Paper: Faradaic Electro-Swing Reactive Adsorption For CO Capture

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Faradaic electro-swing reactive adsorption for

CO2 capture†
Open Access Article. Published on 01 October 2019. Downloaded on 9/18/2023 7:15:28 PM.
Cite this: Energy Environ. Sci.,

2019, 12, 3530
Sahag Voskian and T. Alan Hatton *
Carbon capture is one of the foremost methods for curtailing greenhouse gas emissions. Incumbent
technologies are inherently inefficient due to thermal energy losses, large footprint, or degradation of
sorbent material. We report a solid-state faradaic electro-swing reactive adsorption system comprising
an electrochemical cell that exploits the reductive addition of CO2 to quinones for carbon capture. The
reported device is compact and flexible, obviates the need for ancillary equipment, and eliminates the
parasitic energy losses by using electrochemically activated redox carriers. An electrochemical cell with
a polyanthraquinone–carbon nanotube composite negative electrode captures CO2 upon charging
via the carboxylation of reduced quinones, and releases CO2 upon discharge. The cell architecture
Received 28th July 2019, maximizes the surface area exposed to gas, allowing for ease of stacking of the cells in a parallel passage
Accepted 30th September 2019 contactor bed. We demonstrate the capture of CO2 both in a sealed chamber and in an adsorption bed
DOI: 10.1039/c9ee02412c from inlet streams of CO2 concentrations as low as 0.6% (6000 ppm) and up to 10%, at a constant CO2
capacity with a faradaic efficiency of 490%, and a work of 40–90 kJ per mole of CO2 captured, with
rsc.li/ees great durability of electrochemical cells showing o30% loss of capacity after 7000 cylces.
Broader context
There is a clear scientific consensus on the role of anthropogenic greenhouse gas (GHG) emissions in the unusually wild fluctuations of global climate patterns
over the last century, to which carbon dioxide is the largest contributor. This has generated a scientific tide in the study of carbon removal techniques over the
last three decades, which has slowly gathered momentum, culminating in the 2015 Paris Agreement, which heavily emphasized the role of carbon removal by
tackling emissions or via negative emissions technologies. While a path forward for carbon capture is being shaped by a mix of incumbent actors and
newcomers, the great majority of the proposed processes rely on conventional concepts. Moreover, most of these processes have a large balance of plant which
hinders their potential to flexibly adapt to the multi-scale nature of carbon capture. Herein, we demonstrate a new approach which presents a paradigm shift in adsorption
type processes and carbon capture. The electro-swing basis of our process allows its linear scaling with desired capacity and lends it geometric flexibility. It also allows
carbon capture from streams of any concentration, and its release into any carrier streams, including pure CO2, with a low balance of plant.
Introduction mainly amine scrubbing,5 and oxyfuel combustion,6 which

