Accepted Article

Title: Oxidatively-Stable Linear Poly(propylenimine)-Containing

Adsorbents for CO2 Capture from Ultra-Dilute Streams

Authors: Simon H Pang, Ryan P Lively, and Christopher W Jones

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To be cited as: ChemSusChem 10.1002/cssc.201800438

Link to VoR: http://dx.doi.org/10.1002/cssc.201800438

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ChemSusChem
FULL PAPER
Oxidatively-Stable Linear Poly(propylenimine)-Containing
Adsorbents for CO2 Capture from Ultra-Dilute Streams
Simon H. Pang,[a] Ryan P. Lively,[a] and Christopher W. Jones*[a]
Abstract: Aminopolymer-based solid sorbents have been widely
investigated for CO2 capture from dilute streams such as flue gas or
ambient air. However, the oxidative stability of the widely-studied
aminopolymer, poly(ethylenimine) (PEI), is limited, causing it to lose
its CO2 capture capacity after exposure to oxygen at elevated
temperatures. Here we demonstrate the use of linear
poly(propylenimine) (PPI), synthesized via a simple cationic ring-
opening polymerization, as a more oxidatively-stable alternative to
PEI with high CO2 capacity and amine efficiency. The performance
of linear PPI/SBA-15 composites is investigated over a range of CO2
capture conditions (CO2 partial pressure, adsorption temperature) to
examine the tradeoff between adsorption capacity and sorption site
accessibility, which may be expected to be more limited in linear
polymers relative to the prototypical hyperbranched PEI. Linear
PPI/SBA-15 composites are more efficient at CO2 capture and retain
65-83% of their CO2 capacity after exposure to a harsh oxidative
treatment, compared to 20-40% retention for linear PEI. Additionally,
we demonstrate long-term stability of linear PPI sorbents over 50
adsorption/desorption cycles with no loss in performance. Combined
with other strategies for improving oxidative stability and adsorption
kinetics, linear PPI may play a role as a component of stable, solid
adsorbents in commercial applications for CO2 capture.
Introduction
Research into materials for direct capture of CO2 from dilute
streams such as flue gas or ambient air has focused on solid
adsorbents due to the potential for reducing the energy required
for material regeneration compared to the benchmark
technology of aqueous solutions of amines.[1–4] In particular,
amines supported in a variety of solids (oxides,[5–15],
polymers,[16–18] metal-organic frameworks,[19–21] for example)
have been studied due to their high heats of CO2 adsorption[22–
24]
and the consequently higher capture and separation
efficiencies[25] achievable. However, these high heats of
adsorption require high temperatures to regenerate the material,
and these harsh conditions can cause material degradation.
Amine-containing sorbents are known to degrade via a
number of different mechanisms that are accelerated at the high
temperatures required for sorbent regeneration: oxidative
degradation,[26–29] formation of urea in CO2-rich atmospheres,[30–
32]
and loss of aminopolymer at high temperature via evaporation
[a] Dr. S. H. Pang, Prof. R. P. Lively, Prof. C. W. Jones
School of Chemical & Biomolecular Engineering
Georgia Institute of Technology
311 Ferst Drive, Atlanta, GA 30332 (USA)
E-mail: cjones@gatech.edu
Supporting information and the ORCID identification numbers for the
authors of this article can be found under
https://dx.doi.org/10.1002/cssc.xxxxxxxxx.
This article is protected by copyright. All rights reserved.
10.1002/cssc.201800438
or leaching in the presence of steam.[33,34]
For direct air capture, oxidative degradation is a major
concern, due to the abundance of O2 in the air. The oxidation of
amines is known to occur through a radical-mediated process,
Accepted Manuscript
and though is typically catalyzed by transition metal ions, can
occur in the absence of such ions at elevated temperatures.[35,36]
The susceptibility of various types of amines to oxidation has
been studied for molecularly grafted, isolated aminosilanes, with
the major finding that primary and tertiary amines are relatively
resistant to oxidative degradation, whereas secondary amines
and secondary-amine-containing molecules degrade via
formation of imines or amides.[26,27]
In the case of polymeric amines, randomly-branched
poly(ethylenimine) (PEI), which is the best studied
aminopolymer for CO2 capture, is known to readily degrade in
oxidizing environments.[37–39] Ahmadalinezhad and Sayari
investigated the structures created during oxidation of PEI via
detailed NMR studies. They suggest that aminopolymers that
only contain primary amines should be the most resistant to
degradation, followed by aminopolymers that contain only
secondary amines, with highly branched aminopolymers that
contain primary, secondary, and tertiary amines being the least
stable.[39] This is supported by studies utilizing poly(allyl amine)
(PAA)-based sorbents, which are more resistant to oxidative
degradation than PEI-based sorbents.[38,40]
However, one of the downsides of aminopolymers that
only contain primary amines is that they will rapidly deactivate in
CO2-rich atmospheres at elevated temperature via formation of
urea. A study by Sayari et al. demonstrates that branched PEI
and PAA deactivate via urea formation more rapidly than linear
PEI.[31] They propose that the primary amines on branched PEI
and PAA react with CO2 and dehydrate to form isocyanate
species, which readily react with another amine to form ureas
that bridge two molecules. However, the secondary amines
present on linear PEI form cyclic ureas between two neighboring
amines through dehydration of an ammonium carbamate
intermediate. This pathway is hypothesized to be slower than
the isocyanate pathway, possibly due to secondary amines
being more sterically hindered.[37,41] Therefore, though linear PEI
is susceptible to oxidative degradation, linear aminopolymers
may be desirable for preventing deactivation through urea
formation.
