CO2 emissions that
can aggravate global warming. As an alternative to conventional
liquid amine scrubbing technology, adsorption-based pro-
cesses using solid adsorbents have been proposed as an
admirable approach for CO2 capture, as it can possibly reduce
the energy demand relative to current capture processes.1–3
Among the wide array of adsorbent materials studied for CO2
removal from both ambient air and flue gas streams, solid
amine adsorbents have been identified as one of the most
promising materials due to their less equipment corrosion,
high selectivity, simple and scalable synthesis, high regener-
ability, and more importantly, improved capacity in the pres-
ence of water when compared to conventional physical
sorbents.4–6 Solid amine adsorbents were fabricated by
loading amines through impregnation or grafting onto
different types of supports, including zeolites,5,6 carbon,7,8
organosilica, and surface-modified silica.9,10 Yang et al.11
a
PCFM Lab, School of Chemistry and Chemical Engineering, Sun Yat-Sen University,
Guangzhou 510275, PR China. E-mail: cescsx@mail.sysu.edu.cn;
Fax: +86-20-84034027
b porous substrates. However, the amine of an excessive loading
Materials Science Institute, Sun Yat-Sen University, Guangzhou 510275, PR China
† Electronic supplementary information (ESI) available. See DOI: 10.1039/
c6gc01416j
(G-silica) sheets could serve as an efficient support for PEI
(denoted as PEI/G-silica) via a nanocasting technology, and as
a consequence, PEI/G-silica sheets exhibited a high CO2
adsorption capacity (4.32 mmol g−1) and a good cycling stabi-
lity for CO2 capture. Lin et al.12 synthesized polyamine/metal–
organic framework composites (PEI/MIL-101(Cr)) by impreg-
nating PEI into MOFs, which also showed a high CO2 adsorp-
tion capacity (3.6 mmol g−1). Chaikittisilp et al.13 developed a
new method to prepare hyperbranched polyamine–oxide
hybrid materials through vapor-phase transport, in which an
oxide support was exposed to the vapor of small nitrogen-con-
taining heterocyclic monomers, and the adsorbent showed a
good cycling stability for CO2 capture, while its adsorption
capacity was only 0.93 mmol g−1 due to the low amino density.
Jones et al.14 synthesized hyperbranched amino silica (HAS)
adsorbents via the ring-opening polymerization of aziridine in
the presence of a mesoporous silica SBA-15 support, whose
adsorption capacities varied from 2.0 to 5.6 mmol g−1 at 25 °C
with the amine loadings (2 to 10 mmol N per g adsorbent),
demonstrating that the hyperbranched structure can signifi-
cantly increase the adsorption capacity and efficiency. For the
above materials, the CO2 adsorption capacity mainly depends
on the amine loading amount and the pore volume of the
amount will block the pore volume of the porous substrate,
thus reducing the adsorption capacity of CO2.10,15 So it is of