target high CO2 concentration streams (410%). These approaches
With the alarming increase in the atmospheric concentration have a large footprint and, when retrofitted to a process, can
of carbon dioxide (CO2) and its implications for global climate require major modifications to the plant. Consequently, there has
pattern developments,1,2 mitigation of climate change through been a major effort to develop new materials and processes for
curtailment of anthropogenic CO2 emissions has been one of high efficiency CO2-capture, including sorbents for pressure and
the most urgent socioeconomic and scientific problems in the temperature swing adsorption systems,7 and membranes for
global arena over the last decade.3 To this end, a number of selective transport of the CO2.8 Furthermore, many potential
technologies have been developed for the large-scale capture applications of carbon capture require compact devices due to
of CO2 from combustion and other industrial processes to space limitations, such as in the direct capture of CO2 from
produce high-purity CO2 streams for storage or valorization.4 tailpipe exhausts on board mobile sources, in which there is
The most mature of these technologies are solvent scrubbing, growing interest given the large contribution of transportation
exhaust to greenhouse gas emissions (33.5% of U.S. CO2 emissions
Department of Chemical Engineering, Massachusetts Institute of Technology,
in 2016).9
Cambridge, MA 02139, USA. E-mail: tahatton@mit.edu In addition to the capture of CO2 from direct combustion
† Electronic supplementary information (ESI) available. See DOI: 10.1039/c9ee02412c processes, there is a need to remove CO2 from enclosed spaces
3530 | Energy Environ. Sci., 2019, 12, 3530--3547 This journal is © The Royal Society of Chemistry 2019
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for ventilation purposes in buildings and car cabins, or for In this work, we develop a compact electrochemical device
cabin environmental control systems on board spacecraft and for CO2 capture that eliminates the requirement for complex
submarines, where the maximum allowed CO2 concentration in flow systems, and that can be effective in the treatment of both
habitable spaces is 5000 ppm (or 0.5%).10 The first of such high and low concentration feed streams. A quinone-utilizing
systems was developed by Winnick et al., for the electrochemical faradaic electrochemical cell that fulfils these requirements
capture of CO2 in spacecraft cabins using molten carbonates.11 and operates as an Electro-Swing Adsorption (ESA) process is
However, the low concentration of CO2 in such applications illustrated schematically in Fig. 1. The cell is comprised of
poses a challenge, mainly due to the low driving forces for mass two cathode electrode substrates coated with a CO2-binding
transfer and the large quantities of other species present in air quinone–carbon nanotube (Q–CNT) composite sandwiching an
in addition to CO2.12 Thus, carbon capture is a multi-scale anode electrode substrate coated with a ferrocene–CNT (Fc–CNT)
problem, where the CO2-rich streams to be treated vary greatly composite, with separator membranes between the electrodes.
in volume, concentration and composition, and different criteria This cell architecture is employed to maximize the CO2-binding
need to be fulfilled to ensure optimal processing depending on surface area of the cell exposed to gas flow in a parallel passage
whether sources are industrial or small-scale (e.g., power plants adsorbent contactor design where stacks of these cells form
or oil and gas heaters), concentrated or dilute (exhausts from parallel gas channels. The Fc–CNT electrode serves as an electron
combustion or air in confined spaces), and clean or contaminated source and sink for the reduction and oxidation, respectively, of
with other pollutants. the Q–CNT electrodes to regulate the uptake and release of the
Many of the CO2-capture chemical processes that involve a CO2. Wetting of porous non-woven carbon fiber mats used as the
capture agent such as amines or solid sorbents require temperature electrode substrates by a room temperature ionic liquid (RTIL)
and/or pressure swings to release the captured CO2 and regenerate electrolyte enables effective ionic currents to pass through the
the agents for further capture. These swings result in inefficiencies electrolyte on activation and deactivation of the electrodes, and
due to energy wasted in heating solvents and sorbents, pressurizing permits the diffusion of CO2 into the electrolyte-wetted cathodes
feed gas, or drawing a vacuum for desorption. Electrochemical during capture.
systems can minimize such parasitic energy losses as they can be The effectiveness of the electro-swing concept for CO2 capture
operated at near isothermal conditions, with significantly higher and release was demonstrated in a sealed system in which cell
efficiencies than their thermal-swing (TSA) and pressure-swing (PSA) polarity was cycled to regulate the activation and deactivation of
adsorption counterparts.13 One mode of electrochemical capture of the carrier, i.e. reduction and oxidation of the redox active
CO2 is through the use of a redox-active carrier. quinone. This was in lieu of the advection of the carrier electrolyte
Electrochemically mediated selective transport of chemical solution between two electrodes with a difference in potential.19 The
species was first reported by Ward et al.,14 where a redox-active performance of flow-through modules constructed with stacks of
carrier (ferrous ion) was used to transport nitric oxide across a the assembled electrode cells was also assessed. The CO2 capture
membrane. Since then, a number of systems have been developed processes were modelled to provide greater insight into the
for transporting chemical species by redox-active carriers that are operational principles for this technology.
activated at one electrode, to bind with the target species, and Ultimately, the goal of this work was to demonstrate an
deactivated at the opposite electrode, to release the target and electrochemically activated packed parallel passage contactor
regenerate the carrier.15,16 Systems that have been proposed for adsorption system for the removal of CO2 from flue gas and
the concentration of CO2 through this approach have been based other CO2-rich streams. The regeneration of the bed takes place
on a number of different carrier molecules, such as quinones,17–20 on reversal of the polarity of the stack in an ESA, with analogies
4,4 0 -bipyridine,21 and thiolates.22,23 Quinones are of particular to PSA systems, where adsorption takes place at high pressure
interest to this work for their superior electrochemical performance, and desorption at a lower pressure,24 or TSA systems, where
serving as redox-active carriers for CO2 in electrochemically adsorption takes place at low temperatures and the fixed bed is
mediated separation processes. DuBois et al. demonstrated regenerated at higher temperatures.25
this possibility, and studied the thermodynamics of an electro-
chemical CO2 pumping system that utilizes quinones.18 More
work followed, where Scovazzo et al. demonstrated the electro- Results and discussion
chemical separation of CO2 from o1% concentration gas
mixtures using 2,6-di-tert-butyl-1,4-benzoquinone as a carrier Design of the electrochemical cell
in ionic liquid (IL) and organic solvent electrolytes media,19 Thin films of crystallized organic compounds have been studied
while Gurkan et al. screened a number of ILs to serve as suitable as a means of immobilizing CO2 redox-active carriers onto
electrolytes for quinone carriers in an electrochemically mediated electrode substrates.26 Redox-active polymers have long been
selective transport system for CO2.20 All of these systems, however, the preferred electrode material when using organic molecules
require the transport of the electrolyte and the dissolved carrier in electrochemical cells, however, because polymers are less
molecules between two electrodes in an electrochemical cell for soluble in the electrolyte than their corresponding redox-active
capture and release of CO2. This limits their implementation in repeating units, and thus the self-discharge of the cell can be
a number of applications where the requirement for flow avoided, and its cycling performance improved.27 For example,
systems and pumping, and the large footprint, are problematic. quinone polymers have been investigated as suitable cathode
This journal is © The Royal Society of Chemistry 2019 Energy Environ. Sci., 2019, 12, 3530--3547 | 3531
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Fig. 1 Schematic of a single electro-swing adsorption electrochemical cell with porous electrodes and electrolyte separators. The outer electrodes,
coated with poly-1,4-anthraquinone composite, can capture CO2 on application of a reducing potential via carboxylation of quinone, and release the
CO2 on reversal of the polarity. The inner polyvinylferrocene-containing electrode serves as an electron source and sink for the quinone reduction and
oxidation, respectively.
materials in lithium-ion batteries,28 and pseudocapacitive energy process in which 100% CO2 recovery is achieved, puts the
storage devices.29 These polymers are usually made into com- technology much closer to the upper-right corner on the recovery-
posites with conductive high-surface area carbon materials, purity Pareto plot than those based on current CO2 sorbents.32,33
such as carbon black, graphite or carbon nanotubes (CNT), to Polyanthraquinone electrodes. Poly(1,4-anthraquinone) (P14AQ),
enhance the overall conductivity of the electrode material and shown in Fig. 1, was synthesized and incorporated into an ink
increase the area of the polymer exposed to the electrolyte.30 with multi-walled carbon nanotubes (MWCNT) in N-methyl-2-
Here, we used a polyanthraquinone–CNT (PAQ–CNT) composite pyrrolidone (NMP). Non-woven carbon fiber mat electrode sub-
for the cathode and polyvinylferrocene–CNT (PVFc–CNT) composite strates of thickness 150 mm (35 g m2) were dip-coated in the
for the anode.31 The electrolyte used was the RTIL 1-butyl-3- ink and dried very slowly to obtain a composite that uniformly
methylimidazolium bis(trifluoromethylsulfonyl)imide ([Bmim]- coated the substrate at B1.2 mg cm2, shown in Fig. 2(a). The
[TF2N]), selected for its low volatility, which allows for flow of composite structure allows for a greater utilization of the
gas over the wetted electrodes without loss of electrolyte to anthraquinone repeating units in the polymers, and thus larger
evaporation or entrainment. currents under applied potentials. The CNT mesh, shown in
A sealed chamber was constructed in which CO2 capture and Fig. 2(f), provides a backbone to improve the conductivity of the
release on electrochemical activation and deactivation of the conjugated PAQ via p–p interactions with the anthraquinone
quinones, respectively, was indicated by the concomitant pressure units (Fig. S3, ESI†); it also provides a porous matrix decorated
changes in the chamber. A flow cell was also fabricated to house by the polymer chains for better electrolyte penetration. This
stacks of the electrochemical cells to allow for capture of CO2 from results in a larger surface area of the polymer being exposed to
flowing gas streams of compositions similar to those of flue gases, electrolyte, and an increased conductivity in the composite.34
air in aircraft cabins and buildings, and in the ambient environ- The p–p interaction of the polymer chains and CNTs, and the
ment. The adsorption effectiveness was assessed through analysis subsequent decoration of the nanotubes with the polymer
of the breakthrough profiles. chains, shown in Fig. 2(e), also improved the suspension of
The chemical specificity of quinones can provide near 100% the CNTs in the polymer solution, which resulted in very well
purity of released CO2, which, when combined with a well-designed dispersed inks. The ratio of PAQ to CNT was optimized, with the
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Fig. 2 (a) SEM micrograph of the cathode non-woven carbon mat coated with P14AQ–CNT, with details of coated and uncoated areas. (b, c and f) SEM
micrographs of increasing magnification of carbon fibers coated with P14AQ–CNT. (d) SEM micrograph of the uncoated carbon fibers. (e) TEM of
PAQ–CNT showing the amorphous polyanthraquinone decorating the MWCNT, a result of the p–p interaction.
highest current per mass of active material (polymer) obtained anode electrode material for the electrochemical cell with
at a 1 : 3, PAQ : CNT ratio by weight (Fig. S4, ESI†). The cyclic PAQ–CNT cathode was a composite of polyvinylferrocene and CNT
voltammograms in Fig. 3 shown in green (under N2) and red (PVFc–CNT), shown in Fig. 1. This was prepared by dispersing
(under CO2) indicate the strong redox activity of these electrode MWCNTs in a solution of PVFc in NMP. The optimum ratio of
surfaces; the differences in the current response following the composite was found to be 1 : 1, PVFc : CNT, by weight. The
potential scans are discussed later. electrode substrate was dip-coated in the ink and dried slowly
Polyvinylferrocene electrode. A counter electrode with a to yield a composite that uniformly coated the substrate at
reduction potential more positive than the oxidative CO2 release B1.4 mg cm2, as shown in Fig. 4. The CVs of the PVFc–CNT
potential of PAQ–CNT is required to make an electrochemical electrode in N2 and CO2 saturated [Bmim][TF2N] are identical,
cell that can effectively capture and release CO2. Therefore, the and are indicated by the blue line in Fig. 3. PVFc–CNT has a
reduction potential of E0 = 0.03 V, against ferrocene (Fc).
The electrochemical cell. The PAQ–CNT electrodes were
assembled into an electrochemical cell in which CO2 was able
to be captured and released upon potential swings. This was
accomplished by layering a PVFc–CNT counter electrode
between the two PAQ–CNT electrodes to balance the charge of
these electrodes, as shown in Fig. 5(d). In a CO2-rich environment,
this afforded a polymer-based battery with an electrochemical
window of B1.2 V, where all the charge from the ferrocene
oxidation, at its reduction potential, was balanced by the charge
transferred to the two-electron reduction of quinone, at its first
reduction potential. This window is defined by the reduction
potential of PVFc–CNT and the first reduction potential of
PAQ–CNT, shown in Fig. 3 as DV1. However, in the absence of
CO2 or other such electrophiles, mainly under N2, PAQ retains
Fig. 3 Superimposed CVs of PVFc–CNT ( ) and P14AQ–CNT ( ) under
its two one-electron reductions, with half of the charge of the
N2 and ( ) under CO2 in [Bmim][TF2N], at 20 mV s1, vs. Fc, at T B 21 1C. ferrocene oxidation being balanced by the reduction of quinone
The two potential windows are shown; DV1 under CO2 and DV2 under N2. at the first potential and the other half by its reduction at the
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chamber into which the electrodes were inserted. Changes in