Several groups have developed strategies for improving
oxidative stability of PEI-based sorbents. Srikanth and Chuang
have reported that blending of small aminopolymers with
poly(ethylene glycol) (PEG) improves the oxidative stability of
the sorbents by hydrogen bonding with amines.[29,42] This is
proposed to help disperse the aminopolymer and prevent O2
from accessing the amine sites, which retards oxidation.
Following this, Choi et al. have functionalized branched PEI with
1,2-epoxybutane, which incorporates hydrogen bonding groups
directly onto the aminopolymer, to simultaneously suppress urea
formation and oxidative degradation of amines by reducing the
ChemSusChem
FULL PAPER
fraction of primary amines.[43] The same group has extended
their work to incorporating metal chelating groups on the silica
support to help remove ppm levels of residual oxidation-
catalyzing metal ions that remain from the polymer synthesis.[44]
Our previous work has shown that increasing the spacing
of the amines in the backbone, by switching from a
poly(ethylenimine) to a poly(propylenimine) (PPI) drastically
improves the stability against oxidative degradation for small
molecule aminopolymers.[45] This stability improvement was
observed for PPI molecules that both contained and did not
contain secondary amines. This observation is in agreement
with previous work with small molecule amines that suggested
that ethylenimines in oxidizing conditions can undergo chain
rearrangement reactions to form six-membered rings, which are
easily oxidized to piperazinones. In contrast, propylenimines
would form either four- or eight-membered rings, which are
relatively unfavorable, and so do not deactivate as readily.[46,47]
However, for all of these small molecule studies, evaporative
loss of amine during high temperature sorbent regeneration is a
major concern from both an economic and environmental
perspective.
Based on these previous investigations, in this study we
sought to develop an oxidatively-stable aminopolymer-based
sorbent for capture of CO2 from dilute streams based on
poly(propylenimine). To both mitigate urea formation and reduce
evaporative loss of aminopolymer during high temperature
regeneration, we synthesized linear PPI at a range of molecular
weights to probe material stability during CO2 capture from dilute
conditions.
Results and Discussion
Synthesis of linear PPI was carried out via cationic ring-
opening polymerization of 2-methyl-5,6-dihydro-4H-1,3-oxazine
(MeOZI) with methyl p-toluenesulfonate (MeOTs) as the initiator.
The resulting poly(MeOZI) was hydrolyzed under acidic
conditions to remove the protecting groups, and then carefully
neutralized via addition of NaOH and washed copiously with
Scheme 1. Synthesis of linear poly(propylenimine) via cationic ring-opening polymerization of 2-methyl-5,6-dihydro-4H-1,3-oxazine.
This article is protected by copyright. All rights reserved.
10.1002/cssc.201800438
aqueous NH4OH to remove any residual inorganic salt,
generating linear PPI (Scheme 1). The monomer to initiator ratio
was varied to control the resulting molecular weight of the
polymer, and the resulting number-averaged molecular weight
was estimated via 1H NMR by end group analysis (Figures S1-
S4). The ordering of molecular weights was also confirmed via
aqueous GPC (Figure S5). As a starting point, linear PPI at
approximately 1000 g/mol was synthesized to mimic the number
of polymer repeat units contained in the traditionally-studied
randomly-branched PEI (800 g/mol). At all molecular weights
studied, linear PPI was recovered as an off-white solid at room
Accepted Manuscript
temperature; for comparison, the traditionally-studied randomly-
branched PEI is a viscous liquid at room temperature, and
commercially-available linear PEI is a solid at room temperature.
Composites of linear PPI and mesoporous silica SBA-15
were prepared by wet impregnation of a methanolic PPI solution;
the loading of polymer in the composite was controlled by
varying the polymer-to-silica ratio, and the actual loading was
confirmed via TGA (Figure S6). For all of the polymer molecular
weights, the textural properties and distribution of polymer within
the mesopores of SBA-15 was investigated by nitrogen
physisorption and the resulting isotherm was analyzed via the
BJH method to calculate a pore size distribution (Figure 1,
Figure S7, Table S1). The nitrogen physisorption isotherm for
the bare SBA-15 material is characterized by sharp uptake in the
region of P/P0 < 0.01, corresponding to adsorption within the
intra-wall micropores of the silica. This is followed by multilayer
adsorption of N2 and finally capillary condensation within the
mesopores. These adsorption steps correspond to a population
of micropores with diameter below 2 nm, and a larger population
of mesopores with diameter centered around 7.0 nm.
At roughly 10-20 wt% linear PPI loading, the micropores
are essentially inaccessible to nitrogen, suggesting that at these
low polymer loadings, a monolayer of polymer is formed on the
mesopores walls, which either fills or blocks access to the
micropores. This is accompanied by a decrease in the average
pore diameter to approximately 6.5 nm. Further increase in
polymer loading is accompanied by a decrease in the pore
volume with a gradual decrease in the pore diameter until the
ChemSusChem
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pores are nearly completely filled at about 50 wt%. This behavior
is similar to that observed for composites of randomly-branched
PEI and SBA-15, which was also studied via small-angle
neutron scattering, suggesting that, similarly to PEI, linear PPI
first forms a conformal coating on the mesopores walls, followed
by forming aggregates of polymer that grow along the axis of the
pore.[48] Notably, there was no apparent difference in the pore-
filling behavior of linear PPI as the molecular weight was varied
by almost two orders of magnitude, suggesting that the
impregnation method was able to achieve similarly distributed
linear PPI within the pores of SBA-15 in all cases.