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Paper
great significance to develop alternative substrates or to strike
the balance between the amino content and the pore volume
in order to improve the CO2 adsorption performance.
Many studies have demonstrated that all the three types of
amines (1°, 2°, and 3° amines) can adsorb CO2 in the presence
of water, and the adsorbed CO2 is easily desorbed from the
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adsorbents with low energy consumption.9,10 However, in the
absence of water, the imine and amide groups cannot react
with CO2, thus reducing the CO2 adsorption capacity and the
amine utilization efficiency. So, it is significant to control the
amino types to overcome the above defect.
Highly branched polymers have been studied extensively in
recent years. Compared to their corresponding linear poly-
mers, highly branched polymers, such as dendrimers and
hyperbranched polymers, possess unique physical properties
that stem from their different architectures.15–20 By modifying
the highly branched architecture and the large number of
terminal functional groups of hyperbranched macromolecules,
hyperbranched polymers can be tailored for some specialized
purposes.21–24 The tunable topology and functionality of a new
class of amino-terminated hyperbranched polymers
(HBP-NH2) with a high amino content has attracted attention
from industry and academia.17,25–28
In this work, HBP-NH2 was prepared through the reaction
between amines and methyl acrylate (MA) in one-pot. A novel
CO2-“imprinted” hyperbranched polyamine solid amine adsor-
bent (IHBPA-R) with a high amino density was then con-
veniently prepared through crosslinking of the CO2-
“imprinted” HBP-NH2 with glutaraldehyde (IHBPA), followed
by reduction with NaBH4. The chemical construction, adsorp-
tion performance, regeneration ability, and adsorption mech-
anism of materials were also studied.
2. Experimental section
2.1 Materials and reagents
Methyl acrylate (MA), diethylenetriamine (DETA), triethyl-
enetetramine (TETA), tetraethylenepentamine (TEPA), glutar-
aldehyde, methanol, ethanol, and sodium borohydride of
analytical reagent grade were purchased from Guangzhou
Reagent Company. Deionized water was used to prepare all
solutions in the study.
2.2 Preparation of a hyperbranched polyamine adsorbent
(HBPA)
In a typical synthesis procedure of HBP-NH2: 0.5 mol TEPA was
dissolved in 50 mL anhydrous methanol at 0 °C under N2 pro-
tection. 0.5 mol MA was also dissolved in 50 mL anhydrous
methanol and added dropwise to the above TEPA solution.
TEPA reacted with MA through the Michael addition reaction
to produce a light yellow liquid intermediate (addition
product). The intermediate was transferred to a round bottom
flask in rotary evaporation apparatus; and heated at 60 °C for
1 h to remove the methanol solvent, and then kept at 100 °C
for 2 h to carry out the condensation reaction. After that, the
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reaction temperature was elevated to 140 °C and kept for 2 h to
further complete the self-condensation. The generated metha-
nol in the reaction was removed by rotary evaporation in a
vacuum. The obtained amino-terminated hyperbranched
polymer was labeled HBP-NH2.
The preparation of HBPA: 2.00 g HBP-NH2 was dissolved in
10.0 mL water, then 2.2 mL aqueous glutaraldehyde solution
(25 wt%) was added dropwise into the HBP-NH2 solution and
intensely stirred at 25 °C. HBP-NH2 was crosslinked by glutar-
aldehyde to form solid particles. The particles were soaked
with 60% aqueous ethanol solution for 4 h, and then washed
with water, and finally dried at 60 °C. The obtained hyper-
branched polyamine adsorbent was labeled HBPA.
DETA and TETA were also used to prepare HBPA, the prepa-
ration procedure was similar to that by using TEPA. To identify
the kinds of HBPAs using different amines as reactants, the
HBPAs were labeled HBPA(x), x would be DETA, TETA, or TEPA.
2.3 Preparation of a CO2-“imprinted” hyperbranched
polyamine adsorbent (IHBPA)
2.00 g HBP-NH2 was dissolved in 10.0 mL water, and into
which a CO2 stream was fed at 25 °C to get a CO2 saturated
HBP-NH2. 2.2 mL glutaraldehyde (25 wt%) was added dropwise
into the above HBP-NH2 solution with vigorous stirring at
5 °C. HBP particles “imprinted” with CO2 were thus obtained.
After being soaked with 60% aqueous ethanol solution and
then thoroughly washed with water, the particles were heated
at 90 °C under a nitrogen stream to remove CO2 and water,
and the dried CO2-“imprinted” hyperbranched polyamine
adsorbent was labeled IHBPA.
2.4 Preparation of IHBPA-R
2.00 g IHBPA was soaked in 100 mL methanol for 30 min, and
2.00 g sodium borohydride was gradually added into the
IHBPA mixture at room temperature, and then the mixture was
continuously stirred at room temperature for 3 h so that
sodium borohydride can completely reduce the imine groups
in IHBPA to amine groups. After the reaction, the product was
washed with deionized water and dried at 60 °C. The obtained
product was labeled IHBPA-R.
The synthesis principle of the solid amine adsorbent is
shown in Fig. 1.
Based on the above synthesis principle of HBP-NH2, a poss-
ible structure of HBP-NH2 is as follows (Fig. 2).
2.5 Physical and chemical characterization
Elemental analysis (Elementar, Vario EL), infrared (IR) spec-
troscopy (Tensor-27 spectrometer), and X-ray photoelectron
spectroscopy (ESCALAB 250, Thermo-VG Scientific) were
employed to determine the composition and chemical struc-
ture of a hyperbranched polymer. A high performance liquid
chromatograph (Waters 600) and a gel column (TSK-GEL
G2000 SW XL, 7.8 mm × 300 mm) were employed to determine
the molecular weight of the hyperbranched polymer. Test con-
ditions: mobile phase was phosphate buffer (pH = 7.0); detec-
tion wavelength was set at 222 nm; flow rate was 0.5 mL min−1;
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Fig. 1 Synthesis principle of solid amine adsorbents.

