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Microstructural and Interfacial Designs of Oxygen-

Permeable Membranes for Oxygen Separation
and Reaction–Separation Coupling
Xuefeng Zhu and Weishen Yang*

pure oxygen will rapidly increase. Cur-

Mixed ionic–electronic conducting oxygen-permeable membranes can rapidly rently, the commercialized technology for
separate oxygen from air with 100% selectivity and low energy consumption. the generation of pure oxygen is the cryo-
Combining reaction and separation in an oxygen-permeable membrane genic distillation of air. However, the cost
reactor significantly simplifies the technological scheme and reduces the of cryogenic distillation technology for
oxygen separation remains high. There-
process energy consumption. Recently, materials design and mechanism
fore, it is facing a great energy penalty, i.e.
investigations have provided insight into the microstructural and interfacial >10% loss in net output, for oxyfuel and
effects. The microstructures of the membrane surfaces and bulk are closely precombustion power plants using pure
related to the interfacial oxygen exchange kinetics and bulk diffusion kinetics. oxygen produced by cryogenic distillation
Therefore, the permeability and stability of oxygen-permeable membranes with factories.[1] Other than cryogenic distil-
a single-phase structure and a dual-phase structure can be adjusted through lation, pressure swing adsorption and
polymer membranes are the commercial-
their microstructural and interfacial designs. Here, recent advances in the
ized technologies for oxygen separation
development of oxygen permeation models that provide a deep understanding from air, but they are inefficient for the
of the microstructural and interfacial effects, and strategies to simultaneously production of oxygen with purity higher
improve the permeability and stability through microstructural and interfacial than 95%.
design are discussed in detail. Then, based on the developed high-performance Recently, a production method based
on mixed ionic–electronic conducting
membranes, highly effective membrane reactors for process intensification
(MIEC) membranes, which can produce
and new technology developments are highlighted. The new membrane high-purity oxygen with higher energy
reactors will trigger innovations in natural gas conversion, ammonia synthesis, efficiency and lower investment cost than
and hydrogen-related clean energy technologies. Future opportunities and the cryogenic distillation technology, has
challenges in the development of oxygen-permeable membranes for oxygen gained much attention from academic and
separation and reaction–separation coupling are also explored. industrial communities.[2] In contrast to
the physical permeation behavior occur-
ring on microporous membranes and
polymer membranes, this mechanism is
1. Introduction an electrochemical permeation of oxygen through MIEC mem-
branes. This behavior demonstrates that the permeation selec-
Oxygen is an important industrial feed gas that is utilized in tivity of MIEC membranes toward oxygen is 100%. Although
many industries, such as chemical industries, ferrous met- the MIEC membranes are dense ceramics, their oxygen perme-
allurgy, glass making, and environmental protection. If the ability is comparable to that of microporous membranes and
energy consumption for pure oxygen separation can be signifi- is much higher than that of polymer membranes. In the past
cantly reduced, then not only will the production costs of the 20 years, the United States Department of Energy and Air Prod-
abovementioned processes be decreased remarkably but also ucts & Chemicals, Inc. (APCI) have invested hundreds of mil-
less pollution and CO2 will be discharged into the environment. lions of dollars to commercialize MIEC ceramic membranes to
With the development of oxyfuel and precombustion technolo- produce pure oxygen.[3] This revolutionary new technology can
gies for power generation and CO2 capture, the demand for significantly reduce the production cost (>30%) compared to
that of the current cryogenic distillation technology.[3,4]
Macroscopically, the oxygen permeation process includes
Prof. X. Zhu, Prof. W. Yang
three steps, i.e., oxygen surface exchange on the feed side,
State Key Laboratory of Catalysis
Dalian Institute of Chemical Physics ambipolar transport of oxygen ions and electrons across the
Chinese Academy of Sciences membrane bulk (including the grains and grain boundaries
Dalian 116023, China (GBs)), and oxygen surface exchange on the permeation side,
E-mail: yangws@dicp.ac.cn as illustrated in Figure 1a. On the microscopic scale, the oxygen
The ORCID identification number(s) for the author(s) of this article exchange kinetics on the gas–solid interfaces and the diffusion
can be found under https://doi.org/10.1002/adma.201902547.