Figure 1. (a) Nitrogen physisorption isotherms at 77 K and (b) resulting pore
size distributions calculated by the BJH method for linear PPI (1000
g/mol)/SBA-15 composites as a function of polymer loading. Open symbols
indicate the desorption branch of the isotherm. Isotherms and pore size
distributions for additional linear PPI molecular weights can be found in Figure
S7.
The CO2 adsorption performance of these supported linear
PPI composites under direct air capture conditions was studied
gravimetrically in a TGA by a temperature swing process.
Adsorption was performed at 35 °C with simulated air (400 ppm
CO2 in N2), and sorbent regeneration was performed at 110 °C
in UHP N2. Adsorption experiments were performed in triplicate
on different powder samples and the results are plotted in terms
of amine efficiency in Figure 2, and CO2 capacity in Figure S8.
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10.1002/cssc.201800438
As shown in Figure 2, the amine efficiency and CO2
capture capacity of all linear PPI sorbents increased as polymer
loading in the SBA-15 was increased. In the low polymer loading
regime (< 10 mmol N/g SiO2), all molecular weights of polymer
appeared to perform similarly for the adsorption conditions used
in this study. However, at high polymer loading (> 10 mmol N/g
SiO2), the amine efficiency of the polymers appeared to
decrease slightly as the molecular weight of the linear PPI
increased, reaching about 0.16 mmol CO2/mmol N for the lower
molecular weight polymers and only 0.13 mmol CO2/mmol N for
the higher molecular weight polymers. In agreement with this
Accepted Manuscript
trend, the corresponding small molecule linear propylenimine,
tripropylenetetramine (TPTA), achieved higher amine
efficiencies than any of the linear PPIs, though it should be
noted that per molecule, TPTA has two primary amines, which
are expected to be the most efficient for CO2 capture.[49]
Figure 2. Amine efficiencies of linear PPI and PEI impregnated in SBA-15
(adsorption in 400 ppm CO2/N2 at 35 °C, 18 h) over a range of amine loading.
Open symbols indicate samples exposed to oxidative treatment (21% O2/N2 at
110 °C, 24 h) prior to CO2 adsorption. Data for TPTA are replotted from ref. [45].
Error bars indicate the standard deviation of three separate adsorption
experiments on different powder samples.
Similar adsorption experiments were performed for
commercially-available linear PEI at two different molecular
weights. As observed previously, the amine efficiency for the
PEI composites was lower than that for the PPI composites,[45]
likely due to the decrease in the basicity (pKa) of the amines with
decreasing length of the hydrocarbon spacer.[50] Under similar
adsorption conditions, the amine efficiency of linear PEI/silica
composites can be increased to about 0.10 mmol CO2/mmol N
by using a higher pore volume silica,[51] though this value is still
lower than that achievable by linear PPI composites as shown
here.
The best amine efficiency and corresponding CO2 capture
capacity for linear PPI/SBA-15 reported here (0.16 mmol
CO2/mmol N and 1.25 mmol CO2/g composite, respectively, for
the sample made with the 1000 g/mol linear PPI) is better than
that reported for randomly-branched PEI/SBA-15 composites
(1.05 mmol CO2/g composite) under similar conditions and
amine loadings.[52] In addition to the increased basicity of the
ChemSusChem 10.1002/cssc.201800438

FULL PAPER
amines on linear PPI, we hypothesize that the increase in amine
efficiency and CO2 capture capacity for the linear PPI/SBA-15
materials relative to the randomly-branched PEI/SBA-15
materials is in part due to the absence of tertiary amines, which
are present on the branched PEI and are essentially inactive for
CO2 capture under the conditions used here.[49] These values fall
short of the highest reported capacities of about 2.35 mmol
CO2/g composite for PEI impregnated in high pore volume
fumed silicas.[12,14] To test the effect of increased pore volume of
the support, a mesocellular silica foam (MCF) was impregnated
with linear PPI (1000 g/mol) at an amine loading of 14 mmol N/g
and CH2 asymmetric and symmetric stretching (2940, 2873,
2815 cm-1). These same stretches are observed for dendritic
PPI.[53] The stretches observed in the lower wavenumber region
are attributable to formation of ammonium carbamate pairs
(a/symmetric NH2+ at 1640 and 1480 cm-1, and a/symmetric
COO- at 1540, 1420, and 1380 cm-1),[54,55] due to adsorption of
atmospheric CO2. Below this region, the IR spectra for the
composites are dominated by modes from the silica support, but
spectra of the neat polymer display bands predominantly at
1315 and 1110 cm-1 attributable to CH2 wagging and C-N
stretching modes as well (Figure S9).

Accepted Manuscript
SiO2. However, this composite performed no better than linear
PPI/SBA-15 composites (0.17 mmol CO2/mmol N, 1.33 mmol
CO2/g composite), suggesting that the morphology of the
polymer layer was more important than the morphology of the
support in the linear PPI case.