Fig. 2 A possible structure of HBP-NH2.

column temperature was 300 °C; injection volume was instrument (ASAP2020, Micromeritics Corp, USA) in a relative
10 μL. The adsorption–desorption isotherms of nitrogen at pressure range from 10−6 to 1 after degassing the test sample
77.35 K was measured with an automatic gas adsorption at 150 °C. The pore volume (Vtotal ) was calculated based on the

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nitrogen amount adsorbed at P/P0 = 0.95. The BET surface
areas (SBET) and pore size distribution were calculated through
the Brunauer–Emmett–Teller (BET) method and the density
functional theory (DFT) method, respectively.
2.6 CO2 adsorption procedure
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Breakthrough curves were used to characterize the CO2 adsorp-
tion performances of all samples. 1.00 g of the adsorbent
sample was tightly placed in an adsorption column (Φ =
1.3 cm), into which a dry nitrogen flow was introduced at a
flow rate of 30 mL min−1 for 0.5 h to remove the air in the
column. Then, the dry CO2/N2 mixed gas (CO2 : N2 = 1 : 9
(volume ratio)) was introduced through the column at a flow
rate of 30 mL min−1. The inlet/outlet concentrations of CO2
were analyzed every two minutes, using a Techcomp 7900 gas
chromatograph equipped with a thermal-conductivity detector
(TCD). And for the CO2 capture test in the presence of water,
the sample was first immersed in water, then packed in a
column (Φ = 1.3 cm), into which a dry nitrogen flow was intro-
duced at a flow rate of 30 mL min−1 for 0.5 h to remove the air
and excess water in the column. The effect of adsorption temp-
erature on the adsorption was investigated in the range of 10
to 80 °C. After adsorption, pure nitrogen gas at a flow rate of
30 mL min−1 was introduced through the column at 90 °C to
regenerate the used adsorbent sample.
The adsorption capacity was calculated as follows:
ðt
Q ¼ ðCin  Ceff ÞV dt=22:4W ð1Þ
0
where Q represents the adsorption capacity (mmol CO2 per g),
t is the adsorption time (min), and Cin and Ceff are the influent
and effluent concentrations of CO2 (vol%), respectively. V is
the total flow rate, 30 mL min−1; W and 22.4 are the weight of
the sample (g) and the molar volume of gas (mL mmol−1),
respectively.
3 Results and discussion
3.1 Preparation of a hyperbranched polyamine adsorbent
(HBPA)
DETA, TETA, and TEPA were used in the preparation of
HBP-NH2 with a high amino density, in which an equal molar
ratio of amines and MA was mixed. The molecular weights of
HBP-NH2 prepared by using various amines are listed in
Table 1.
As shown in Table 1, it is obvious that the molecular weight
and nitrogen content of HBP-NH2 increased in the order of
Table 1 Molecular weights and amine contents of HBP-NH2 prepared by using DETA, TETA, and TEPA
Amines HBP-NH2 Mw C (wt%) N (wt%) H (wt%)
DETA 7496 53.34 25.40 11.57
TETA 8657 52.07 27.83 12.16
TEPA 9934 51.54 29.25 12.52
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DETA, TETA and TEPA when they were used as reactants,
because the longer chain length, higher amino content and
molecular weight of amines would lead to a higher molecular
weight of the repeating units of the intermediate.17 The CO2
absorption amount correlatively increased with the amino
content in HBP-NH2.
The IR spectra of the addition reaction product (intermedi-
ate) and HBP-NH2 are shown in Fig. 3. Compared with the
intermediate, the characteristic absorption peak at
1736.15 cm−1 disappeared in HBP-NH2, and the peak at
1651.28 cm−1 was weakened in HBP-NH2, indicating that the
ester group in the intermediate reacted with the amino group
to form an amide group. Meanwhile, the strong absorption
peaks of methanol at 1118.54 cm−1 and 3080.86 cm−1 dis-
appeared, and the N–H stretching vibration shifted to
3406.73 cm−1 in the spectrum of HBP-NH2,6,10,29 which
revealed that there was no methyl alcohol existing in
HBP-NH2. These results confirmed that a polycondensation