kinetics across the grain boundaries, as shown in Figure 1b,
DOI: 10.1002/adma.201902547 cannot be neglected. In addition to their use in the separation

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of pure oxygen from air, MIEC membranes are applied as reac-

tors in which the reaction and separation processes can be Xuefeng Zhu is a professor of
coupled to simplify the process and save energy, as shown in Dalian Institute of Chemical
Figure 1c. In MIEC membrane reactors, catalytic reactions are Physics (DICP), Chinese
integrated with the oxygen separation process. For an oxidation Academy of Science (CAS),
reaction with a large negative free energy, the deep oxidation China. He received his Ph.D.
reactions limit the selectivity of the target product. MIEC mem- degree from DICP, CAS in
branes control the oxygen input into the reactor, which results 2007, and then worked in
in a low oxygen partial pressure in the membrane reactor, so Arizona State University
a high selectivity for the target product can be obtained by (USA) as a postdoctoral
avoiding the deep oxidation. For a reducing reaction with posi- researcher in 2008. His
tive free energy, such as water decomposition for the production research interests involve
of hydrogen, its conversion is limited by the thermodynamic mixed conducting ceramic
equilibrium. The MIEC membrane selectively removes oxygen membranes for gas separation, catalytic membrane
from the reactor, thus shifting the reaction equilibrium to the reactors for process intensification, solid oxide cells, and
product side. The requirements for MIEC membranes used for electrocatalysis for energy conversion and storage.
chemical reactions in membrane reactors depend on the reac-
tion conditions. The permeation flux, permeation stability, and Weishen Yang is a chair
structural stability under catalytic reaction conditions are the professor of Dalian Institute
most important performance indicators for the MIEC mem- of Chemical Physics (DICP),
branes. Therefore, many studies have focused on developing Chinese Academy of Sciences
MIEC membranes that can satisfy the operational conditions of (CAS), China. He received his
catalytic reactions. Ph.D. from CAS in 1990. As a
There are several excellent reviews and books that compre- visiting scholar, he worked at
hensively discuss the progress in the study of MIEC membranes Birmingham University (UK)
in recent years.[5,6] In these studies, the basic principles, mate- in 1989, and the University
rial development, membrane reactor properties, experimental of Southern California
methods, and theoretic models were well-introduced. Compo- (USA) in 2001. He works
sition change (or element-doping) is the most commonly used on the rational design and
strategy to develop new membrane materials. However, this molecular-level engineering of functional nanomaterials
strategy does not always effectively improve both the stability for applications in catalysis and separation (e.g., inorganic
and permeability of MIEC membranes. Recently, development membranes).
of the microstructural and interfacial design of MIEC mem-
branes was suggested as an important strategy to enhance the
membrane performance, but this approach has not been thor- permeability of membranes can be improved simultaneously.[8–10]
oughly discussed in a review article. With the help of theoretic In this work, we describe the recent efforts to build models to
model studies, the microstructural and interfacial effects can be aid in the understanding of the important effects of the surface
well described.[7] With the advanced strategies, the stability and and grain boundaries on the stability of the membranes, design

Figure 1.  a) Macroprocess of oxygen permeation. b) Micromechanism of oxygen exchange on the gas–solid interfaces, oxygen transport in the crystals
and across the grain boundaries of a MIEC membrane. c) The reaction–separation coupling in MIEC membrane reactors.

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novel MIEC membrane materials for oxygen transport and cata-
lytic reactions, and utilize the developed membranes to construct
membrane reactors for new separation and reaction processes
with high efficiencies. The goal of this study is to understand
the permeation mechanism; design MIEC membrane materials
with improved performance by controlling the bulk lattice, grain
boundaries and surface structure; and to develop new reaction–
separation couplings for process intensification. Recent develop-
ments indicate that the technology based on MIEC membranes
is promising for the production of pure oxygen and for process
intensification via reaction–separation coupling.
2. Mechanism and Model of Oxygen Permeation
For separation processes that are dominated by the oxygen
ionic–electronic (or oxygen vacancy-hole) ambipolar diffusion
across the MIEC membrane bulk, the Wagner equation can
be used to determine the influence of the temperature, oxygen
partial pressures and membrane thickness on the oxygen per-
meation flux. However, when the interfacial exchange reactions
are fast enough or the membrane thickness is thick enough,
the bulk ambipolar diffusion may be the rate-limiting step. In
most cases, the interfacial oxygen exchange reactions on the two
sides are involved in controlling the permeation process. Several
model equations have been developed to illustrate the mixed
control of the permeation process by the oxygen exchange
reactions on the interfaces and the bulk ambipolar diffusion.