The amine efficiencies of linear PPI/SBA-15 composites
after an accelerated oxidative treatment are also shown in
Figure 2. The as-prepared composite materials at high polymer
loading were exposed to a stream of ultrazero grade air at
110 °C for 24 h to simulate potential exposure to air at the
adsorbent regeneration temperature during the temperature
swing process. In all cases, the loading of polymer changed
almost negligibly (< 5% decrease in amine loading) and all of the
samples retained the capability to capture CO2. In particular for
air capture, the 700 g/mol and 1000 g/mol samples retained
about 65% of their amine efficiency, whereas the higher
molecular weight 6700 g/mol and 36000 g/mol samples retained
over 83%. The retention of amine efficiency for sorbents
prepared from linear PPI after exposure to oxidative treatment at
higher concentrations of CO2 (Figure S10f) is similar to that for
other state-of-the-art materials. In the flue gas capture regime
(10-15% CO2), the 1000 g/mol linear PPI composite retains
about 75% of its amine efficiency, comparable to epoxide-
functionalized PEI reported by Choi et al.[43] (retention of
between 56 and 81% amine efficiency depending on extent of
functionalization). In the 1 bar regime, the 1000 g/mol linear PPI
samples retains about 85% of its amine efficiency, which is
better than blends of tetraethylenepentamine (TEPA) and
poly(ethylene glycol) (PEG) reported by Srikanth and Chuang[29]
(retention of between 37 and 56% amine efficiency depending
Figure 3. FTIR spectra of linear PPI and PEI impregnated in SBA-15 before
on the ratio of TEPA to PEG). (black) and after exposure to oxidative treatment (21% O2/N2 at 110 °C, 24 h)
In comparison, the low molecular weight linear PEI sample (red). Spectra were acquired under a flow of UHP N2 and normalized to the Si-
lost over 80% of its amine efficiency and the high molecular O-Si framework bending mode at 460 cm-1.
weight linear PEI lost between 60 and 75% of its amine
efficiency, depending on the polymer loading. These greater
losses in amine efficiency are expected based on our previous After exposure to the oxidizing conditions, the bands for
results with small molecule aminopolymers.[45] The differences in the linear PPI/SBA-15 composites largely remained the same,
loss in CO2 capture capacity and amine efficiency for the though the intensity of the N-H and CH2 stretches decreased
different aminopolymer molecular weights will be discussed slightly, potentially indicating some small loss of organic content.
within the context of mass transport limitations in more detail However, for the linear PEI/SBA-15 composites, an intense
below. band appeared at 1670 cm-1, attributable to formation of C=N or
Fourier transform infrared (FTIR) spectra for the linear C=O groups, consistent with oxidation of
aminopolymer/SBA-15 composites before and after exposure to poly(ethylenimines).[29,37,38,43] The appearance of this band was
the oxidative treatment are shown in Figure 3. Additionally, accompanied by a significant reduction in intensity of the N-H
spectra for the unsupported, neat linear PPI were acquired in and CH2 stretches, as expected. These features can be
attenuated total reflectance (ATR) mode for comparison (Figure correlated with the loss in CO2 capture capability shown in
S9). Prior to the treatment, the major bands present above 2000 Figure 2.
cm-1 correspond to the linear PPI backbone, evident for both the To examine the applicability of linear PPI sorbent materials
composites and the neat polymer – N-H stretching (3240 cm-1) across a range of CO2 adsorption conditions, CO2 adsorption
isotherms were obtained at a range of temperatures (Figure 4a,

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ChemSusChem
FULL PAPER
Figure S10). For all of the linear PPI sorbents, the temperature-
dependent behavior depended strongly on the CO2 partial
pressure regime under consideration. For partial pressures
relevant to direct air capture (PCO2 = 0.3 Torr), the CO2 capacity
and amine efficiency decreased as the adsorption temperature
increased, consistent with an exothermic chemisorption process
that is thermodynamically-limited. This behavior has been
observed for randomly-branched PEI/SBA-15 composites[56] as
well as for amine-grafted sorbents constructed from
aminosilanes grafted on mesocellular silica foam.[49]
Figure 4. (a) CO2 adsorption isotherms, plotted in terms of amine efficiency,
obtained for the 50 wt% linear PPI (1000 g/mol)/SBA-15 sample from 25 °C to
75 °C. Dashed lines indicate relevant partial pressures for direct air capture
and flue gas capture. (b) CO2 adsorption heating/cooling isobar for the 50 wt%
linear PPI (1000 g/mol)/SBA-15 sample obtained in 10% CO2/N2.
In contrast, at pressures near 1 bar, the CO2 capacity and
amine efficiency increased as temperature increased, reaching a
value of 2.5 mmol CO2/g composite (Figure S10) at 75 °C for the
1000 g/mol linear PPI with an amine efficiency of 0.32 mmol
CO2/mmol N. This CO2 capacity is slightly lower than the highest
value reported for randomly branched PEI/SBA-15 composites
at similar polymer loading (2.7 mmol CO2/g composite) at the
same temperature and partial pressure, though the amine
efficiency reported here is higher due to the lower amine density
of PPI compared to PEI.[40]
This behavior is not consistent with a thermodynamically-
limited process and has been ascribed to high mass transport
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10.1002/cssc.201800438
resistance for diffusion of CO2 within the bulk of the
aminopolymer and an inability for CO2 to access all of the amine
sites. As the temperature is increased, the flexibility and mobility
of the polymer chains increases, as does the diffusivity of CO2.