reaction occurred between the ester and the amino groups of
intermediates, and the ester groups of MA were converted into
amide groups in the prepared HBP-NH2.
Glutaraldehyde was used to crosslink HBP-NH2 to prepare
solid amine particles. Fig. 4 indicates that the needed dosage
of glutaraldehyde to crosslink HBP-NH2 to form HBPA solid
particles was higher for HBPA(DETA) than for HBPA(TETA)
and HBPA(TEPA), which meant more amino groups were con-
verted to imine groups. As a result, CO2 adsorption capacity
Fig. 3 IR spectra of the addition reaction product of TEPA and MA,
namely the intermediate (a) and HBP-NH2 (b).
Amino amount (mmol g−1) CO2 absorption amount (mmol g−1)
18.14 8.07
19.88 10.86
20.89 12.95
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Fig. 4 Effect of glutaraldehyde dosages on adsorption capacity of
HBPA (adsorbent mass: 1.0 g; adsorption temperature: 25 °C; concen-
tration of CO2: 10% (N2: 27 mL min−1; CO2: 3 mL min−1)).
and the amine utilization efficiency of HBPA(DETA) were less
than those of HBPA(TETA) and HBPA(TEPA).
3.2 CO2-“imprinting” of the hyperbranched polyamine
adsorbent
HBP-NH2 solution was firstly subjected to pre-adsorb CO2, and
then the CO2 pre-adsorbed HBP-NH2 was crosslinked with
glutaraldehyde to prepare a CO2-“imprinted” hyperbranched
polyamine adsorbent (IHBPA). By comparing the morphology
of HBPA and IHBPA, it can be found that IHBPA particles were
much looser than HBPA particles. It can be attributed to the
micropores formed during the escape of the adsorbed CO2
from the matrix. Besides, from the SEM image of the IHBPA
(Fig. S2†) it can also be found that the IHBPA(TEPA) sample
consisted of irregular microparticles. The obtained particles
Fig. 5 CO2 adsorption capacities of IHBPA and HBPA (adsorbent mass:
1.0 g; adsorption temperature: 25 °C; concentration of CO2: 10% (N2:
27 mL min−1; CO2: 3 mL min−1)).
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were further purged with a N2 stream at 90 °C to completely
desorb CO2.
From Fig. 5 it is evident that IHBPA had a higher CO2
adsorption capacity than HBPA (the data points without CO2
pre-adsorption). Moreover, with the increase of the pre-CO2
adsorption amount of HBP-NH2, CO2 adsorption capacity of
as-prepared IHBPA increased. The adsorption capacities of
IHBPA(DETA), IHBPA(TETA), and IHBPA(TEPA) that were pre-
pared from CO2 saturated HBP-NH2 have an increment of
1.06 mmol g−1 (36.30%), 1.13 mmol g−1 (29.89%) and
1.27 mmol g−1 (28.22%), respectively. This was because of the
fact that the pre-adsorbed CO2 on HBP-NH2 would occupy the
reactive sites of amino groups, and play the role of “imprint-
ing” in the preparation of the adsorbent, leading to a higher
CO2 retaining amount (2.2–2.8 mmol g−1) in the particles after
the crosslinking step. And after the removal of pre-adsorbed
CO2, the porous structure of the adsorbent could facilitate the
diffusion of CO2 into the particles and its reaction with the
available amino groups.
3.3 Improvement of IHBPA adsorption capacity by the
reduction of imine groups
As we know that the crosslinking reaction between the alde-
hyde groups of glutaraldehyde and the amino groups of
HBP-NH2 would generate imine groups which cannot chemi-
cally adsorb CO2. To efficiently use these imine groups, the
imine groups on IHBPA were reduced by sodium borohydride
and converted to alkyl amine groups, the resulting amine
adsorbent was labeled IHBPA-R.
The IR spectra of IHBPA and IHBPA-R are compared in
Fig. 6. It is obvious that the N–H stretching vibration peak at
3406.73 cm−1, and the peaks at 1458.41 cm−1 and
1118.86 cm−1 that can be ascribed to the amine N–H defor-
mation vibration of nonconjugated C–N and C–N stretching
vibration in IHBPA-R were enhanced,6,10,29 while the stretching
vibration peak at 1651.28 cm−1 that can be ascribed to the
amine N–H deformation vibration or CvN or OvC–NH was
Fig. 6 IR spectra of IHBPA and IHBPA-R.
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Table 2 Amino contents determined by EA and XPS analysis

