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Bio-mimetic Oxygen Separation via Hollow Fiber Membrane Contactor with

O2 Carrier Solutions

Article  in  Chemical Communications · August 2018

DOI: 10.1039/C8CC01457D

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ChemComm
COMMUNICATION
Bio-mimetic oxygen separation via a hollow fiber
membrane contactor with O2 carrier solutions†
Cite this: Chem. Commun., 2018,
54, 9454
Mahdi Fathizadeh, ‡a Konstantin Khivantsev,‡a Travis J. Pyrzynski,b
Received 21st February 2018, Naomi B. Klinghoffer,b Abolfazl (Nabi) Shakouri,a Miao Yu*a and Shiguang Li
Accepted 31st July 2018
DOI: 10.1039/c8cc01457d
rsc.li/chemcomm
A low-cost poly(ethyleneimine)–cobalt (PEI–Co) complex solution with
high O2 absorption capacity (as high as 1.5 L O2 (STP)/L solution) was
developed and used in a bio-mimetic system to produce high-purity O2
from air. An oxygen concentration greater than 99.6% was demonstrated.
Oxygen production from air has a wide range of applications in
oxygen-intensive industries, such as energy production (e.g., oxy-
combustion systems), fuels, chemicals, and other industries.1
Table 1 lists state-of-the-art air separation technologies.2
Among these technologies, cryogenic distillation is the most
mature technology for large scale and high purity (499%) O2
production. However, cryogenic distillation-based air separation is
costly and energy-intensive.1,3,4 Therefore, it is important to
develop new advanced O2 production technologies with low cost.
Adsorption processes could provide up to 95% purity O2 (Table 1),
but the capital cost increases rapidly with the O2 production rate
compared with cryogenic processes, which limits their application
for large-scale O2 production.1,4 Polymer membrane separation
processes are simple and more energy efficient, but they cannot
provide oxygen at high enough purity (495%) required for
gasification. Ion transport membranes (ITMs) can produce
almost pure O2 (499%).6 However, materials for the fabrica-
tion of ITMs are costly. Also, membrane fabrication needs high
temperature (41100 1C) and oxygen separation is operated at
high temperature (4700 1C), meaning high operating costs.
Thus, it might be hard for ITMs to compete with cryogenic
distillation for potential large-scale applications.
Some of the focus in advanced oxygen separation efforts has
been on bio-mimetic processes, such as mimicking hemoglobin.
Hemoglobin is known to be the O2 carrier in blood and is able to
reversibly bond with O2. In 1960, Scholaner first reported the
preparation of hemoglobin-based liquid membranes and their
a
Department of Chemical Engineering, University of South Carolina, Columbia,
SC 29208, USA. E-mail: yum5@rpi.edu
b
Gas Technology Institute, 1700 S. Mount Prospect Road, Des Plaines, IL 60018,
USA. E-mail: shiguang.li@gastechnology.org
† Electronic supplementary information (ESI) available. See DOI: 10.1039/c8cc01457d
‡ These authors contributed equally to this work.
9454 | Chem. Commun., 2018, 54, 9454--9457
*b
Table 1 State-of-the-art air separation technologies5
Technology Current status O2 purity limit (vol%)
Cryogenic distillation Mature 99+
Pressure swing adsorption Mature 95
Polymeric membranes Mature 40
Ionic transport membranes Demonstration 100
potential for air separation.7 He observed that the O2 transport
rate in hemoglobin-based liquid membranes was 8 times higher
than that in pure water, resulting in a maximum of 83% O2 on
the permeate cell. Since then, liquid membranes or facilitated
membranes with various dissolved O2 carriers have been widely
studied and separation selectivity as high as 40 has been obtained.8
These liquid membranes, however, have stability issues; for
example, the loss of liquid leads to a decline of separation
performance, limiting their potential for practical applications.