In turn, more amine sites become accessible for adsorption, and
thus, the CO2 capacity of the material increases. At 1 bar CO2,
this has been observed for PEI/MCM-41,[5] PEI/KIT-6,[8]
PEI/SBA-15 and PAA/SBA-15.[40]
A similar phenomenon occured at partial pressures
relevant to flue gas capture (PCO2 = 76 Torr) – initially the CO2
capacity and amine efficiency increased as temperature
Accepted Manuscript
increased. However, the 1000 g/mol linear PPI/SBA-15
composite reached a maximum amine efficiency at around 55 °C,
after which the amine efficiency decreased. This behavior is
consistent with transitioning from a mass transport-limited
regime where increasing temperature allows access to more
sites for CO2 adsorption to a regime where accessibility of amine
sites is no longer a limiting factor, and the adsorption behavior
can follow the expected thermodynamic response. The
temperature at which this transition occurred appeared to be
dependent on the molecular weight of the polymer; the higher
molecular weight polymers reached a maximum in amine
efficiency around 65 °C (Figure S10). This is likely related to the
decreasing mobility of the polymer chains as molecular weight
increased.
It is expected that this transition from a transport-limited
regime to a thermodynamically-limited regime would occur in
both the air capture and 1 bar CO2 regimes as well, though the
temperature at which the maximum efficiency occurs appears to
be outside of the range of temperatures studied here. The
pressure-dependence of the optimum adsorption temperature
can be rationalized by considering the mechanism for CO2
capture by amines in dry conditions. The formation of
ammonium carbamate ion pairs requires two amines per CO2
captured; this creates a crosslink that can occur within a single
polymer chain, or in between nearby polymer chains. These
crosslinks decrease the effective diffusivity of CO2 by limiting the
mobility of the polymer chains. The density of crosslinks is
directly related to the amount of CO2 captured; in low partial
pressures of CO2, fewer crosslinks are formed and so higher
temperatures are not required to overcome barriers to mass
transport. However, at high partial pressure of CO2, a large
fraction of the polymer is crosslinked, and so higher temperature
is required to increase the effective diffusivity of CO2 to the point
where all of the amine sites can become accessible.
To demonstrate the difference in site accessibility, a CO2
adsorption isobar was collected with 10% CO2/N2 to examine the
temperature-dependent hysteresis (Figure 4b, Figure S11). As
expected from the isotherm studies, the CO2 capacity and amine
efficiency increased as the adsorption temperature was
increased from 25 °C to 55 °C, after which the efficiency
decreased. Upon cooling the sample stepwise from 95 °C to
25 °C, the CO2 capacity and amine efficiency consistently
increased, as would be the expected thermodynamic response.
This suggests that CO2 was adsorbed on sites that were
previously inaccessible when adsorption started from low
temperature, and therefore the material was more easily able to
approach the thermodynamically-limited CO2 capacity of 2.4
mmol CO2/g composite at 25 °C (Figure S11). In principle, this
ChemSusChem
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capacity could also be reached at low temperature by extending
the time for adsorption.
The difference in CO2 capacity and amine efficiency at
high polymer loading for the different molecular weights of linear
PPI observed in Figure 2 is related to these differences in site
accessibility. There was a clear decrease in the rate of CO2
adsorption as molecular weight of the linear PPI was increased,
as shown in Figure 5, again related to the decreasing mobility of
the polymer chains. We hypothesize that this is also the reason
for the improved resistance to oxidative degradation for the
higher molecular weight linear PPI – by decreasing the mobility
of the polymer chains, oxygen is not as easily able to penetrate
the polymer bulk to initiate degradation reactions. This
phenomenon has also been observed in comparison of
branched and linear PEI/silica composites -- similarly to linear
PPI, linear PEI is a solid at room temperature, and thus adsorbs
CO2 more slowly than the more mobile branched PEI, resulting
in differences in both the rate of adsorption and CO2 capacity.[57]
Interestingly, site accessibility and CO2 adsorption kinetics can
be improved slightly in a larger pore volume silica such as MCF
(Figure S12). However, as mentioned above, it appears that the
polymer morphology may be more important than the support
morphology when the polymers are solids under the adsorption
conditions.
Figure 5. Dynamic CO2 uptake profiles for high polymer loading samples,
normalized against their pseudoequilibrium value reported in Figure 2.
Adsorption in 400 ppm CO2/N2 at 35 °C.
The CO2 adsorption isotherms in Figure 4a can be
modeled using a dual-site temperature-dependent Toth isotherm
(Supporting Figure S13a), which has been used previously to
model the adsorption of CO2 on supported amines.[58] Using this
model, the zero-coverage heat of adsorption is estimated to be
105 kJ/mol for CO2 adsorption on the 50 wt% linear PPI (1000
g/mol)/SBA-15 sample. The isosteric heats of adsorption as a
function of amount of CO2 adsorbed can also be estimated using
the isotherm data and the Clausius-Clapeyron equation
(Supporting Figure S13b). Values around 100 kJ/mol are
estimated for loadings of CO2 up to about 1.5 mmol/g, beyond
which the heat of adsorption decreases. These heats of
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10.1002/cssc.201800438
adsorption are somewhat larger than those reported for
adsorption of CO2 on other branched PEI/SiO2 composites
(typically 50-80 kJ/mol).[56,59,60] However, it should be noted that
this method of estimating the heats of adsorption tends to
underestimate the true value obtained via microcalorimetry,[23,61]
and thus the values for linear PPI reported here can be taken as
a lower bound. Nonetheless, CO2 appears to adsorb more
strongly on PPI than PEI, possibly due to the increased basicity
of propylenimines compared to ethylenimines.