Determination
method EA analysis XPS analysis

Amino content Amide Imino Alkyl amino 1° amino 2° amino 3° amino

Material (mmol g−1) content (%) content (%) content (%) content (%) content (%) content (%)
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IHBPA(DETA) 11.76 12.16 19.35 68.49 27.03 18.38 23.08

IHBPA(TETA) 13.16 10.69 17.37 71.94 30.82 19.17 21.95
IHBPA(TEPA) 14.16 8.85 15.96 75.19 34.39 19.91 20.89
IHBPA(TEPA)-R 14.15 8.74 0 91.26 34.37 35.93 20.96

significantly diminished. All these facts indicate the conver-
sion of the imino groups of IHBPA to 2° amino groups.
Total amino contents of the amine adsorbents by EA ana-
lysis are listed in Table 2. The nitrogen-containing groups were
further resolved into amide, imine and alkyl amine (including
1°, 2°, 3° amino) by N 1s peak processing of XPS spectra
(Fig. 7), and their contents are listed in Table 2. It can be
found that the 2° amino content of IHBPA(TEPA)-R increased
to 35.93%, while IHBPA(TEPA) was only 19.91%. The incre-
ment (16.02%) was similar to the imino group content of
IHBPA(TEPA) (15.96%), indicating that all the imino groups of
IHBPA(TEPA) were reduced to 2° amino. It can also be found
that relative contents of both the amide and imino groups
decreased in the order of IHBPA(DETA), IHBPA(TETA) and
IHBPA(TEPA), instead, the contents of alkyl amine and total
amine increased in the order of IHBPA(DETA), IHBPA(TETA)
and IHBPA(TEPA), which meant that the longer chain of TEPA
could increase the effective amino density of the prepared
solid amine adsorbents.
CO2 adsorption capacities of IHBPA and IHBPA-R are listed
in Table 3. Compared with the IHBPA adsorbent, the CO2
adsorption capacities of IHBPA(DETA)-R, IHBPA(TETA)-R and
IHBPA(TEPA)-R were improved by 1.80 mmol g−1 (45.23%),
1.81 mmol g−1 (36.86%) and 1.88 mmol g−1 (32.58%), due to
the conversion of the imino group into a CO2-adsorbable
amine group.
As presented in Fig. 7 and Tables 2 and 3, the imino con-
tents of IHBPA(DETA), IHBPA(TETA), and IHBPA(TEPA) were

Fig. 7 N 1s peak processing of XPS of IHBPA(DETA) (a), IHBPA(TETA) (b), IHBPA(TEPA) (c), and IHBPA(TEPA)-R(d).