pressure were measured as CO2 was adsorbed and then
released on cycling of the potential applied to the electrodes.
The second approach used a flow adsorption in which the CO2
exiting the device was monitored, with the breakthrough point

reflecting the overall capacity of the electrodes. All carbon
capture experiments were conducted at T B 21 1C.
CO2 capture and release in a batch system. An electrochemical
cell (4 cm2 of total exposed area) with the three layers, such as
that illustrated in Fig. 1, was tested for the capture and release of
CO2 in a sealed chamber, shown in Fig. 5. This cell had B4.8 mg

of PAQ–CNT deposited, i.e. 5.8 mmol of quinone, or a capacity for
11.6 mmol of CO2. From the monitored pressure changes in the
chamber of known internal void volume, the number of moles of
CO2 captured and released upon charge and discharge of the cell
at constant potentials, were calculated. The chamber was purged
with CO2 at the desired concentrations and sealed at atmospheric
pressure. The pressure inside was allowed to equilibrate at
Fig. 4 (a) SEM micrograph of the anode non-woven carbon mat coated constant temperature before the electrochemical experiments
with PVFc–CNT with details of coated and uncoated areas. (b and c) SEM were started.
micrographs of carbon fibers coated with PVFc–CNT, the squares indicates the The performance of the electrochemical cell was evaluated
region which is magnified in the next micrograph. (d) SEM micrograph of the
in chronoamperometric (potentiostatic) experiments, with capture
magnified polymer-coated CNTs from a different area on the electrode.
at 1.3 V and release at 0.5 V, i.e. DV = 0.8 V. Fig. 6(a) shows the
change in the number of moles of CO2 captured from pure gas
second potential. This results in a wider electrochemical window, over 10 cycles (blue), along with the charge transferred to and
shown in Fig. 3 as DV2, and the behavior of the cell resembles that from the cell (red). It shows that B65% of the quinone units
of an asymmetric pseudocapacitor.35 were utilized, i.e. 7.4 mmol of CO2 captured. This may be due to
The capacities of the anode and cathodes of the cell, incomplete charging of the quinones that are not exposed to
evaluated by gravimetric charge calibration of the two electrode electrolyte. From the charge transferred during charging and
composite materials (Fig. S5, ESI†), were balanced by requiring discharge (B800 mC), and the moles of CO2 captured and
that mP14AQ–CNT = 1.12mPFVc–CNT, which allowed for some excess released, a faradaic efficiency
PVFc–CNT.
nF
ZFarad ¼ (1)
Carbon capture Q
Two different types of units were fabricated to demonstrate the of up to 90% was estimated, with some of the charge lost to
effectiveness of the electro-swing process. The first was a sealed double layer charging of the porous electrodes. Here, F is
Fig. 5 (a) Custom-made sealed chamber for closed system experiments with pressure transducer to monitor the changes in pressure as CO2 is
adsorbed and desorbed upon cycling of the cell potential. The internal of the sealed chamber (b) with and (c) without the insulating cup. (d) Layers of the
electrochemical cell assembled in the sealed chamber.
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Fig. 6 (a) Changes in the number of moles of CO2 captured upon charging and discharge of the electrochemical cell over 10 cycles, normalized by the
moles of quinone on the electrode ( ). The CO2 captured from and released to the chamber tracks the charge applied to the electrochemical cell,
normalized by the area of the cell ( ). (b) The CO2 captured under different feed concentrations. (c) Capacity of cell over 7000 cycles. In a different set
of experiments using a larger cell and cavity, (d) shows the effect of varying charging potential for a 1000 s capture and (e) shows the effect of varying the
capture duration at 1.8 V capture potential. These experiments were conducted at T B 21 1C.
Faraday’s constant, Q is the charge transferred, and n is the In a different set of experiments where a larger cell (B450 cm2 of
number of moles of useful electrons transferred in the reaction, total exposed area) was used, CO2 transport limitations became
i.e. used for the capture of CO2, which in this reaction, is more prominent due to the larger internal volume of the cavity
equivalent to the number of moles of CO2. This efficiency results used. In this set, the effect of applying an overpotential was studied,
in B86 kJ per mole of CO2 captured and released, as determined by where capture potentials of greater than DV1 (in Fig. 3) were applied
the relation during a 1000 s capture experiment. Fig. 6(d) shows that upon
FDV increasing the applied capture potential more CO2 is captured for
E ¼ QDV or E=nCO2 ¼ (2) the duration of the experiment, which indicates the activation of
ZFarad
more quinone units on the electrodes during the charging half-
where DV is the difference between the applied charge and cycle. Charging the system at 1.8 V for varying durations, Fig. 6(e),
discharge potentials. shows that the system is fully charged after 2000 s, but more CO2 is
Fig. 6(b) shows similar results for the capture of CO2 from captured, i.e. more of the quinones are utilized, at increasing
gases of different concentrations ranging between 15 and durations of capture. This demonstrates the transport limitations
100%. Again, quinone utilization was high, but dependent on of the electrodes, as explained in later sections.
the initial gas concentration, owing not to capacity limitations, CO2 capture and release in flow systems. The adsorption bed
but to a reduction on sorption dynamics due to mass transfer assembled consisted of a few electrochemical cells stacked in
limitations with lower concentration driving forces. The electro- the flow device to allow the flow of gas in between, as illustrated
chemical cell showed great stability with o30% loss in capacity in Fig. 7(a). The blue regions indicate the presence of CO2, and
over 7000 cycles of capture and release, Fig. 6(c). The gradual the decrease in blue intensity within the channel indicates the
loss in capacity is mainly due to the electromigration of the adsorption front, ahead of which the bed is still empty, and
shorter polymer chains, Fig. S1 (ESI†), from the electrode and behind which the bed, i.e. the electrode assembly, is saturated
into the electrolyte, towards the opposite electrode. with CO2 and cannot adsorb more. A number of different cells
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DV22 to guarantee the complete reduction of the all accessible

quinone units prior to adsorption. Experiments with an initial
half activation, i.e., at DV1, followed by adsorption at constant
potential, did not result in different breakthrough curves,
mainly because the kinetics of the reduction and the adsorption

reactions are much faster than the rates of mass transfer of CO2
into the film, as discussed later.
The breakthrough profiles obtained for one flow system are
shown in Fig. 8(a). Breakthrough was achieved at smaller bed
volumes of gas treated for higher feed CO2 concentrations,
where the bed volume is a time measure which represents the