Bouwmeester et al. introduced an important concept, the char-
acteristic thickness, to modify the Wagner equation to fit the
oxygen permeation process.[11] No clear relationship between the
permeation flux and the oxygen partial pressure was provided
in the modified equation. Jacobson and coworkers analyzed the
net oxygen interfacial exchange flux on the surfaces of MIEC
membranes and developed a general equation.[12] This equation
is too complicated to exhibit a clear dependency relationship
between the oxygen permeation flux and the experimental con-
ditions (i.e., temperature, membrane thickness, and oxygen
partial pressure). Lin et al. proposed a general equation by con-
sidering the diffusion of charged species in the bulk region of
membranes and the oxygen exchange reactions on the gas–solid
interfaces.[13] Xu et al. simplified Lin’s model by introducing
several assumptions to fit perovskite MIEC membranes.[14] This
simplified model is widely applied in permeation modeling,
but it is only applicable to a few membranes with low oxygen
vacancy concentrations, and it cannot give a unique solution to
fit the model parameters.[15] A proper model is important for
understanding the permeation mechanism of a MIEC mem-
brane. With the model equation, researchers can evaluate the
observed relationships between the oxygen permeation flux and
the experimental conditions, which can provide guidance for the
development of membranes and catalysts to accelerate the bulk
diffusion and the interfacial exchange reactions, respectively,
and can aid in the understanding of the degradation mecha-
nisms and approaches to improving the stability.
We built an oxygen permeation model by considering the
oxygen ionic and electronic transport across the membrane
bulk and the two gas–solid interfaces, as illustrated in Figure 2a.
To establish the model, three assumptions were made. 1) The
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transport characteristics of the electrons (or holes) and oxygen
ions (or oxygen vacancies) in a given region are constant regard-
less of the location and chemical potential of oxygen. 2) The
diffusion of the gaseous oxygen is fast enough for the concen-
tration polarization to be ignored. 3) All the steps of the oxygen
permeation are under isothermal conditions, and the law of
mass action is applicable to the oxygen exchange reactions on
the gas–solid interfaces. A detailed deduction process is shown
in the literature.[7] The general transport equation, including
the limitation of the bulk ambipolar diffusion and interfacial
exchange, is expressed as
1 1 1 1
jO2 = ∆µOtot2 = 2 2 tot ∆µOtot2 (1)
4 F r ′ + r + r ′′
2 2 b
4 F r
where r′, rb, and r″ are the permeation resistance through the
interface I, bulk region and interface II, respectively; rtot is the
total permeation resistance across the membrane; F is the Far-
aday constant; and ∆µOtot2 is the oxygen chemical potential gra-
dient across the membrane. The interfacial resistances depend
on the oxygen partial pressure, i.e.,
r ′ = r0′ (POI2 /P0 )
−0.5
(2)
r ′′ = r0′′ (POII2 /P0 )
−0.5
(3)
where POI2 and POII2 are the oxygen partial pressures of the
feed and permeation sides, respectively, P0, r′0, and r″0 are the
oxygen partial pressure at 1 atm and the permeation resist-
ance constants of the interfaces I and II, respectively, at oxygen
partial pressure of 1 atm, and r′0, r″0, and rb are the kinetic
parameters that are obtained by fitting the experimental data to
Equations (1)–(3). This permeation model has been success-
fully used to fit the permeation data of perovskite-type MIEC
membranes (Figure 2b) and dual-phase (DP) membranes.[15]
The kinetic parameters, i.e., the oxygen diffusion coefficient
(DO) and the interfacial exchange coefficients (k′ and k″), are
derived from the three permeation resistances
RT L
DO ≈ Dambi = (4)
4F 2c Ob2− r b
RT 1
k′ = (5)
4F 2c ′O2− r ′
RT 1
k ′′ = (6)
4F 2c ′′O2− r ′′
where Dambi is the ambipolar diffusion coefficient; if the ionic
conductivity is much lower than the electronic conductivity for
the MIEC material, DO ≈ Dambi; R is the gas constant; T is the
temperature; L is the membrane thickness; c Ob2−, c O′ 2−, and c O′′2− are
the concentrations of oxygen ions in the membrane bulk, inter-
face I, and interface II, respectively. The kinetic parameters of
MIEC materials are usually determined through tracer diffusion
or electrical conduction relaxation techniques. The kinetic
parameters obtained via tracer diffusion are in an equilibrium
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Figure 2.  a) Schematic graph of the oxygen permeation process for Zhu’s model. a) Reproduced with permission.[15] Copyright 2017, American Insti-
tute of Chemical Engineers, published by John Wiley and Sons. b) Comparison of the model data calculated by Zhu’s model with the experimental
data for Ba0.5Sr0.5Co0.8Fe0.2O3−δ (BSCF). The solid circles represent the experimental data and the colored surfaces represent the calculated results.