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Table 3 Adsorption capacities and amino utilization efficiencies of serious pore blockage and CO2 diffusion resistance even with a
IHBPA and IHBPA-R (adsorbent mass: 1.0 g; adsorption temperature: high amino content, and therefore its adsorption capacity
25 °C; concentration of CO2: 10% (N2: 27 mL min−1; CO2: 3 mL min−1))
could be significantly improved, verifying the superiority of
our synthetic route.
Adsorption
Amino content capacity Utilization
Materials (mmol g−1) (mmol g−1) efficiency (%) 3.4 Effect of temperature on CO2 adsorption performance
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IHBPA(DETA) 11.92 3.98 33.39 IHBPA(TEPA)-R (amino content: 14.15 mmol g−1) was chosen
IHBPA(TETA) 13.46 4.91 36.48 to investigate the adsorption performances of the solid amine
IHBPA(TEPA) 14.16 5.77 40.75 adsorbent at different temperatures. According to the result of
IHBPA(DETA)-R 11.85 5.78 48.78
IHBPA(TETA)-R 13.42 6.72 50.07 XPS analysis, the alkyl amino ratio of nitrogen in this adsor-
IHBPA(TEPA)-R 14.15 7.65 54.06 bent was 91.26%, namely, its alkyl amino content reached up
to 12.91 mmol g−1.
The results in Fig. 8(a) indicate that CO2 could be comple-
19.35%, 17.37%, and 15.96%, respectively. After reduction, tely adsorbed by the IHBPA(TEPA)-R adsorbent at the early
their theoretical adsorption capacities should have an incre- stage. It could last for a longer time for the adsorbent to com-
ment of 2.28 mmol g−1, 2.29 mmol g−1, 2.26 mmol g−1, pletely adsorb CO2 and to break through the fixed bed when
respectively. The increments of their experimental adsorption the adsorption temperature was lower. The increasing adsorp-
capacities were 1.80 mmol g−1, 1.81 mmol g−1, and 1.88 mmol tion temperature would facilitate the breakthrough of CO2
g−1, respectively, which were 79–83% of their theoretical from the adsorption bed. Fig. 8(b) also showed that the
adsorption capacities, confirming that the imino groups were adsorption capacity and utilization efficiency were higher at
successfully reduced to 2° amine groups. lower adsorption temperatures. The CO2 adsorption capacity of
Unlike CO2 adsorption, as the adsorption capacities of IHBPA(TEPA)-R at 10 °C could reach 9.04 mmol g−1, which was
HBPA(TEPA), IHBPA(TEPA), and IHBPA(TEPA)-R for N2 were 73.85% more than that at 80 °C (5.20 mmol g−1). As is well
mainly attributed to the physical adsorption of the adsorbent, known, adsorption of CO2 with the amino group was an
all the samples showed a very low N2 adsorption capacity of exothermic reaction, and low temperatures were beneficial to
only 0.36–0.49 mmol g−1 (Table 4). But due to the higher poro- the adsorption of CO2 on an amine adsorbent.
sity of the IHBPA(TEPA) adsorbent that was brought about by
3.5 Regeneration performance
CO2 imprinting (Fig. S1†), IHBPA(TEPA) had a slightly higher
N2 adsorption capacity than HBPA. The adsorbed CO2 on IHBPA could be completely desorbed at
Compared with other reported amine-supported meso- 90 °C. The adsorbent was processed for 10 cycles of adsorption
porous adsorbents,12,14,30–34 IHBPA-R showed a higher adsorp- (at 25 °C)–desorption (at 90 °C), and the results are shown in
tion capacity under moisture (Table 5). IHBPA-R can avoid Fig. 9. After 10 cycles, no significant change in CO2 adsorption
capacity was observed, and the adsorption capacities of (HBPA
(TEPA), IHBPA(TEPA), and IHBPA(TEPA)-R) remained at 4.40 ±
0.1 mmol g−1, 5.70 ± 0.1 mmol g−1 and 7.60 ± 0.1 mmol g−1,
Table 4 N2 adsorption capacities of HBPA(TEPA), IHBPA(TEPA), and respectively. It was evident that the amino-terminated hyper-
IHBPA(TEPA)-R
branched polyamine solid amine adsorbent could stay stable
after multiple regeneration cycles and maintain its adsorption
HBPA IHBPA IHBPA
(TEPA) (TEPA) (TEPA)-R capacity for CO2.