total volume of gas treated at any given time relative to the
volume of the bed itself. The breakthrough curves superimpose
when normalized by the inlet CO2 concentration, shown in
Fig. 8(b), which indicates a consistent behavior of the bed, i.e.
equal utilization of the overall adsorption capacity regardless of
the inlet concentration, an indication of a rectangular equilibrium
isotherm. Note in this particular module that, although the break-
through curves themselves were sharp, prior to breakthrough there
was a consistent effluent concentration of 20% of the feed
concentration, the result of a bypassing of the active cells by
20% of the total gas flow. The overall capacity of the bed can be
calculated from the area between the line at Cout/Cin = 1 and the
Fig. 7 (a) Schematic illustration of the parallel passage electrochemical
normalized breakthrough curve. A contactor bed of a desired
cell contactor. The blue region indicates the saturated zone and the overall capacity can be designed by linear scaling from this overall
development of the mass transfer zone. (b) Photograph of a flow bed capacity. With a larger bed, CO2 was fully captured from a stream
with a stack of the electrochemical cells. at 10% inlet concentration, which is on the higher end for carbon
capture applications as it mimics combustion exhaust. Up to
were constructed in the flow bed configuration shown in 10 bed volumes of feed were treated before breakthrough was
Fig. 7(b). The exposed area of a typical cell was 18 cm 10 cm, achieved, indicating capacity of greater than one bed volume of
with B0.2 g of P14AQ–CNT composite; at B70% useful quinones, pure CO2. It has similarly been shown that complete removal of
this amounted to the adsorption of B9–14 cm3 of CO2. The CO2 with a smaller stack of cells (a scaled down contactor), five
channels between the cells were typically B500 mm thick, and replicate capture experiments were conducted on an inlet
bed volumes were about 35 cm3 with a total bed weight of stream of B0.8% CO2, Fig. 8(d), which mimics conditions for
B1.5 g bringing the productivity of the bed to 0.01–0.02 kg CO2 ventilation of confined living spaces, such as space modules,
per kgbed tb, where tb is the breakthrough time, i.e. the time to submarines and buildings. The breakthrough curves were
reach saturation of the electrodes or for the outlet CO2 concen- unaffected by the prior history of the bed, indicating that
tration to begin to increase. At feed flow rates of B10 mL min1 complete regeneration and restoration of the bed capacity was
and 15% CO2, this productivity is on par with the TSA systems attained during the desorption following each adsorption run.
reported by Ntiamoah et al.36 The broadness of the breakthrough profiles in Fig. 8(c) and (d)
It can be shown that axial flow dispersion within individual can be attributed to the variation in channel width. Since the
channels was minimal at most flow rates, and that the transport electrochemical cell stacks are hand-assembled and fitted into the
resistances resided primarily within the electrodes. Imperfect bed, some variation in channel width along the same channel and
packing of the cells in the flow device by hand did, in some the parallel channels can cause an uneven distribution of flow
cases, lead to significant channeling and large-scale device axial resulting in overlapping of multiple breakthrough profiles, which
dispersion, however, with broad breakthrough curves, but it is culminate in a broad overall profile. Also, mass-transfer dispersion
anticipated that under optimal manufacturing conditions these plays a significant role in the broadness of the profiles. As is
effects can be reduced significantly. evident from the long durations for an effective capture in Fig. 6(e),
The chronoamperometric experiments performed in the and discussed later, mass transfer of CO2 into the electrodes is the
sealed system were repeated in a flow system. Mixtures of N2 rate controlling step, and this causes axial dispersion that widens
and CO2 at different compositions were flown past the stack the mass transfer zone in the channel, illustrated in Fig. 7(a),
of assembled electrochemical cells. Upon reduction of the resulting in broad breakthrough profiles in this case.
PAQ–CNT electrodes, CO2 was removed (captured) from the
inlet stream, and the decrease in the concentration of CO2 was Mechanism of CO2 capture
detected at the outlet stream. In these experiments the bed was Mizen and Wrighton first demonstrated the reductive addition
fully activated by charging at a constant potential greater than of CO2 to 9,10-phenanthrenequinone in aprotic electrolytes.
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Fig. 8 (a) Breakthrough profiles obtained at four inlet concentrations. (b) Same breakthrough profiles in (a) normalized by the inlet concentrations.
(c) Breakthrough profile obtained from a large system operating at B10% inlet concentration. (d) Breakthrough profiles obtained from five replicate runs
of a smaller system operating at B0.8% inlet concentration. These experiments were conducted at T B 21 1C.
Quinones undergo two reversible one-electron reductions in carbonate salt. Semiquinones with lower electron density –
aprotic electrolytes, at two reduction potentials, as shown in due to attached electron withdrawing groups – do not have
Scheme 1(a) for anthraquinone. But in the presence of CO2, a the nucleophilic strength to react with CO2.38 A semiquinone
single two-electron quasi-reversible reduction takes place at the carboxylated by the reductive addition of CO2 has its negative
first reduction potential, as shown in Scheme 1(b), where the charge isolated from the rest of the molecule by a s-bond,
CO2 molecule carboxylates the quinone resulting in a carbonate rendering the carboxylated quinone aromatic ring(s) relatively
salt.37 Upon the first reduction of a quinone molecule, a semi- neutral. Hence, the two-electron reduction of the parent qui-
quinone radical anion is produced. Some semiquinones, with none under CO2 occurs at the first reduction potential. The
sufficient electron density, i.e. sufficient Lewis base strength, second reduction generates another nucleophilic center, i.e. the
can react with CO2 in a nucleophilic addition to form a second oxygen of the quinone, which reacts with a second CO2
Scheme 1 (a) Two single-electron reduction waves of anthraquinone in the absence of electrophiles. (b) One two-electron reduction wave of
anthraquinone in the presence of CO2.
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molecule to form a bis(carbonate) dianion salt – the quinol dianion layer in the porous electrode.44 While the ratio of polymer to
diadduct. A similar behavior is observed when quinones are reduced CNT was optimized for the greatest gravimetric capacity, it is
in protic electrolyte media and the reduced quinones react with not the ideal ratio for conductivity. Some of the conductivity
protons to form two hydroxyl groups via a two-electron reduction.39 takes place through the backbone of the polymer, which con-
The nucleophilic addition reaction of reduced quinones tributes to the slow electron transfer. This, however, does not
occurs only with electrophiles with sufficient Lewis acidity, such present a problem in the design of the contactor separation
as CO2, and not N2, hence the great selectivity in adsorption. unit, since the rate limiting step in the CO2 capture process is
Furthermore, water, in the treated gas stream, has minimal the transport of CO2 and not electron transfer.
effect on carbon capture, mainly because the hydrophobicity of The double carboxylation (CO2 addition) of anthraquinone
the IL used presents a considerable mass transfer resistance for to form the bis(carbonate) dianion follows an ECEC mechanism,
water with very little retention,40 and any residual water in the IL as shown in Scheme 2(a). During a constant-current charging of
phase merely stabilizes the reduced quinones,41 with no significant the cell in the presence of a flux of CO2 towards the quinone units
change to the electrochemical or chemical steps of the carbon equal to, or higher than, the rate of the electrochemical reduction
capture process.20 While the presence of oxygen can cause the of the quinones, both of the reduction electrochemical reactions
oxidation of some reduced quinones with a sufficiently negative take place at the first reduction potential, E01. The molar flux of
reduction potential, through the formation of the superoxide radical CO2, NCO2, towards the electrode (moles per unit area per second)
anion O2 , it is possible to avoid any reactions with oxygen in the should match the current density, J, at the electrode (charge per
feed stream by carefully tuning the electron density of the quinone unit area per second), as in,
polymer.42
J
The cyclic voltammogram (CV) of the PAQ–CNT composite NCO2 ¼ (3)
F
on the electrode substrate in [Bmim][TF2N] saturated with N2,
the green line in Fig. 3, shows two redox couples corresponding Conversely, if the flux of CO2 is lower than the rate of reduction,
to the two reduction potentials of anthraquinone. The cathodic some of the semiquinones produced in the first reduction are not
and anodic peaks, however, are broader than those reported for carboxylated but are instead reduced to quinol dianions at the
solutions of quinone molecules in electrolytes,20 which can be more negative second potential, E02, as shown in Scheme 2(b). In
ascribed to the slower electron exchange between differently- this case, for the same number of moles of semiquinone being
reduced redox units, i.e. neutral quinone, semiquinone (radical reduced, and hence electrons, i.e. charge, transferred, more
anion) and quinol dianion, along the p-conjugated backbone of energy is required in accordance with eqn (2).
the polymer,43 and also to the diffusion and electromigration of CO2 deprivation was not a problem in the highly saturated
electrolytic species into and out of the porous PAQ–CNT film.44 electrolyte in the CV electrochemical characterizations, where
The expected disappearance of the second redox couple of the the concentration of CO2 in the electrolyte was about 20 times
CV under CO2 was observed, as shown by the red line in Fig. 3, higher than that of the quinones on the electrode. However, in
and attributed to the carboxylation of the reduced quinone an adsorption system, where the electrolyte is not saturated
units along the polymer chain facilitating the second electron with CO2 there needs to be a careful balance between the
reduction of anthraquinone at the first reduction potential, advective and diffusive fluxes of CO2 towards the anthraqui-
with the consequent increase in the current at that potential. none cathodes for reductive addition, and the rate of the
The PAQ–CNT electrode can therefore be used to remove CO2 reduction of anthraquinone. This can be better controlled by
selectively from a gas mixture via nucleophilic addition, and charging the cell, i.e. reducing the anthraquinone, at a constant
regenerated via an electrochemical oxidation, with release of potential that is sufficient to drive the first reduction of
the CO2, as shown earlier. The two reduction potentials under anthraquinone but not the second, i.e. charging the cell at a
N2 are E01 = 1.21 V and E02 = 1.63 V, vs. Fc. Under CO2 these potential difference that is between DV1 and DV2. With operation
two potentials coalesce to yield a single quasi-reversible redox at this constant potential, the flux of CO2 does not affect the
couple at the first reduction potential observed under N2, i.e. E01. energy of binding, since the second electron is acquired by a
The separation of the oxidation and reduction peaks in the semiquinone at the first reduction potential, but only after the
CVs reported is large, indicating sluggish electron transfer to first CO2 addition occurs; following this second reduction, a
the quinone repeat units on the polymer, and a thick diffusion second CO2 molecule can bind to the dianion monoadduct.
Scheme 2 Reaction steps of the double carboxylation of quinones (a) in high and (b) low CO2 fluxes towards the anthraquinone electrode. E represents
an electrochemical reaction step. C represents a chemical reaction step.
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When the first reduction is allowed in a CO2-lean environment at