Finally, to investigate the long-term stability of linear PPI
sorbents, rapid temperature-swing adsorption/desorption
Accepted Manuscript
cycles[62,63] for direct air capture were performed. The CO2
adsorption/desorption cycles are shown in Figure 6a, and the
working amine efficiency for each cycle is shown in Figure 6b.
Due to the rapid decrease in the rate of adsorption seen in
Figure 5, adsorption was limited to one hour, rather than the 18
hours required to achieve pseudo-equilibrium. Despite this, 60%
of the pseudo-equilibrium value was reached with fully reversible
adsorption; the linear PPI/SBA-15 sorbent was able to maintain
stable operation with a working capacity of 0.76 mmol CO2/g
composite. This suggests that that the sorbent did not deactivate
due to formation of strongly-bound species like urea, which are
less likely to form from linear aminopolymers,[31,37] or
deteriorate/lose polymer during the high temperature desorption.
Indeed, analysis of the organic content of the composite after
the cycling test indicated that less than 0.3% of the polymer
mass had been lost, suggesting that polymer molecular weights
as low as 1000 g/mol were sufficient for preventing volatilization
of the polymer. The slowly decreasing baseline observed in
Figure 6a, then, is likely due to slow loss of small amounts of
water from the hydrophilic aminopolymer/silica composite, which
is not expected to impact performance significantly.
Figure 6. (a) CO2 adsorption/desorption working capacity profile for the 50
wt% linear PPI (1000 g/mol)/SBA-15 sample over 50 consecutive temperature
swing adsorption cycles. Adsorption was performed in 400 ppm CO2/N2 at
35 °C for 1 h; desorption was performed in UHP N2 at 110 °C for 10 min. (b)
Amine efficiency as a function of the temperature swing adsorption cycle.
ChemSusChem
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Conclusions
This work demonstrates the potential for using linear
poly(propylenimine) (PPI) in CO2 sorbent materials for capture of
CO2 from dilute sources such as ambient air or flue gas. At high
polymer loading, lower molecular weight species of linear PPI
were more efficient at CO2 capture due to more rapid adsorption
kinetics compared with higher molecular weight species. Under
similar adsorption conditions and sorbent characteristics, linear
PPI performed better than the traditionally-studied randomly-
branched PEI, though it is expected that improvements in the
adsorption kinetics and performance can be made by changing
the textural properties of the support material. Importantly, linear
PPI largely retained its CO2 capture capacity after exposure to
an accelerated oxidative treatment, unlike related linear PEI
materials. CO2 adsorption isotherm and isobar hysteresis
experiments suggest that the significant mass transport
limitations imposed by high polymer loading can be overcome by
starting adsorption at elevated temperature to increase the
adsorption site accessibility by improving polymer chain mobility
and the effective diffusivity of CO2, and then reducing the
temperature to increase the thermodynamically-limited capacity.
The results presented here suggest that improvement in
adsorption kinetics will allow PPI-based sorbents to be a
promising, oxidatively-stable, alternative to the traditionally-
studied PEI-based sorbents for use in CO2 capture from dilute
sources.
Experimental Section
Chemicals, Materials and Chemical Characterization
Chemicals for syntheses reported below were obtained from Sigma-
Aldrich and Alfa Aesar and used directly without further purification. Ultra-
high purity N2, ultra-high purity He, ultra-zero grade air, research grade
CO2, 400 ppm CO2/N2, and 10% CO2/N2 were obtained from Airgas.
1H NMR spectra were recorded on a Bruker AVIII-400 spectrometer (400
MHz). Chemical shifts are reported in parts per million (ppm) either
referenced to 0.0 ppm for tetramethylsilane or to the center line of a
quintet at 3.312 ppm for methanol-d4. The following abbreviations are
used to explain multiplicities: s = singlet, t = triplet, q = quintet. 13C NMR
spectra were recorded on a Bruker AVIII-400 spectrometer (100 MHz),
and were fully decoupled by broad band proton decoupling. Chemical
shifts are reported in ppm referenced to either the center line of a triplet
at 77.2 ppm for chloroform-d or to the center line of a septet at 49.15
ppm for methanol-d4.
Gel permeation chromatography was performed on a Shimadzu HPLC
system with refractive index detector (RID-10A) and TSKgel G3000-
G6000-PWxl-CP Guard, G3000-PWxl-CP, and G5000-PWxl-CP columns.
Samples were prepared and flowed in an eluent phase of 0.4 M acetic
acid with 0.3 M NaNO3 at 1 mL/min.
Synthesis of SBA-15
SBA-15 was synthesized according to our previously published
procedure.[64] 24.0 g of Pluronic P-123 block copolymer
((EO)20(PO)70(EO)20) was dissolved in 636 g of deionized water and 120
mL of 12.1 M HCl. The components were stirred vigorously for 3 h, until
everything dissolved. 46.6 g of tetraethyl orthosilicate (TEOS) was added
dropwise to the mixture and stirred at 40 °C for 20 h, during which time a
white precipitate formed. The solution was then heated to 100 °C and
held for 24 h in the absence of stirring. The reaction was quenched with
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10.1002/cssc.201800438
400 mL deionized water and the precipitate was filtered and washed
copiously with deionized water. The filtered precipitate was dried for 12 h
in an oven at 75 °C and then calcined according to the following program:
heat to 200 °C at 1.2 °C/min, hold at 200 °C 1 h, heat to 550 °C at
1.2 °C/min, hold at 550 °C for 12 h, cool to room temperature. The
resulting white powder was stored in ambient lab conditions.