Polymeric membranes, incorporated with O2 carriers, were
developed to address these stability issues.9,10 In these studies,
the concentrations of O2 carriers were low in order to maintain
the good mechanical stabilities of the mixed membranes. Because
the polymer phase itself allowed N2 to permeate through, only a
slight increase in O2/N2 selectivity was observed for the O2 carrier
incorporated polymer membranes.
Herein, we report a novel concept to produce high-purity oxygen
from air via a hollow fiber membrane contactor with an oxygen
carrier solution as the solvent. In this concept, as illustrated in
Fig. 1, air is sent into a membrane absorber and passes through
small-diameter membrane tubes (hollow fibers with porous walls),
while a lean O2 carrier solution flows counter currently on the shell
side of the membrane. The O2 permeates through the membrane
pores and is absorbed in the O2 carrier solution.
The O2-rich carrier solution can be regenerated in a second
membrane module (desorber) operated in a reverse process.
In that case, the O2-rich carrier solution is fed to the shell
side of the hollow fibers and the O2 is pulled out from the
solvent using vacuum or sweep gas on the bore side of the
hollow fibers.
This journal is © The Royal Society of Chemistry 2018
Communication ChemComm

Fig. 1 Diagram of gas and liquid flows in a membrane contactor.

The membrane with hollow fibers and O2 carrier solution

mimics ‘‘blood vessels’’ and ‘‘blood’’ in the bio-mimetic hollow
fiber membrane contactor process. Both the membrane and Fig. 2 O2 uptake kinetics of PEI–Co complex solutions with different
carrier are critical for high-purity O2 production. This concept volume ratios of the PEI solution to CoCl2 solution at 20 1C. The
concentration of both the PEI (based on N) and CoCl2 solution is
has been demonstrated in our study.
1 mol L 1; the CoCl2 solution volume is fixed at 1 mL.
Oxygen solvent. A polyethyleneimine (PEI)–cobalt complex
(PEI–Co) solution for O2 absorption was prepared by simply mixing
PEI with CoCl2 aqueous solutions under vacuum; typically,
To understand how the O2 molecule bonds with the PEI–Co
1 mol L 1 CoCl2 aqueous solution was mixed with different
complex, the reaction was monitored by attenuated total reflectance-
volume ratios (5–20) of 1 mol L 1 (based on PEI units) PEI
infrared (ATR-IR), electron paramagnetic resonance (EPR) and
solution. Table 2 shows that the viscosity of the fresh PEI–Co
ultraviolet-visible (UV-Vis) spectroscopy. ATR-IR difference spectra
complex solution increases slightly with decreasing PEI to
during the exposure of the PEI–Co solution to O2 at room tempera-
CoCl2 volume ratio and is approximately two times the viscosity
ture revealed the growth of a complex set of weak bands in the
of water; O2 absorption after exposure to air for 30 min increased
B1200–1050 cm 1 region, indicating O–O stretches of Co(II)–O2
the viscosity to about 3 times the viscosity of water. This may
adducts and Co(III)–O2* superoxo complexes (Fig. 3a). Indeed,
result from the increased cross-linking due to O2 bonding with
Zecchina et al.11 found that Co2+ on the surfaces of diluted
Co. A relatively low viscosity is favorable for the membrane
Co(II)–MgO solid solutions reversibly binds oxygen at low temperature
contactor process by lowering the operation energy cost.