a constant potential, the current observed after the initial surge,
which results from the first reduction, is proportional to the flux
of CO2 towards the anthraquinone electrode. Nevertheless, this
current ultimately diminishes due to the decrease in the number

of semiquinones available to react with CO2. In a CO2-rich
environment, at constant potential charging, the observed current
after the initial surge is proportional to the transport of CO2 into the
electrode and the rate of the addition reaction which follows the
nucleophilic addition mechanism between semiquinones and
dissolved CO2,
R = kCQ CCO2,IL (4)
where R is the rate of the reaction and k is the rate constant.

The electrochemical steps proceed at a faster rate than the
chemical reactions, but both types of reactions have rates that
are faster than the rate of diffusion of CO2 in the IL, leading to a
Fig. 9 Cross-section of the electrochemical cell used in the simulations.
large Damköhler number,
kCQ CCO2 L
Da ¼ 1 (5) Q(CO2) respectively. The standard reduction potential for
DCO2 ;IL
both reactions is E01. While the first of the two electrochemical
where CQ is the initial concentration of anthraquinone repeat reactions in Scheme 2(b) is the same as that of Scheme 2(a), the
units on the electrode, CCO2 is the concentration of CO2 in the second reaction has Q2 as the reduced species and Q as the
IL, L is the thickness of the IL-wetted porous electrode, which is species with higher oxidation number, with a standard reduction
about 150 mm, and DCO2,IL is the diffusion coefficient of CO2 in potential of E02. Likewise, in the anode oxidation reaction, Fc+
the IL and is about 4 1010 m2 s1. While it is the semi- (ferrocenium) is the oxidized species and Fc (ferrocene) is the
quinone that participates in the reaction here, the initial reduced species at E0 = 0.03 V. The current densities of these
concentration CQ is a good approximation for estimating the reactions were described by the Butler–Volmer equation,
order of magnitude of Da. The rate constant can be estimated !
ð1aÞFZ
to be 102 M1 s1,37 resulting in Da B104. Large values of Da i ¼ i0 e
aFZ
RT e RT
(7)
indicate that mass transfer will control the process and thus the
charging and subsequent carboxylation of the quinones can be
assumed to be in equilibrium with the prevailing CO2 concentration where Z is the overpotential and a, the symmetry factor, was
at any position and at any time. Therefore, with a reduced thickness approximated to be 0.5 for all the electrochemical reactions. The
of the electrodes, the CO2 mass transfer rates will approach that of exchange current, i0, is given by
the nucleophilic addition reaction. i0 = k0[red]a[ox](1a) (8)
Modeling of CO2 capture The governing mass transfer equations for all the species
To further understand the behavior of the cell during constant- involved in the electrochemical reaction, including the supporting
current and constant-potential charging at various CO2 concen- electrolyte cations and anions, is
trations, a two-dimensional model of the cell and the adjacent @Ci
þ r Ni ¼ R i (9)
gap was set up in COMSOLs, with the geometry shown in Fig. 9. @t
The model accounted for all the chemical and electrochemical
where Ci is the concentration of the species, Ri is the rate of
reactions described in Scheme 2, in addition to the electrochemical
reaction in which the species is involved and Ni is the flux, which is
oxidation of the ferrocene. The equilibrium potentials of all electro-
zero for all immobilized faradaic species: anthraquinone in its
chemical reactions were predicted by the Nernst equation
different oxidation and binding states, and ferrocene. For mobile
RT ½red species, mainly the supporting electrolyte ions, the flux is given by
E ¼ E0 log (6)
nF ½ox
Ni = DirCi ziuiFCirF (10)
where E0 is the standard reduction potential, n is the number
where zi is the valence, ui is the molar mobility, F is Faraday’s
of moles of electrons involved, R is the gas constant, T is the
constant and F is the electric potential. The current density can
temperature, [red] is the concentration of the reduced species and
be obtained from the flux of charged mobile species in the
[ox] is the concentration of the reactant with high oxidation number.
electrolyte
In the first two electrochemical reactions shown in Scheme 2(a),
X
the reduced species are Q and Q(CO2)2, while the species of i¼F zi Ni (11)
higher oxidation number in these two reactions are Q and i
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and the overall electroneutrality is maintained by ensuring that where b is the adjusted Henry’s constant which accounts for the
X equilibrium partition of CO2 between the gas and IL phases.
zi Ci ¼ 0 (12)
i
The purpose of this simulation is to obtain a semi-
quantitative analysis of the behavior of the cell under different
The boundary conditions for these equations are ground conditions, and, therefore, order of magnitude estimates are
(F = 0 V) for the anthraquinone electrode (colored grey in made for the electrochemical parameters of the model.
Fig. 9), and either constant current or constant potential at the Model results for batch system. The simulation of constant-
ferrocene electrode (pink). The electrochemical model is the current charging at 0–5% CO2 concentrations in the sealed
same for both sealed and flow systems, although the transport system in which the gas channel shown in Fig. 9 served as a gas
of CO2 in the gas phase (shown as a transparent block) is headspace, shows results that are consistent with the afore-
different in the two scenarios. mentioned mechanism of CO2 capture. In addition to the cell
In the sealed system, CO2 transport occurs via diffusion voltage, the concentrations of all the cathode quinonic species
toward the electrode only, while in flow CO2 is also advected were studied during the charging process. Fig. 10 shows the cell
down the channel. In the sealed system, the partial pressure of voltages at 0–5% CO2 and the concentration profiles of cathode
the gas decreases during capture, while in flow the CO2 species at 0, 2, and 5% CO2. The cell voltage profiles in
concentration changes along the gas channel with time, and Fig. 10(a) show that as the concentration of CO2 increases, less
the concentration of the gas leaving the device is a measure of of the cell charging occurs at the higher potential. At 0% CO2
the total effectiveness of the adsorption bed capacity and the cell simply traverses both reduction potentials of the
transport and kinetic limitations within the system. The total quinone, and the species profiles in Fig. 10(b) show two
transport of CO2 is modelled by transport equations in each of consecutive conversions; the first is the reduction of quinone
the two phases, gas and IL. In the gas phase, the mass transfer to semiquinone, and the second is the reduction of semiqui-
governing equation in the sealed system is given by none to quinol dianion. The second reaction starts only after all
@CCO2 ;gas the quinone is converted to semiquinone, and to further
¼ DCO2 ;gas r2 CCO2 ;gas (13)
@t accommodate the incoming electrons at the constant current,
the second, more energetic reduction takes place until all
where CCO2,gas is the concentration of CO2 in the gas phase,
faradaic reactions are exhausted. Here, the simulation was
obtained from its partial pressure and the ideal gas law. This
stopped just short of full conversion to avoid numerical com-
governing equation has a no-flux boundary condition at the
plications that arise from the exhaustion of faradaic material,
three walls
i.e. complete charging. At 2% CO2, upon generation of the
@CCO2 ;gas semiquinone, shown in Fig. 10(c), the modest diffusive flux of
¼0 (14)
@O walls CO2 allows for the formation of the semiquinone monoadduct
which soon accepts a second electron at the first reduction
and at the gas–IL interface, the fluxes normal to the interface
potential of quinone, hence extending the cell charging period
are set to be equal
spent at the lower potential. This dianion monoadduct can
dCCO2 ;gas dCCO2 ;IL then react with a second CO2 molecule, to form the dianion
DCO2 ;gas ¼ DCO2 ;IL (15)
dx dx diadduct. But, upon the depletion of CO2 in the vicinity of the
where CCO2,IL is the concentration of dissolved CO2 in the IL cathode, due to a charging rate that is faster than the diffusive
phase. In the flow system, the flux of CO2 has an advective flux of CO2 into the electrolyte at 2% headspace concentration,
component as well and the governing equation becomes the semiquinone is converted to the dianion at the higher
second potential, while the concentrations of the dianion
@CCO2 ;gas
¼ DCO2 ;gas r2 CCO2 ;gas þ urCCO2 ;gas (16) monoadduct and the dianion diadduct remain constant. This
@t
is reflected in the potential profile at 2% CO2 in Fig. 10(a).
where u is the velocity of the gas flowing in the channel. The However, at 5% CO2, the diffusive flux of CO2 is adequate, and
inlet is set at a constant concentration inflow and the outlet at barely any semiquinone can be detected since it is converted to
zero gauge pressure. The mass transfer governing equation for semiquinone monoadduct, and other subsequent species, soon
dissolved CO2 in the IL phase, for both sealed and flow systems, after generation, shown in Fig. 10(d). Here, all the electro-
is given by chemical reactions take place at the first potential and none
@CCO2 ;IL of the semiquinone is converted to quinol dianion.
¼ DCO2 ;IL r2 CCO2 ;IL þ R (17)
@t Hence, the optimum charging method of the cell, i.e. CO2
capture, is to operate at a constant potential just larger than the
where R is a bulk reaction term describing the rate of the
first potential window DV1. The greater the charging voltage,
chemical reactions shown in Scheme 2(a). Simple rate equations,