Synthesis of 2-methyl-5,6-dihydro-4H-1,3-oxazine
Synthesis of 2-methyl-5,6-dihydro-4H-1,3-oxazine (MeOZI) was adapted
from published procedures.[65,66] Anhydrous ZnCl2 (5.5 g, 0.04 mol) was
dispersed in anhydrous MeCN (115 mL, 2.2 mol). To this solution, 3-
Accepted Manuscript
aminopropanol (150.2 g, 2.0 mol) was added dropwise at room
temperature under stirring. The mixture was then purged with dry argon
and heated to 95 °C with stirring for 48 h, allowing NH3 gas to evolve and
vent from the system. The reaction mixture was cooled to room
temperature and excess MeCN and NH3 were removed by rotary
evaporation at 30 °C. MeOZI was isolated by distillation under vacuum
(~400 mTorr, 65 °C), cooling the distillate with a dry ice/isopropyl alcohol
mixture, to afford a clear, colorless liquid which was stored in ambient lab
conditions.
1
H NMR (400 MHz, CDCl3, δ): 4.144 (t, J = 5.4 Hz, 2H), 3.338 (t, J = 5.8
Hz, 2H), 1.879+1.851 (s+q, J = 5.7 Hz, 5H).
13
C NMR (100 MHz, CDCl3, δ): 157.85, 65.00, 42.41, 22.06, 21.78.
Synthesis of linear poly(MeOZI)
Cationic polymerization of MeOZI was adapted from published
procedures.[67,68] Prior to polymerization, MeOZI and MeCN were dried
over CaH2 by stirring at 65 °C. Dried MeOZI and MeCN was collected
into a Straus flask by distillation under vacuum (~400 mTorr, 65 °C and
30 °C, respectively), cooling the distillate with a dry ice/isopropyl alcohol
mixture. MeOZI and MeCN were stored under dry argon and transferred
into a dry box. 10 g dried MeOZI in the dry box was transferred into a
round bottom flask, to which 50 mL dried MeCN was added. An amount
of methyl p-toluenesulfonate (MeOTs) was added, based on the desired
final molecular weight of the polymer. The round bottom flask was sealed
with a rubber septum and heated to 90 °C with stirring to initiate
polymerization. Polymerization was allowed to proceed for 48 h, after
which 2.0 equivalents of 1,3-diaminopropane (based on MeOTs) was
added to quench the reaction. MeCN and excess 1,3-diaminopropane
were removed by rotary evaporation at 50 °C to afford a viscous, yellow
liquid as crude poly(MeOZI).
Synthesis of linear poly(propylenimine)
Linear poly(propylenimine) (PPI) was synthesized by acidic hydrolysis of
poly(MeOZI), adapted from a previously published procedure.[69] 200 mL
of 5 M aqueous HCl was added to the crude poly(MeOZI) residue and
stirred at 100 °C for 48 h. After cooling to room temperature, the residual
polymer was concentrated by rotary evaporation at 60 °C, which caused
the polymer to precipitate from solution. The concentrated polymer
solution was cooled to 0 °C in an ice bath and carefully brought to pH 13
using concentrated aqueous NaOH, which caused to polymer to first
become fully dissolved, and then precipitate as an off-white powder.
Linear PPI was recovered by centrifugation (14000 rpm, 10 min) and
washed copiously with 10% NH4OH to remove any residual inorganic salt.
The final polymer was dissolved in MeOH and dried under high vacuum
to afford an off-white solid (~75% yield based on 10 g monomer). The
absence of residual inorganic salt was verified by TGA. The number-
averaged molecular weight was estimated by 1H NMR by end group
analysis, Figures S1-S4 (400 MHz, methanol-d4, δ): 3.625 (t, -
CH2CH2CH2NH2, 2H), 2.612 (t, -CH2CH2CH2NH-, 4nH), 2.361 (s, CH3-,
3H), 1.709 (q, -CH2CH2CH2NH-, 2nH).
Linear PPI/SBA-15 composite preparation
ChemSusChem
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SBA-15 was impregnated with linear PPI by wet impregnation. SBA-15
was dried overnight under vacuum (< 20 mTorr) at 110 °C. The desired
amount of linear PPI was dissolved in 15 mL methanol and added to the
desired amount of SBA-15. The mixture was allowed to stir at room
temperature for at least 6 h. Methanol was removed by rotary
evaporation at room temperature. The resulting powder was dried
overnight under vacuum (< 20 mTorr) at room temperature. The resulting
dried powder composites were stored in ambient lab conditions. An
identical procedure was used to prepare linear PEI/SBA-15 composites,
except these powder composites were stored in dry Ar to prevent
unwanted oxidation.
Physical Characterization
Nitrogen adsorption isotherms were obtained on a MicrotracBEL
BELSORP-max at 77 K. Prior to analysis, the samples were degassed
under vacuum on a BELPREP-vac II below 10-2 kPa for 12 h at 110 °C.