c) Permeation fluxes of the BCF membranes coated with various catalyst layers. c) Reproduced with permission.[8] Copyright 2016, American Institute
of Chemical Engineers, published by John Wiley and Sons. d) Changes in the permeation resistances with operation times for the BSCF membrane.
Reproduced with permission.[9] Copyright 2015, American Institute of Chemical Engineers, published by John Wiley and Sons.

state, and those obtained via the electrical conduction relaxa-
tion are in a nonsteady state. MIEC membranes are used for
oxygen permeation under steady state conditions; thus, the data
obtained in equilibrium or a nonsteady state cannot reflect the
real kinetics of the oxygen permeation under the steady state
conditions. However, the kinetic parameters obtained from
modeling the permeation data to the equations were close to the
values for the membrane in a real working steady state.
The activation energy of each step can be obtained from the
model analysis, which aids in the evaluation of the kinetic pro-
cesses of the bulk diffusion and interfacial exchange. For example,
the permeation flux of the 0.5 mm thick BaCe0.05Fe0.95O3−δ (BCF)
membrane was slightly improved (<6%) by applying porous
Sm0.5Sr0.5CoO3−δ (SSC) layers to both surfaces, and the apparent
permeation activation energy was almost unchanged (Figure 2c).
A superficial but reasonable explanation to the above results is that
the oxygen permeation through the 0.5 mm thick BCF membrane
was controlled by the bulk diffusion. However, the model analysis
shows that the bulk diffusion resistance is only 30–40% of the total
resistance. The SSC layer decreased the interfacial exchange resist-
ances but simultaneously increased the bulk diffusion resistance
due to the reaction between the SSC and BCF.[8] When the porous
catalyst layer was changed from SSC to BCF, the permeation flux
of the 0.5 mm thick BCF membrane was improved by 30–45%.
The distribution of the three permeation resistances can dis-
tinctly reveal which step dominates the oxygen permeation pro-
cess. The rate-determining step may change with operational
temperature, oxygen partial pressure of both sides, and the thick-
ness of the membranes. The resistance distribution map can be
used to easily determine how to improve the permeation flux and
to what extent it can be improved.[7–9] Another important applica-
tion of the permeation model is to reveal the degradation mecha-
nism of membranes. The increases in the three permeation
resistances may result in performance degradation. The perfor-
mance degradation of the BSCF membrane was regarded as the
result of the phase transformation at intermediate-to-low tem-
perature (ILT) in the literature.[5,6,16] However, the model analysis
showed that the phase transformation in the membrane bulk
made a small contribution to the degradation, but the increase
in the interfacial exchange resistance predominated, as shown in
Figure 2d.[9] A detailed discussion of the degradation mechanism
of MIEC membranes is presented in a following section.
Each model applies to specific ranges, since models are devel-
oped based on appropriate assumptions. In Zhu’s model, the
transport properties of the electrons/holes and oxygen ions/
vacancies in a given zone were assumed to be constant, regardless
of their positions and the oxygen chemical potentials.[7] There-
fore, Zhu’s model is applicable to MIEC materials whose oxygen

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vacancy concentrations have a weak dependence on the oxygen
partial pressure, such as BSCF, BCF, and DP membranes. To
model the oxygen permeation process for oxygen separation by
MIEC membranes, the model equations can be modified to show
the process taking place in a MIEC membrane reactor. The inter-
facial exchange resistances are replaced by the reaction polariza-
tion resistances, which can be derived from the equation for the
catalytic reaction rates.[17] However, the reaction conditions need
to be in accordance with the assumptions used to derive these
models to avoid incorrect results and conclusions.