the faster the reduction reaction due to the larger overpotential.
first order in all reactants, are used. A no-flux boundary condition
For practical reasons, and to avoid large current surges, the cell
is set at the walls. At the gas–electrode interface, the concentration
can be charged at a constant current until the desired charging
of dissolved CO2 is set to
potential difference is reached. This will be between DV1 and
CCO2,IL = bCCO2,gas (18) DV2 based on the rate of charging desired. At this point the bed
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is activated for capture by making half the total capture capacity concentration for a given cell voltage, respectively. The number
available. Then the cell can be set at that constant potential of bed volumes required increases with decreasing feed con-
until saturation of the cathodes is achieved. The second half of centrations, a result of the fixed overall bed capacity and the
the capture capacity is made available as more CO2 flows in. rectangular nature of the adsorption isotherm of this system. In
It is also possible to fully activate the bed by charging at a the absence of transport and reaction limitations, all break-
potential difference DVHigh 4 DV1, at which point the cells are through curves should collapse when the bed volume is multiplied
disconnected and allowed to saturate with no further supply by the feed fraction of the adsorbate; the fact that this is not exactly
of current, until breakthrough is achieved, and the bed is so in Fig. 11(d) indicates that mass transfer limitations do play a
regenerated by discharging the cell and releasing pure CO2. role in the uptake of CO2 by the activated electrodes. Nevertheless,
The energy recovered however, cannot exceed QDV1, resulting the overall capacity, indicated by the trapezoidal area under
in an energy loss of greater than Q(DVHigh DV1). Cout/Cin = 1 and the breakthrough curves, remained constant. How-
Model results for flow system. The model described above ever, the effect of a stronger driving force on improved mass transfer
was also used to simulate the capture of CO2 from a channel is evident in Fig. 11(b), where at charging potentials that are closer to
under flow conditions. The gas flowed parallel to the electrodes DV2, more of the dianion is generated in a Nernstian distribution,
in the cell, a cross-section of which is shown in Fig. 9. The which provides two reaction sites for CO2. This results in a stronger
simulated concentration profiles in the channel and the qui- driving force in the adsorption of CO2 and hence improved mass
none electrode are shown as a function of the number of bed transfer, which yields a sharper breakthrough profile.
volumes in Fig. 11(a). The gas phase profiles are consistent with Fig. 11(e) and (f) show the current across the electrochemical
a dispersed plug flow in the channels, with a reasonably sharp cell during the capture experiments in (c) and (b) respectively.
adsorption front, while the linear CO2 profiles in the electrode are Fig. 11(e) shows that at low potential charging, i.e. 1.3 V, an
a result of the significant diffusional limitations in this region. Of initial spike in current is observed which results from the
particular interest is the depletion of unbound quinonic species reduction of the quinones on the electrodes to semiquinone, as
in the cathode as removal of CO2 from the channel proceeds; as explained earlier. This is followed by a region of constant current
the cathode becomes saturated with CO2, the concentration of which is proportional to the flux of CO2 into the electrodes, since
CO2 increases along the length of the channel until break- it reacts with the semiquinones and allows them to accept a
through is achieved at around 8 bed volumes, after which second electron at the low potential. As the electrodes become
further saturation is allowed until the outlet concentration is saturated and all the semiquinone is depleted, the current
equal to the inlet concentration at around 10 bed volumes. decreases. This region of constant current followed by the sharp
Fig. 11(b) and (c) show the breakthrough profiles as a function decrease is very broad for the 10% case, but much shorter for the
of cell voltage for a given feed concentration, and of feed 50% case, where there is a brief transition from the initial spike
Fig. 10 Simulation of charging the electrochemical cell at different CO2 concentrations at constant current. (a) Potential difference of the cell. The
change in concentration of quinone with charge is shown at (b) 0%, (c) 2% and (d) 5% CO2.
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Fig. 11 (a) Breakthrough profiles from simulation at 50% CO2 and charging potential of 1.7 V; inset: the concentration of CO2 in the channel and the
concentration of unbound quinonic species in the cathode with bed volume. (b) Breakthrough profiles at multiple capture potentials at 50% inlet
concentration. (c) Breakthrough profiles from simulation at multiple inlet concentrations at a charging potential of 1.3 V. (d) Normalized breakthrough
profiles of the capture experiments in (c). (e) The current across the electrochemical cells during the capture experiments in (b). (f) The current across the
electrochemical cells during the capture experiments in (c).
to the decreasing current region manifested in a shoulder. are in their doubly charged states and no further electron
However, Fig. 11(f) shows that as the applied capture potential transfer occurs. This double peak behavior of the current is
increases, the current profile for the same inlet concentration the result of the balance between the rate of electron transfer
changes dramatically. This is elucidated in Scheme 3; as the and the flux of CO2, which relates to the earlier discussions. At
applied potential approaches DV2, all of the quinone is reduced to charging potentials higher than DV2 e.g. DVHigh, not shown here,
semiquinone and a Nernstian distribution of semiquinone and a larger first peak is expected where all the quinone is converted
quinol dianion is generated, evident by the increasing current in to semiquinone then dianion, i.e. two consecutive single-electron
the first peak. reductions, after which the current drops to zero and only
Thus, CO2 reacts with the Nernstian mixture of semiquinone chemical addition reactions occur, Scheme 2(b).
and quinol dianion, where in the case of the latter no further
reaction, chemical or electrochemical, occurs, but in the case of Energetic analysis of CO2 release
the former a semiquinone monoadduct species is formed, The applied release potential determines the energy recovered
which can be reduced to the dianion monoadduct at DV1. from the cell upon the release of CO2, and must, therefore, be
Therefore, the applied potential presents a large overpotential selected carefully. While quinones under N2 are expected to be
for this reaction, hence the second increase in the current reduced and oxidized reversibly without any significant loss of
which corresponds to the electron transfer for this reduction. energy, in an electrophile-rich environment, such as CO2, the
Following these steps, all the quinone moieties in the electrodes reduction is only quasi-reversible due to the energetic penalty
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Scheme 3 The reduction of anthraquinone at a potential higher than its second reduction potential with a limited flux of CO2.
of breaking a bond formed with CO2. Therefore, some of the Consequently, to reduce energy losses per cycle, a less positive
energy is lost in the process, and it is imperative to minimize potential can be used in a constant potential discharge. While the
this loss, since it is directly related to energy per mole of CO2 capture cell voltage can be maintained at fairly minimal levels by
concentrated (captured and released) in a CO2 capture process. setting it close to DV1, with some diminishment in rate, release at
The last step in the CO2 capture, Scheme 1(b), i.e. the addition of a high cell voltages can result in a partial release of CO2, due to the
second molecule of CO2 to the semiquinone monoadduct to form partial oxidation of the bis(carbonate) quinone units (dianion
a dianion diadduct, is chemically irreversible for the duration of diadduct units), and a subsequent underutilization of anthraqui-
the cycle,37 and the release reaction takes place via an electro- none. After a few cycles of capture and release at a higher potential,
chemical oxidation of the diadduct. This oxidation occurs at a a constant equilibrium rate of utilization of anthraquinone is
more positive potential than the first reduction potential E01. Thus, achieved. This is akin to the working capacity of a pressure-swing
the more positive the release potential, the larger the overpotential adsorption system.45 Thus partial release can be achieved at higher
and the faster and more complete is the release of the bound CO2. cell discharge potentials as shown in Fig. 12. This allows for a much
However, a more positive release voltage corresponds to less smaller window of operation, which at the B90% faradaic efficiency
energy recovered during discharge, and thus more work done reported earlier, an energy use of B43 kJ mol1, with 60%
per cycle of capture and release, which is given by eqn (2). utilization of accessible quinone is possible. This is on par with
Fig. 12 Fraction of CO2 released from the PAQ–CNT electrode with release voltage. At a constant capture cell voltage of 1.3 V, less of the bed is
recovered with increasing release cell voltage, but the energy per mole of CO2 captured and released also decreases.
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other carbon capture systems in efficiency and energy con-