The free space measurement was performed after analysis. Surface area
was analyzed by applying BET theory in the range of P/P0 from 0.05 to
0.2, total pore volume was calculated based on the total amount of N2
adsorbed at P/P0 of 0.95, and pore size distributions were calculated by
the BJH method with Broekhoff-de Boer thickness curve, implemented in
the MicroActive software package by Micromeritics.
Organic content of the samples was estimated on a Netzsch STA409PG
TGA. Mass loss from 125 to 900 °C under a flow of nitrogen-diluted air
was recorded and normalized by the residual mass at 900 °C.
Fourier transform infrared (FTIR) spectra were recorded in transmission
mode in a flow of N2 on a Thermo Nicolet iS10 with an MCT detector.
Approximately 5 mg of the sample was diluted by 110 mg KBr and
pelletized for analysis.
Gravimetric CO2 Adsorption
Pseudo-equilibrium CO2 adsorption capacities were measured
gravimetrically on a TA Instruments Q500 TGA. The samples were
pretreated by heating to 110 °C at a ramp rate of 10 °C/min under a flow
of N2 and held for 2 h. The samples were cooled to 35 °C and
equilibrated at this analysis temperature for 1 h. Subsequently, the gas
flow was switched to a premixed gas containing 400 ppm CO2/N2 for 18 h
and the rate of mass change was less than 5 × 10-6 %/min. The mass
gain was recorded and normalized by the dry mass of the sample.
Pseudo-equilibrium capacities were obtained in triplicate and the
reported error bars indicate the standard deviation of these
measurements.
The CO2 adsorption isobar was obtained similarly, but the sample was
not treated at high temperature in between adsorption points. Following
pretreatment and equilibration at 25 °C, the gas flow was switched to a
premixed gas containing 10% CO2/N2 for at least 6 h, or until the rate of
mass change was less than 5 × 10-6 %/min. Following this, the
temperature was increased to 35 °C at a rate of 10 °C/min in the flow of
premixed gas and again held for at least 6 h, or until the rate of mass
change was less than 5 × 10-6 %/min. This procedure was repeated up to
95 °C to collect the heating curve for the isobar. Following the 95 °C
measurement, the temperature was decreased to 85 °C, and the same
procedure was repeated down to 25 °C to collect the cooling curve for
the isobar.
Cyclic adsorption/desorption experiments were performed similarly, with
sorbent regeneration in between each adsorption cycle. The sample was
initially pretreated at 110 °C for 2 h, and then equilibrated at 35 °C for 1 h.
Cycles of adsorption for 1 h and desorption for 10 min were then
performed, allowing for 10 min of equilibration time at the adsorption
temperature to determine the starting mass for adsorption for each cycle.
Volumetric CO2 Adsorption
Pseudo-equilibrium CO2 adsorption isotherms were measured
volumetrically on a Micromeritics ASAP 2020. Prior to analysis, samples
This article is protected by copyright. All rights reserved.
10.1002/cssc.201800438
were degassed under dynamic vacuum on the instrument (< 5 mTorr) at
110 °C for 12 h. The free space measurement was performed prior to
analysis followed by a series of 180 sec leak tests to ensure that the
helium from the free space measurement had been completely
evacuated from the sample. An equilibration interval of 60 sec was used
for pressures less than 20 Torr and 30 sec for all other pressures. For a
given composite, all isotherms were collected using the same sample to
avoid introducing weighing error, and the order in which the isotherms
were collected was randomized to avoid potential temperature-hysteresis.
For the 1000 g/mol linear PPI sample, the 35 °C isotherm measurement
was repeated after all other isotherms had been collected, to ensure that
no degradation or loss of aminopolymer had occurred (Figure S10f).
Adsorption isotherms for N2 and O2 at 35 °C were obtained similarly,
Accepted Manuscript
demonstrating that these gases adsorb only through weak physisorption,
whereas CO2 adsorbs via strong chemisorption (Figure S14). Therefore
the presence of N2 or O2 during the mixed gas CO2 adsorption process
(such as in the gravimetric uptake experiments) is not expected to impact
the amount of CO2 adsorbed.
Accelerated Oxidative Treatment
Linear aminopolymer/SBA-15 composites were exposed to an
accelerated oxidative treatment in a TA Instruments Q500 TGA. The as-
prepared composites were heated to 110 °C under a flow of ultra-zero
grade air and held for 24 h.
Acknowledgements
Funding for this work was provided as a part of UNCAGE-ME,
an Energy Frontier Research Center funded by the U.S.
Department of Energy, Office of Science, Basic Energy
Sciences, under award no. DE-SC0012577, and by Global
Thermostat, LLC. We also thank Dr. Michele Sarazen for help
with the GPC experiments.
Keywords: adsorption • amines • polymers • carbon storage •
mesoporous materials
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HaPPI to Capture CO2: S. H. Pang, R. P. Lively, C. W. Jones*
Poly(propylenimine)-containing solid
adsorbents are demonstrated for CO2 Page No. – Page No.

Accepted Manuscript
capture from ambient air. These
Oxidatively-Stable Linear
materials are more resistant to
Poly(propylenimine)-Containing
oxidation than their poly(ethylenimine)
Adsorbents for CO2 Capture from
counterparts and show stable
Ultra-Dilute Streams
adsorption/desorption performance
over many cycles.

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