(B100 K), forming molecular species characterized by a similarly
We measured the maximum O2 capacity of the PEI–Co
complex set of weak O–O stretching frequencies in the 1160–1015 cm 1
complex solution by exposing the solution to air and then
range. They concluded that O2 is adsorbed in the superoxide form
monitoring the pressure change in a batch system (Fig. S1 in
and that more than one type of species is formed. Additionally, they
ESI†). Before measuring O2 uptake from air, we also measured pure
also described that even at such a low temperature some irreversibly
N2 absorption and confirmed negligible N2 uptake. Therefore, the
bound oxygen was present (B15–20%). The nature of irreversibly
pressure change in the sealed container with air is primarily due to
bound oxygen was not described. In our case, 1145 cm 1 is the most
O2 absorption. The maximum O2 uptake increases with decrease of
prominent feature, with peaks at B1195–1200 and 1050 cm 1 less
the volume ratio of the PEI solution to CoCl2 solution, which can be
pronounced. Notably, another peak grew at wavenumbers below
mainly attributed to the increase of Co concentration and the
900 cm 1 (B850 cm 1) with time, it can be assigned to O–O in either
relatively constant Co to O2 ratio (Table 2). We selected the PEI–Co
peroxo adducts Co(III)–O–O–Co(III) or hydroperoxo Co(III)–OOH
complex with a ratio of 10 as the O2 carrier solution for demon-
complexes.12 These results indicate that both O2 bonds, reversible
strating O2 separation performance in the membrane contactor
and irreversible, grew quickly after O2 was introduced. Fig. 3b
due to its high O2 capacity, fast uptake kinetics (Fig. 2), and
shows the electron paramagnetic resonance (EPR) spectroscopy
moderate viscosity, especially after air exposure (Table 2).
results. The original Co(II)–amine complex in water prepared in a
glove-box (absence of O2) was EPR silent. This seems unusual since
Co(II) ions have a d7 electronic configuration and are expected to
Table 2 Properties of PEI–Co complex solutions at 20 1C
have unpaired electrons. Indeed, EPR is an important technique for
Volume ratio of PEI to Viscosity,b Maximum O2 uptake, investigating Co(II) complexes in solution due to the inherent
CoCl2 solutionsa mPa s L(STP)/L solutionc paramagnetism of mononuclear Co(II) ions;13 we also recently
20 2.02 (2.95) 0.59 (1.83) demonstrated that mononuclear Co(II) ions embedded into
15 2.19 (2.95) 0.78 (1.80) siloxane rings are able to form EPR-active Co(II)1O4 sites.14 Thus,
10 2.31 (3.04) 1.1 (1.85) the absence of an EPR signal (except for the broad line caused by
7.5 — 1.3 (2.03)
5 — 1.5 (2.49) the cavity effect) is an interesting finding. Only limited studies can
a be found in the literature on the complexation of PEI and M(II)
The concentration of PEI (based on CH3CH2N units) and CoCl2 is
1 mol L 1. b Values in parentheses are viscosities after exposure to ions. Kislenko et al. studied in detail the complexation of cobalt(II),
air for 30 min. c Values in parentheses are the Co to O2 ratios. nickel(II) and iron(II) ions with PEI solution.15 They concluded that

This journal is © The Royal Society of Chemistry 2018 Chem. Commun., 2018, 54, 9454--9457 | 9455
ChemComm
Fig. 3 Characterization of the PEI–Co complex and its bonding with O2:
(a) ATR-IR spectra of PEI–Co after exposure to air for 1, 5, 10 and 30 min
(from bottom to top); (b) EPR spectra of PEI–Co before (blue) and after
(red) exposure to O2 for 3 min; and (c) time-resolved cobalt species
distribution diagram (relative amount vs. time).
complexation between Co(II) and PEI starts with the formation of a
binuclear Co(II) hydroxo complex with a Co2(OH)x core (where x is
1 or 2); the amine groups of PEI replace terminal H2O molecules
from the first coordination sphere of Co forming NyCo(OH)xCoNy.
Therefore, absence of the EPR signal is likely due to the formation
of this type of dimeric complex with antiferromagnetically coupled
Co(II) centers. Moreover, it is in excellent agreement with the
published titration data, further confirming the validity of the
titration approach to describing the complexation behaviour of
PEI and M(II) ions. The formation of dimeric hydroxo-bridged
9456 | Chem. Commun., 2018, 54, 9454--9457
Communication
species is also well-documented for Pt(II) with polyamidoamine
and polypropyleneimine dendrimers that have structures similar to
the amine employed in our study.16
Upon exposure to molecular O2 via bubbling, the EPR signal
of the Co–O2 superoxo species was immediately detected
because of its unpaired electrons. This result is fully consistent
with ATR-IR findings. Note that the peroxo species does not
have paired electrons, and thus no EPR signal can be detected.