sumption,46,47 including thermal swing systems.48
Solid sorbent materials used in carbon capture applications
have enthalpies of CO2 adsorption of the same order, e.g., Metal–
Organic Frameworks (MOFs) with 30–50 kJ mol1 for some types

of MOF-74,49 and B100 kJ mol1 for some amine functionalized
MOFs,50 or zeolites, such as 13X at 40 kJ mol1.51 However, these
are not process energetics but rather enthalpies of adsorption.
Therefore, processes which are designed to utilize these materials
incur greater energetic penalties associated with the techniques
used for delivering the energy for desorption, i.e. heat and
pressure change, whereas the energetics reported herein corre-
spond to that of the process, which unlike those utilizing solid
sorbents, has a binary affinity for CO2.
Moreover, if a precise rate of release is desired, the cell can
be discharged at a constant current. In this case, the flux of the
released CO2 is proportional to the current density, as given by
eqn (3). The discharge current and time, control the charge
transferred, which is the extensive variable in the work of the
process. This method of release is seldom utilized in swing
adsorption processes, because it is the intensive, rather than
the extensive variable, that is modulated, e.g., temperature in
thermal swing, pressure in pressure swing, and, here, potential.
Nevertheless, this can be useful for fast regeneration of the bed at
high currents, where long periods of capture and short periods of
release are desired. But due to the incomplete discharge of the
electrochemical cells, in analogy with high current discharge of
batteries,30 the bed will only be partially regenerated.
Swing operations
The electro-swing adsorption (ESA) technology developed in
this work has a number of perceived advantages over other
swing technologies such as temperature- (TSA) and pressure-
swing (PSA) adsorption in terms of both its mode of operation
and its thermodynamic adsorption characteristics, as illustrated Fig. 13 Comparison of temperature- (TSA), pressure- (PSA) and electro-
in Fig. 13. Temperature-swing operations require heating and (ESA) swing operations showing the impact of sorption isotherms on total
working capacity.
cooling of the entire adsorption matrix to release the adsorbed
compounds, rather than just targeting the adsorption sites
themselves, which introduces many thermal inefficiencies regeneration of the adsorbent, or the partial pressure of the
to the operation. The heating is typically accomplished with recovered adsorbate in the sweep stream. The electro-swing
high-temperature steam as the sweep gas, with subsequent adsorbents, on the other hand, are characterized by a rectan-
condensation of the steam to recover the pure CO2 product gular adsorption isotherm in which the saturation loading
stream, whereas cooling is achieved during the blowdown phase in capacity in the activated state is independent of the gas phase
preparation for the next sorption cycle. With pressure-swing opera- concentration, so the adsorbent is equally effective over a wide
tions, the release of the captured material occurs on reduction of the range of feed concentrations from ambient conditions through to
adsorbate partial pressure in the sweep to reverse the mass transfer those characteristic of large scale power and industrial facilities.
driving force, which can be achieved either by drawing a vacuum on When deactivated, the adsorbent has negligible capacity for the CO2
the bed, or by using low pressure steam as the sweep gas. The even at high CO2 gas phase concentrations such that the working
product leaving the bed is dilute, and requires a second separation capacity of the adsorbent is independent of operating conditions.
step, such as the condensation of steam, and external compression Thus, the sweep stream during the desorption process can be pure
of the resulting CO2 to bring it to the desired pressures for CO2 at the desired pressure, subject primarily to equipment design
subsequent utilization or for transportation and subsurface seques- constraints, which greatly simplifies the adsorption/desorption cycle
tration in geologic formations. Moreover, in both TSA and PSA relative to those of the TSA and PSA processes. The results in
operations, the working capacity is strongly dependent on the shape Fig. 6(a) show that release into a pure CO2 gas environment is facile
of the Langmuir- (or Freundlich-) type isotherm, with significantly and fast, and complete if sufficient time is allowed to account for
lower capacities at lower concentrations, which limits the degree of the kinetics of the process.
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Conclusions battery separator was purchased from Celgard. Stainless steel