3. Perovskite MIEC Membrane Materials
Perovskite oxides with the formula ABO3 are typical MIEC
membrane materials. The critical radius (rc), free volume (FV),
and average bonding energy (ABE) of the MO bonds are fre-
quently considered when discussing the relationship between
the structure and oxygen ionic diffusion for perovskite MIEC
materials. In a cubic perovskite oxide, the oxygen ionic diffusion
follows the ⟨110⟩ direction via a trigonal window constructed by
a B-site cation and two A-site cations (Figure 3a). The apothem
of the trigonal window, which is known as the “critical radius,”
decreases as the A- and B-site cations become larger, assuming
that the perovskite maintains its cubic structure.[5,6] The devi-
ations in the positions of the cations from the normal lattice
positions under the squeezing action of oxygen ions allow the
oxygen ionic diffusion across the window. This kind of lattice
relaxation is temperature-dependent, so it is intimately con-
nected to the diffusion activation energy of the oxygen ions in
a perovskite lattice. Therefore, small A- and B-site cations are
wanted to obtain a high oxygen ionic conductivity for perovskite
MIEC materials. The FV is defined by the difference between
the volume of a single cell and that of the overall ions, and it
decreases as the B-site cationic radii increase. A larger FV pro-
vides more room for lattice relaxation; therefore, increasing the
FV facilitates the diffusion of the oxygen ions in the membrane
bulk and reduces the transport activation energy of the oxygen
ions. The ABE indicates the level of difficulty to break the MO
bonds in the perovskite structure. Cations located at the A and
B-sites with low oxidation states enhance the conductivity of the
oxygen ions; however, low-valent cations with larger ionic radii
decrease the critical radius. Thus, changes in the critical radius,
free volume, and ABE cannot simultaneously favor an increase
in the ionic conductivity.
In addition, the stability of the perovskite structure should
be considered during the design of MIEC materials. The sta-
bility of a perovskite oxide depends on two factors, i.e., ther-
modynamics and kinetics. The ABE and tolerance factor are
the two most important factors influencing the thermodynamic
stability of a perovskite oxide. High ABE values correspond to
high stability but low mobility of oxygen ions in the perovskite.
For a tolerance factor close to 1, the BO6 octahedron has less
distortion in the perovskite structure, and the corresponding
perovskite therefore has a higher stability. The kinetic stability
of a perovskite MIEC membrane is related to the diffusion
rate of the A- and B-site cations in the material. As a chemical
potential gradient of oxygen is applied on a MIEC membrane,
not only oxygen ions but also cations are forced to direction-
ally move from one side to the other side. Since the diffusion

Figure 3.  a) Diffusion of oxygen ions in a perovskite oxide. b) Oxygen permeation fluxes of BaxSr1−xCo0.8Fe0.2O3−δ membranes with different Ba contents.
b) Reproduced with permission.[21] Copyright 2001, Elsevier B.V. c) Oxygen permeation flux of an asymmetric BSCF membrane. Reproduced with per-
mission.[23] Copyright 2011, Elsevier B.V. d) Effect of the cooling–heating cycle on the oxygen permeation fluxes of the BaFeO3−δ and BaCe0.05Fe0.95O3−δ
membranes. Reproduced with permission.[29] Copyright 2006, Elsevier B.V. e) Possible oxygen ion transport paths. f) Oxygen ionic migration barrier
energies of oxygen ions via different paths in a Ba8Fe7GdO24 supercell. e,f) Reproduced with permission.[27] Copyright 2016, Royal Society of Chemistry.

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coefficient of oxygen ions is typically five orders of magnitude
higher than that of cations,[6] there is no observable change
in the elemental compositions of the membrane surfaces in
a short-term oxygen permeation test. However, the inevitable
kinetic demixing of cations is expected after a long-term opera-
tion. The rate of kinetic demixing largely depends on the dif-
fusion rates of the cations. The diffusion rates of the cations
depend on the temperature, atmosphere, chemical potential
gradient of oxygen, oxygen exchange rates at the interfaces,
and membrane microstructure. Usually, the lower ABE value
for a perovskite material corresponds to higher diffusion coef-
ficients for both the oxygen ions and the cations. Therefore, it
is difficult to combine the excellent permeability and stability
simultaneously in a membrane material. Thus, there is a need
for further study of the design of MIEC materials according to
the target applications.