N2 adsorption capacity (mmol g−1) 0.37 0.48 0.49 3.6 Primary exploration of the adsorption mechanism
To better interpret the adsorption behavior and adsorption
kinetics of IHBPA-R, the pseudo first-order, pseudo second-
Table 5 Comparison of CO2 adsorption capacities of amine-supported order, and Avrami kinetic models were applied to fit the
adsorbents
dynamic CO2 adsorption data at different temperatures (see
Adsorption
the details in the ESI†). The result indicates that the pseudo
capacity first-order and pseudo second-order kinetic models cannot fit
Substrate Amine (mmol g−1) Ref. the experimental data well, and therefore the physisorption or
IHBPA-R — 7.65 This work chemisorption is not the only rate-controlling step. It can be
MOF PEI 3.60 12 observed that Avrami’s kinetic model fits well with the experi-
SBA-15 Hyperbranched 5.60 14 mental data, and the correlation coefficients R2 for the
amine
Mesoporous PEI 4.82 30 measured temperatures in Table S2† are in the range of 0.997
carbons to 0.999, while the equilibrium adsorption capacities (qe) are
Activated carbons TETA 1.96 31 close to the experiment values, indicating that Avrami’s kinetic
CNTs/ACF PEI 2.75 32
HP2MGL PEI 4.05 33 model can accurately describe the CO2 adsorption. The kinetic
Y-type zeolite TEPA 4.31 34 orders (na) are in the range of 1.3 to 1.5, demonstrating that

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Fig. 8 Breakthrough curves of CO2 adsorption on IHBPA(TEPA)-R (a) and the adsorption capacities (b) at different temperatures (adsorbent mass:
1.0 g; concentration of CO2: 10% (N2: 27 mL min−1; CO2: 3 mL min−1)).

branched polyamine adsorbents. Therefore, in order to gain a

further insight of the rate-controlling step and the CO2
diffusion mechanism, the experimental kinetic data are ana-
lyzed by using diffusion models such as an interparticle
diffusion model, an intraparticle diffusion model and Boyd’s
model.35
The interparticle diffusion model is expressed as:
 2 
@q @ q 2 @q
¼ Dc þ ð2Þ
@t @r 2 r @r

qt 6
1 ¼ expðn2 k1 tÞ ð3Þ
qe π2

k1 ¼ π2 Dc =r 2 ð4Þ

The intraparticle diffusion model is expressed as:

Fig. 9 Adsorption capacities of fresh and regenerated adsorbents
qt ¼ k2 t 1=2 þ b ð5Þ
(amino contents of HBPA(TEPA), IHBPA(TEPA), and IHBPA(TEPA)-R were
14.12 mmol g−1, 14.16 mmol g−1, 14.15 mmol g−1, respectively; adsor- Boyd’s film-diffusion model is expressed as:
bent mass: 1.0 g; adsorption temperature: 25 °C; concentration of CO2:
10% (N2: 27 mL min−1; CO2: 3 mL min−1)). 6X 1
1
F ¼1 expðn2 Bt Þ ð6Þ
π2 n¼1 n2

qt
physisorption and chemisorption are both the rate-controlling F¼ ð7Þ
qe
factors for CO2 adsorption on IHBPA(TEPA)-R.
The adsorption breakthrough curves and adsorption For F > 0.85,
capacities of HBPA, IHBPA, and IHBPA-R are illustrated in
Bt ¼ 0:4977  lnð1  FÞ ð8Þ
Fig. 10. As shown in Fig. 10(a), complete adsorption happened
for all adsorbents at the beginning, and then a sharp break- and for F < 0.85,
through was observed, which indicated that all adsorbents sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
 2 ffi!2
showed good performance for CO2 diffusion and mass trans- pffiffiffi π F
fer. In Fig. 10(b), it can also be found that their adsorption Bt ¼ π π ð9Þ
3
capacities increased significantly at the early stage of complete
adsorption until its breakthrough. where qe (mmol g−1) and qt (mmol g−1) refer to the amount of
As all the steps concerned with the CO2 adsorption process CO2 adsorbed at equilibrium and at a given point of time,
are lumped together, pseudo-first-order and pseudo-second- respectively; t (min) refers to the adsorption time; Dc refers to
order models cannot provide any idea regarding the actual the effective diffusion coefficient based on the concentration;
rate-controlling step and the diffusion mechanism associated r refers to the average particle radius; b refers to the constant;
with the CO2 adsorption on the amino-terminated hyper- k1 (mmol g−1) and k2 (mmol g−1) refer to the interparticle