(SS) mesh (316, 500 500) was purchased from Gerard Daniel
The electro-swing operations outlined in this paper offer a new International. DMF was dried over 3 Å molecular sieves over
approach to the exploitation of electrochemically mediated three stages and purged with N2 for 12 h. All other reagents were
complexation of CO2 with redox-active species for the mitigation used without further modification.
of CO2 emissions, and for control of CO2 levels in confined
environments. Electro-swing adsorption has been shown to be Methods
equally effective, at a constant capacity, for the capture of CO2 at Synthesis of poly(1,4-anthraquinone) (P14AQ). The synthetic
concentrations typical of fossil fuel combustion flue gases procedure followed the work of Yamamoto et al.43 A solution
(B10%) and in confined ambient environments (0.6–0.8%). of 1.510 g (5.45 mmol) 1,4-dichloroanthraquinone in 20 mL
These advances have been made possible by the development
DMF (dry and O2-free), was added dropwise to a solution of

of new electrode materials in which redox-active moieties, such 2.000 g (7.27 mmol) of bis(1,5-cyclooctadiene)nickel(0), 1.134 g
as quinones, that can bind CO2 in one oxidation state but not in (7.27 mmol) of 2,2 0 -bipyridyl and 0.7 mL (5.45 mmol) of 1,5-
another are immobilized onto the electrode substrates. These cyclooctadiene in 50 mL DMF (dry and O2-free), stirring at 65 1C
functionalized electrodes were incorporated into an electro- under Nitrogen. The mixture reacted at 65 1C for 72 h. After
chemical cell assembly to facilitate their cyclical electrochemical cooling to room temperature, 100 mL of 1 M hydrochloric acid
reduction and oxidation. The cells demonstrated exceptional (HCl) was added to reaction mixture and allowed to stir at room
capture and release of CO2 over more than 7000 cycles at temperature for 1 h. The mixture was then filtered and washed
60–70% quinone utilization, 90% faradaic efficiency, and with 200 mL of 1 M HCl, twice with 200 mL of de-ionized water,
90 kJ mol1 at 100% bed utilization and 43 kJ mol1 at 60%. twice with 100 mL DMF followed by 100 mL water and 100 mL
A significant advantage of the quinone-functionalized electrodes is methanol washes. The residue was dried under vacuum for
that they have a CO2 capacity that is essentially independent of the 24 h. The procedure yielded 1.084 g polymer (96% yield). The
inlet feed concentration, in contrast to the capacities of sorbents resulting solid was extracted for low molecular weight chains
typically used in PSA or TSA operations, where Langmuir-type via Soxhlet extraction with DMF for 5 h, to obtain 0.890 g of
equilibria limit capacity at lower concentrations. long chain polymers.
The strong performance of the electro-swing process allows Polymer–multi-walled carbon nanotube (MWCNT) composites
for numerous applications where CO2 removal and/or storage is P14AQ–CNT. The composite was made by ultra-sonicating using
of interest. The ESA device can be easily integrated into Cole-Parmer 750 Watt Ultrasonic Processor a suspension of
processes in a plug-and-play fashion due to its simple design, 40 mg of P14AQ (as made) in 40 mL of NMP at 5 1C for
and minimum requirement for ancillary equipment, primarily a 20 minutes, followed by adding 120 mg MWCNT into the polymer
regulated power source and sink (load). An initial techno- suspension to be sonicated for 20 minutes, resulting in a well-
economic analysis (not reported here) shows that such carbon dispersed 4 mg mL1 ink.
capture systems can be economically feasible with costs ranging PVFc–CNT. The composite was made by ultra-sonicating
from $50–$100 per tonne CO2 depending on the feed concen- using a suspension of 160 mg of PVFc in 40 mL of NMP at
trations and applications under consideration. 5 1C for 20 minutes, followed by adding 160 mg MWCNT into the
It is projected that further optimization of the ESA process polymer suspension to be sonicated for 20 minutes, resulting in a
can be obtained through refinement of the electrode chemistries well-dispersed 8 mg mL1 ink.
and their assembly into compact adsorption devices to address a Preparation of electrodes. Non-woven carbon mat were dip-
wide range of CO2 mitigation strategies. coated into the polymer–CNT inks multiple time to deposit a
certain mass of the composite. These were dried for 40 min in
Experimental an oven at 120 1C and ambient pressure between dips, and then
dried at the same conditions for 12 h after the final dip. These
Materials were used for electrochemical characterizations and for cell
Dichloro-1,4-anthraquinone (498%) and 2,2 0 -bipyridyl (499%) assembly.
were purchased from TCI America. Bis(1,5-cyclooctadiene)- Electrochemical cell assembly. Each electrochemical cell
nickel(0), 1,5-cyclooctadiene (499%), MWCNT (498%, O.D. was assembled by carefully laminating 9 layers and the ILs in
L 6–13 nm 2.5–20 mm), anhydrous N,N-dimethylformamide the following order: SS current collector; P14AQ–CNT coated
(DMF, 499.5%) and N-methyl-2-pyrrolidinone (NMP, 498%) carbon mat; IL; electrolyte separator; IL; PVFc–CNT coated
were purchased from Sigma-Aldrich. Poly(vinylferrocene) (PVFc, carbon mat electrolyte separator; SS current collector; PVFc–CNT
MW B 50 000 g mol1) was purchased from Polysciences, Inc. coated carbon mat; IL; electrolyte separator; IL; P14AQ–CNT coated
1-Butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide carbon mat; SS current collector. The electrolyte separators
(499%) was purchased from IOLITEC, Ionic Liquids Technologies were either Whatman-2 cellulose filter paper, and the IL was
GmbH. Bone dry 3.0 grade carbon dioxide and industrial grade [Bmim][Tf2N].
nitrogen gases were purchased from Airgas. Non-woven carbon Electrochemistry. Electrochemical measurements were carried
mat (34 g m2) was purchased from Marktek, Inc. Whatman-2 out using a Parstat 3000-DX potentiostat with VersaStudio soft-
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Energy &

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Faradaic electro-swing reactive adsorption for

Cite this: Energy Environ. Sci.,

Introduction mainly amine scrubbing,5 and oxyfuel combustion,6 which

Paper Energy & Environmental Science

Energy & Environmental Science Paper

Paper Energy & Environmental Science

Energy & Environmental Science Paper

chamber into which the electrodes were inserted. Changes in

exiting the device was monitored, with the breakthrough point

CO2 in a sealed chamber, shown in Fig. 5. This cell had B4.8 mg

Paper Energy & Environmental Science

Energy & Environmental Science Paper

DV22 to guarantee the complete reduction of the all accessible

mainly because the kinetics of the reduction and the adsorption

where the bed volume is a time measure which represents the

Paper Energy & Environmental Science

Energy & Environmental Science Paper

Paper Energy & Environmental Science

When the first reduction is allowed in a CO2-lean environment at

current ultimately diminishes due to the decrease in the number

R = kCQ CCO2,IL (4)

where R is the rate of the reaction and k is the rate constant.

Energy & Environmental Science Paper

Paper Energy & Environmental Science

Energy & Environmental Science Paper

Paper Energy & Environmental Science

Energy & Environmental Science Paper

other carbon capture systems in eﬃciency and energy con-

Organic Frameworks (MOFs) with 30–50 kJ mol1 for some types

Paper Energy & Environmental Science

Conclusions battery separator was purchased from Celgard. Stainless steel

DMF (dry and O2-free), was added dropwise to a solution of

Energy & Environmental Science Paper

B20 mbar and purged with N2 or CO2 for 30 min before

conducted at T B 21 1C. C. Jack, Geophys. Res. Lett., 2001, 28, 3317–3320.

Paper Energy & Environmental Science

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