3.1. Improvement of Stability and Permeability
by Adjusting the Crystal Structure
The cobalt-based perovskite oxides, in particular
SrCo0.8Fe0.2O3−δ, show high oxygen permeability. However, for
oxygen partial pressures lower than ≈0.1 bar and temperatures
lower than ≈790  °C, the cubic SrCo0.8Fe0.2O3−δ is not stable,
and it transforms to an orthorhombic brownmillerite structure
(A2B2O5) with ordered oxygen vacancies.[18–20] Partial substi-
tution of Sr by La in the A-site is effective to enhance the sta-
bility of the membrane materials. Similarly, doping high-valent
and less reducible cations (Ti4+, Zr4+, Nb5+, etc.) in the B-site
is effective to maintain the cubic phase. However, the stability
increase is accompanied by a permeability decrease. Because
the substitution reduces the oxygen vacancy concentration and
free volume, the ABE value increases as well. All these changes
decrease the oxygen diffusion coefficients of materials.
However, we found that the stability and permeability
were simultaneously improved by Ba doping in the Sr-site in
SrCo0.8Fe0.2O3−δ. The BaO bond had a similar bond energy
to that of the SrO bond, so the partial substitution of Sr by
Ba had little effect on the ABE value. The oxygen vacancy con-
centration was increased after the Ba doping. As expected,
the Ba0.5Sr0.5Co0.8Fe0.2O3−δ (BSCF) exhibited a higher oxygen
permeation flux than did the SrCo0.8Fe0.2O3−δ (Figure 3b).[21]
Although the BSCF membrane was first reported by Yang’s
group in 2000,[22] it has the highest known oxygen permeability
to date. A high oxygen permeation flux of 50 mL cm−2 min−1
was obtained on a BSCF membrane with a dense separation
layer of 70 µm at 900 °C (Figure 3c).[23] The incorporation of
Ba in the A-site led to a decrease in the trapped oxygen vacan-
cies in the lattice, which inhibited the order–disorder transi-
tion occurring on the SrCo0.8Fe0.2O3−δ.[18] BSCF has widely
gained the attention of researchers from not only the field of
MIEC membranes but also the fields of solid oxide fuel cells
and electrocatalysis because of its outstanding catalytic activity
toward the oxygen activation reactions. Long-term operation of
BSCF membranes has been proofed up to 17 000 h.[24] Thus,
BSCF is considered a promising material for pure oxygen pro-
duction due to its high permeability and stability at elevated
temperatures.
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In addition to the production of pure oxygen from air,
another important application of MIEC membranes is the inte-
gration of catalytic reactions with oxygen separation into mem-
brane reactors. The common behaviors of these reactions are
inputting or producing strong reducing gases at elevated tem-
peratures. Therefore, membrane materials that can sustain the
perovskite structure under a reducing atmosphere are needed
for these reactions. BaFe1−xMxO3−δ (M = Y, Zr, Ce, Gd, Sm, etc.)
is another typical series of cobalt-free MIEC perovskite mem-
branes.[25–29] The as-prepared BaFeO3−δ has a complex phase
composition at room temperature, comprising monoclinic,
rhombohedral, orthorhombic, hexagonal, and cubic phases.
The phase transformation to cubic at 800 °C is accompanied
by a sharp increase in the electronic and ionic conductivities. In
addition, the BaFeO3−δ maintains its perovskite structure even
at oxygen partial pressure of 10−17 atm and 827 °C.[29] We found
that the most effective strategy to maintain the cubic high-tem-
perature phase at room temperature is to dope large and high-
valent cations in the B-site with a low doping amount (5–10%),
as shown in Figure 3d. Although doping high-valent cations
in the B-site increases the ABE value, the oxygen permeation
flux is significantly enhanced, and the activation energy of per-
meation decreases to as low as 30–40 kJ mol−1,[26,27,29] which is
even lower than that of BSCF. This abnormal phenomenon was
explained by a first-principles calculation.[27] A 2 × 2 × 2 super-
cell of Ba8Fe7GdO24 with an Fe atom replaced by a Gd atom
was constructed to fit the first-principles calculation on the
Gd-doped BaFeO3−δ, as shown in Figure 3e. Based on the dif-
ference in the distances from Gd cations, the anions/vacancies
in the supercells have three types, i.e., O1/VO1, O2/VO2, and
O3/VO3. A fast path of oxygen ion diffusion in the supercell was
observed such that the migration barrier for O2 to VO1 was as
low as 0.17 eV (Figure 3f), although the migration energies of
oxygen from the O1 site to the adjacent VO1 (1.62 eV) and VO2
(0.99 eV) were higher than that in the cubic BaFeO3 pristine
lattice (0.91 eV). This result indicates that the oxygen migration
was more difficult for those near the large, high-valent doped
cations and less difficult for those far from the dopants. Too
much dopant would inhibit the oxygen diffusion because of the
dopant binding to the oxygen anions. The BaFe1−xMxO3−δ mate-
rials even maintained the cubic perovskite structure after being
exposed to 5% H2/Ar at 900 °C. However, the perovskite struc-
tures of the Ba0.5Sr0.5Co0.8Fe0.2O3−δ and La0.5Sr0.5Ga0.3Fe0.7O3−δ
were destroyed after reduction under the same conditions.[29]
Therefore, the BaFe1−xMxO3−δ materials are promising for con-
structing membrane reactors if the reaction atmosphere con-
tains little or no CO2.