Combined IR and EPR findings highlight the unique reactivity of
the Co(II)–PEI system with oxygen with the formation of a mixture of
dioxygen, superoxo and peroxo complexes in water at room tempera-
ture. Please note that water is normally considered very detrimental for
the reactivity. More specifically, Jeffrey R. Long and co-workers demon-
strated in a series of papers17–19 that M(II) sites in some M(II)–MOFs
have a significantly higher affinity for O2 over N2 and thus might serve
as potential candidates for O2/N2 separations at low temperatures
(below 70 1C): however, Fe2(dobdc) irreversibly oxidizes at tempera-
tures above 50 1C, while Cr(II) MOFs exhibit capacity losses over
multiple cycles, with these framework materials decomposing when
exposed to humid air. More recently,19 it was demonstrated by the
same group that Co(II)–MOFs Co–BTTri and Co–BDTriP can perform
O2/N2 separation with O2 adsorption at 70 1C and O2 desorption at
60 1C. Notably, the material did not significantly degrade upon
exposure to humid air at room temperature. Clearly, the presence of
Co(II) sites capable of binding O2 is crucial for this unique reactivity. In
Fe(II) materials, including hemoglobin, the high pressure of oxygen
destroys the active site very quickly. In our case, this separation can be
performed even in water at room temperature unlike most other
systems described in the literature in which low temperature and/or
organic solvents are required.20
We then employed stopped-flow UV-Vis measurements to provide
us with a realistic interpretation of the kinetics of Co–amine interaction
on a millisecond time scale and deconvolute the complex behaviour
and formation of a few O2-containing species: singular value decom-
position (SVD) analysis was used to obtain spectral signatures of the
relevant cobalt species (Fig. S3 in the ESI†). Thereafter, we obtained the
time-dependent species distribution, shown in the ‘‘concentration
versus time’’ plot (Fig. 3c). These results are consistent with the FTIR
data that indicate the formation of four oxygenated species that can be
seen from UV-Vis measurements (Fig. 3c). Complex A corresponds to
the PEI–Co and N group, which forms initially; complexes B and C are
inferred to be two different PEI–Co(II) complexes with O2, most likely,
Co(II)–O2 and Co(III)–O2*, which can be reversibly deoxygenated under
vacuum; the 4th type of the complex (D), the PEI–Co(III) complex with
O2, is slowly produced with time. Interestingly, the amount of complex
D increases with decreasing amount of complex C. In other words, the
oxygenated species forms quickly and then converts into more stable
species C which, at a much slower rate, converts into species D. We
suggest that species D is a Co(III) oxygen complex (probably peroxo). As
soon as Co(III) is formed, an electron is transferred to the antibonding
orbital of O2, thus leading to the significant lengthening of the O–O
bond, with the formal bond order changing from 2 to 1; it is much
more difficult to remove oxygen in the molecular form from such a
species.11 Indeed, heating is required in some cases to semi-reversibly
decompose the peroxide species – however, in water this reaction
competes with water hydrolysis with the irreversible formation of
This journal is © The Royal Society of Chemistry 2018
Communication
Table 3 Concentrations of O2 and N2 in the retentate side
Air flow rate N2 concentration O2 concentration
(mL min 1) (vol%) (vol%)
5 99.4 0.6
10 95.3 4.7
15 92.5 7.5
Co(III)–OH; analogous Fe(III)–OH and Fe(III)–O–Fe(III) adducts are known
to be the cause of deactivation of heme iron complexes.20
Therefore, a fast desorption process is expected to decrease
the amount of oxidized Co(II) to Co (III) and improve the
reversibility of the PEI/Co complex.