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Fig. 10 The adsorption breakthrough curves (a) and adsorption capacities (b) of HBPA, IHBPA, and IHBPA-R (adsorbent mass: 1.0 g; adsorption
temperature: 25 °C; concentration of CO2: 10% (N2: 27 mL min−1; CO2: 3 mL min−1)).

diffusion and the intraparticle diffusion rate constant, respect-
ively; F is the fractional attainment of equilibrium at a given
point of time; Bt is a mathematical function of F; and n is a
natural number (1,2, 3, to n).
Hence, diffusion models were applied to fit the adsorption
kinetic data to investigate whether diffusion controls the CO2
adsorption kinetics on different adsorbents. Fig. 11(a) shows
Boyd’s film-diffusion plots for CO2 adsorption on different
adsorbents, the plot of Bt against time t are nonlinear. According
to Boyd’s film diffusion model, if the plot is not a straight line,
the film-diffusion step would also play an important role in the
adsorption rate. Hence, the initial adsorption stage is attributed
to the diffusion of the CO2 molecule from the bulk gas phase to
the exterior surface of HBPA, IHBPA, and IHBPA-R.

Fig. 11 Plots of diffusion models for CO2 adsorption on different adsorbents. (a) Plots of Boyd’s film diffusion model for Bt against time, (b) linear
fitting of the intraparticle diffusion model, (c) non-linear fitting of the interparticle diffusion model.

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Paper
Fig. 11(b) shows the intraparticle diffusion plots for CO2
adsorption on different adsorbents. At the initial stage of
adsorption and the adsorption equilibrium stage, the experi-
mental data points significantly deviate from the fitting
straight line. The result indicates that the intraparticle
diffusion model cannot fit the experimental data well, and
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intraparticle diffusion is not the rate-controlling step.
Fig. 11(c) shows that interparticle diffusion plots for CO2
adsorption on different adsorbents are non-linear, and the R2
values obtained are higher than 0.99, indicating that the inter-
particle model fits the experimental data well, and interparti-
cle diffusion should also be the rate-controlling step.
A conclusion regarding the mass transfer mechanism can
be reached from the analysis of data by diffusion models. It
can be used in predicting the mechanistic steps involved in
the adsorption process, i.e. whether the rate of CO2 adsorption
is determined via the particle diffusion or film diffusion mech-
anism. For the adsorbents in this study, at the initial stage of
adsorption, film diffusion resistance controls the adsorption
rate. And after a CO2 molecule diffuses through the gas film,
the interparticle diffusion is the rate-limiting step until the
adsorption equilibrium is reached.
4. Conclusions
A novel CO2-“imprinted” hyperbranched polyamine adsorbent
(IHBPA) was prepared by using glutaraldehyde to crosslink the
pre-CO2 adsorbed HBP-NH2, which was prepared through the
reaction between amines and MA in one-pot. Using CO2 as a
template to prepare the imprinted IHBPA adsorbent could
effectively create a porous structure of the adsorbent, thus evi-
dently increase its CO2 adsorption capacities and amine
efficiency. The imino groups on the adsorbent could be
further reduced by NaBH4 to form 2° amino groups so as to
increase the amino utilization efficiency. Specifically, the
reduction product IHBPA(TEPA)-R showed a remarkable CO2
adsorption capacity (7.65 mmol g−1) in the presence of water
at 25 °C, with more than 1.8 mmol g−1 increment in adsorp-
tion capacity. HBPA, IHBPA, and IHBPA-R also showed promis-
ing regeneration performance, whose CO2 adsorption
capacities could be maintained almost the same after 10
adsorption and desorption recycles. The study of the adsorp-
tion mechanism demonstrates that the film diffusion resist-
ance was the control step of the adsorption rate at the initial
stage, and after the CO2 molecule diffused through the gas
film, the interparticle diffusion became the rate-limiting step
until reaching the adsorption equilibrium.
Acknowledgements
The authors gratefully acknowledge the financial support pro-
vided by the National Natural Science Foundation of China
(Grant No. 51473187) and the Natural Science Foundation of
Guangdong Province (2014A030313192).
5868 | Green Chem., 2016, 18, 5859–5869
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