3.2. Degradation Induced by Microstructural
and Interfacial Changes
The high operating temperature (700–1000 °C) is a distin-
guishing feature of MIEC membranes. With the improvements
in the fabrication technology for asymmetric membranes, the
dense layer for oxygen permeation has been reduced from
the typical 0.5–2 mm to >0.01 mm. As a result, it is pos-
sible to achieve commercial-valued permeation fluxes at ILT
(350–700  °C). The operation of MIEC membranes at ILT has
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many significant advantages compared with its high-temper-
ature operation. The creep rate drops sharply with decreases
in the temperature since the activation energy of perovskite
ceramic creep is as high as 300–500 kJ mol−1.[6,30] The creep
induced by the pressure loading on a MIEC membrane would
result in a macroscopic deformation at elevated temperatures
during a long-term on-stream operation;[31] thus, failure of the
MIEC membranes is inevitable. However, reducing the run-
ning temperature to ILT would greatly reduce the creep rate
and thus prolong the lifetime of the MIEC membranes. Less
energy is needed to heat air to high temperatures and less
expensive stainless steel and other materials can be used to
construct the membrane separation unit if the MIEC mem-
branes are operated at ILT. In addition, the great challenge in
maintaining perfect sealing of MIEC membranes under large
pressure gradients (<2 MPa) and long running periods (>5
years) becomes less difficult at ILT. Because of these advan-
tages, MIEC membranes used for pure oxygen production
have become more competitive compared with the traditional
technologies.
However, the quick degradation of the permeation flux at
ILT is inevitable for MIEC membranes. This problem occurs
in many of the high-performance membranes, such as BSCF,
La1−xSrxCo1−yFeyO3−δ, (Ba,Sr)Co1−x−yFexMyO3−δ, and BaFe1−xMx
O3−δ. In general, the performance degradation becomes more
severe at higher temperatures for materials. The abnormal
phenomenon occurring on the MIEC membranes at lower
temperatures indicates the degradation mechanisms are dif-
ferent from that described by the conventional wisdom. Three
mechanisms were suggested to explain the degradation at ILT
for perovskite MIEC membranes, i.e., oxygen vacancy ordering,
phase transformation and kinetic demixing. Kruidhof et al.
treated La0.6Sr0.4CoO3−δ at 700 °C for 100 h and found ordered
oxygen vacancies in small microdomains (5–20 nm).[19] An
endothermic peak was observed at 910 °C during the heating
of a disk-type La0.6Sr0.4CoO3−δ in air, indicating there was a
change from an ordered defect structure at lower tempera-
tures to a disordered defect structure at higher temperatures.
Phase transformations of membranes such as SrCoO3−δ,
Ba0.5Sr0.5Co0.8Fe0.2O3−δ, and BaFeO3−δ, from the cubic perov-
skite phase to phases with ordered oxygen vacancies result
in their degradation at lower temperatures. The performance
degradation of phase-stable MIEC membranes usually was
regarded following the kinetic demixing mechanism. Kinetic
demixing of cations is caused by the chemical potential gra-
dient of oxygen through the MIEC membrane and results in
a change of phase structure in both the bulk and the surfaces.