Membrane absorption. In a membrane absorption test, air was fed
to the bore side of a hollow fiber membrane module (3M, part
number G543). The module has X50 type polypropylene fibers with a
polycarbonate housing and polyurethane potting material. The total
permeation area of the membrane was around 0.2 m2. A PEI–Co
solution with a PEI/Co ratio of 10 was added to the shell side and the
concentrations of O2 and N2 in the retentate side were measured
using an O2 analyzer. A mass flow controller was used to control the
air feed flow rates at 5, 10, and 15 mL min 1.
Table 3 shows that the N2 concentration was as high as
99.4% at an air flow rate of 5 mL min 1, indicating that the
majority of the O2 was absorbed by the O2 solvent.
Integrated membrane absorption/desorption. Two membrane
modules of the same type were used in integrated membrane
absorption/desorption testing. The desorption process was
performed in a batch mode. After sealing the desorber, a
vacuum was applied on the tube (gas) side. After a vacuum
was established, argon sweep gas was flowed through the tube
side to remove desorbed gases. The gas composition was
measured with a gas chromatograph (SRI 8610C) with a zeolite
3A column. This measurement was performed at 25 1C and
atmospheric pressure. Initially, only nitrogen was detected, but
over time the concentration of oxygen increased. The nitrogen
is likely dissolved in the solution, which is easily removed in
the desorption membrane. The maximum measured oxygen
concentration was 99.6% on an argon-free basis. The adsorp-
tion and desorption experiments were carried out with one
hollow fibre membrane. The performance of the hollow fibre
membrane was constant during the performance experiment,
more than 3 months.
In conclusion, we developed a novel hollow fibre membrane
contactor with an oxygen carrier solution that can produce
oxygen with 99.6% purity. The carrier solution has an extremely
high oxygen adsorption capacity (up to 1.5 liters per litre
solution) and it consists of earth-abundant Co(II) and a cheap
polyethyleneimine polymer (PEI, bulk price o7 cents per gram)
in water. Spectroscopic characterization revealed that binuclear
cobalt hydroxo complexes are able to produce molecularly and
superoxo bound cobalt–oxygen complexes in water which are
the true reversible oxygen carriers.
We gratefully acknowledge support from the US Department
of Energy National Energy Technology Laboratory (NETL) under
Award Number DE-FE0024080.
This journal is © The Royal Society of Chemistry 2018
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Conflicts of interest
There are no conflicts to declare.
Notes and references
1 A. R. Smith and J. Klosek, A review of air separation technologies
and their integration with energy conversion processes, Fuel Process.
Technol., 2001, 70(2), 115–134.
2 J. D. Costa, S. Smart, J. Motuzas, S. Liu and D. Zhang, State of art
(SOTA) report on dense ceramic membranes for oxygen separation from
air, Global CCS Institute, p. 112031.
3 L. V. Van der ham and S. Kjelstrup, Energy analysis of two cryogenic
air separation processes, Energy, 2010, 35(12), 4731–4739.
4 S. S. Hashim, A. R. Mohamed and S. Bhatia, Oxygen separation from
air using ceramic-based membrane technology for sustainable fuel
production and power generation, Renewable Sustainable Energy
Rev., 2011, 15(2), 1284–1293.
5 Advanced Carbon Dioxide Capture R&D program: Technology
Update, May 2013, Oxygen Production.
6 J. M. Repasky, L. L. Anderson, V. E. Stein, P. A. Armstrong
and E. P. Foster, ITM Oxygen technology: scale-up toward clean
energy applications, International Coal Conference, Pittsburgh,
Pennsylvania, 2012.
7 P. F. Scholander, Oxygen transport through hemoglobin solutions,
Science, 1960, 131(3400), 585–590.
8 A. Figoli, W. F. C. Sager and M. H. V. Mulder, Facilitated oxygen
transport in liquid membranes: review and new concepts, J. Membr.
Sci., 2001, 181(1), 97–110.
9 Y. He, J. P. Yang, H. S. Li and P. C. Huang, The effect of oxygen
carriers on gas transport through polysiloxane and ethylcellulose
membranes, Polymer, 1998, 39(15), 3393–3397.
10 H. Nishide, Y. Tsukahara and E. Tsuchida, Highly selective oxygen
permeation through a poly(vinylidene dichloride) cobalt porphyrin
membrane: Hopping transport of oxygen via the fixed cobalt por-
phyrin carrier, J. Phys. Chem. B, 1998, 102(44), 8766–8770.
11 A. Zecchina, G. Spoto and S. Coluccia, Surface dioxygen adducts on
MgO–CoO solid solutions: Analogy with cobalt-based homogeneous
oxygen carriers, J. Mol. Catal., 1982, 14(3), 351–355.
12 B. Shin, K. D. Sutherlin, T. Ohta, T. Ogura, E. I. Solomon and J. Cho,
Reactivity of a Cobalt(III)–Hydroperoxo Complex in Electrophilic
Reactions, Inorg. Chem., 2016, 55(23), 12391–12399.
13 J. G. Schmidt, W. S. Brey and R. C. Stoufer, Complexes of cobalt(II).
IV. Electron paramagnetic resonance spectra of some magnetically
anomalous complexes of cobalt(II), Inorg. Chem., 1967, 6(2), 268–271.
14 K. Khivantsev, A. Biancardi, M. Fathizadeh, F. Almalki, J. L. Grant,
H. Ngoc Tien, A. Shakouri, D. A. Blom, T. M. Makris, J. R. Regalbuto,
M. Caricato and M. Yu, Catalytic N–H Bond Activation and Breaking
by a Well-defined Co(II)1O4 Site of a Heterogeneous Catalyst,
ChemCatChem, 2018, 10, 736–742.
15 V. N. Kislenko and L. P. Oliynyk, Complex formation of poly-
ethyleneimine with copper(II), nickel(II), and cobalt(II) ions,
J. Polym. Sci., Part A: Polym. Chem., 2002, 40, 914–922.
16 R. W. G. Scott, O. M. Wilson and R. M. Crooks, Synthesis,
Characterization, and Applications of Dendrimer-Encapsulated
Nanoparticles, J. Phys. Chem. B, 2005, 109(2), 692–704.
17 E. D. Bloch, L. J. Murray, W. L. Queen, S. Chavan, S. N. Maximoff,
J. P. Bigi, R. Krishna, V. K. Peterson, F. Grandjean, G. J. Long,
B. Smit, S. Bordiga, C. M. Brown and J. R. Long, Selective Binding of
O2 over N2 in a Redox–Active Metal–Organic Framework with Open
Iron(II) Coordination Sites, J. Am. Chem. Soc., 2011, 133(37),
14814–14822.
18 L. J. Murray, M. Dinca, J. Yano, S. Chavan, S. Bordiga, C. M. Brown
and J. R. Long, Highly-Selective and Reversible O2 Binding in
Cr3(1,3,5-benzenetricarboxylate)2, J. Am. Chem. Soc., 2010, 132(23),
7856–7857.
19 D. J. Xiao, M. I. Gonzalez, L. E. Darago, K. D. Vogiatzis, E. Haldoupis,
L. Gagliardi and J. R. Long, Selective, Tunable O2 Binding in
Cobalt(II)–Triazolate/Pyrazolate Metal–Organic Frameworks, J. Am.
Chem. Soc., 2016, 138(22), 7161–7170.
20 G. Q. Li and R. Govind, Separation of Oxygen from Air Using
Coordination Complexes: A Review, Ind. Eng. Chem. Res., 1994, 33,
755–783.
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