The degradation of many membranes with stable perovskite
structures has been attributed to the kinetic demixing mecha-
nism. The kinetic demixing process is related to the activated
diffusion of cations. Thus, the degradation rate is probably
faster at high temperatures than at low temperatures. Demixing
occurs when an oxygen chemical potential gradient is applied
across a membrane, but alkaline earth element segregation
occurs when the perovskite materials are treated in an oxi-
dizing atmosphere.[32] Therefore, the above three mechanisms
cannot explain the degradation of most MIEC membranes with
stable crystal structures, i.e., no ordering of oxygen vacancies
and phase transformation at ILT.
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3.2.1. Gas–Solid Interfacial Degradation
Recently, we reported that nonmetallic impurities containing
sulfur and silicon elements, would diffuse from the membrane
bulk region to the gas–solid interfaces and lead to a significant
decrease in oxygen reduction and evolution rates on both of
the gas–solid interfaces.[8,33–35] Three perovskite membranes,
BaCe0.1Co0.4Fe0.5O3−δ (BCCF),[36] BaZr0.2Co0.4Fe0.4O3−δ (BZCF),[37]
and BaCo0.7Fe0.22Nb0.08O3−δ (BCFN),[38] reported by different
authors, have stable phase structures for oxygen permeation but
show quick performance degradation at 600 °C (Figure 4a,b).[33,34]
For example, a significant degradation of the permeation flux
by 80% after operating for 480 h at 600 °C was observed on the
BCCF membrane. After a long-term stability test, BaSO4 crystals
were observed on the surfaces of all the membranes, and the
amount of BaSO4 crystals on the permeation-side surface was
more than that on the feed-side surface (Figure 4c,d). In addi-
tion to BaSO4, Zr(SO4)2 was detected on the permeation-side
surface of a BZCF membrane. The chemical precursors, i.e.,
nitrates, oxides and carbonates, were found to be the sources
of the sulfur impurities after a series of characterizations and
analyses. The elemental sulfur content was ≈ 20 ppm in the
perovskite oxide, even though high-purity chemical precursors
were used. However, this low sulfur content caused a significant
degradation of the permeation flux at 600 °C. Silicon impurities
commonly appearing in the starting chemical precursors and the
ceramic vessel, and dust were found in the perovskite materials
as well. Elemental silicon enriches to the surfaces of membranes,
showing behavior similar to that of elemental sulfur (Figure 4a,f).
Therefore, membranes containing silicon impurities have degra-
dation mechanisms similar to those containing sulfur impurities.
Slater and coworkers found that oxyanions, such as sulfate,
silicate, and phosphate groups, are good dopants to stabilize
the hexagonal perovskite phases and orthorhombic brown-
millerite phases to cubic perovskite phases with low doping
amounts (<5 at%).[39,40] They reported that the perovskite lat-
tice allowed high doping amounts of the silicate group of up
to 15 at%.[40] High temperature calcination in air was required
to ensure the incorporation of these oxyanions into the perov-
skite lattice. However, the oxyanions tended to move outside
of perovskite lattices, as the as-sintered membranes were
annealed in air or helium at 600 °C. More impurities were
found on the samples treated in helium.[8,33] The above results
indicate that at a low temperature, the chemical potentials of
oxyanions in perovskite lattices are greater than those on the
gas–solid interfaces, and the chemical potentials in air are
higher than those in helium. The membrane was operated
with one side fed with air and the other side fed with helium.
Impurities were enriched on the surfaces of both sides during
the initial stage but only on the surface of the permeation side
after a long-term operation. The migration of oxyanions is indi-
rectly related to the oxygen chemical potential gradient. The
chemical potential of the oxyanions at the gas–solid interface is
a function of the oxygen partial pressure. At the initial stage of
the oxygen permeation, the chemical potential of the oxyanions
in the membrane bulk was higher than those on the air–solid
and helium–solid interfaces, so the diffusion of oxyanions to
both sides was observed with the air side enriched with fewer
impurities than the helium side (Figure 4g). However, after a
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Figure 4.  a) Time-dependent oxygen permeation fluxes of the uncoated BCCF perovskite membranes and the same BCCF perovskite membranes
coated by SSC porous catalyst layers at 600 °C. b)Time-dependent oxygen permeation fluxes of BZCF (red) and BCFN (blue) membranes with both
surfaces coated and uncoated by SSC porous catalyst layers at 600 °C. c) Feed-side surface. d) Permeation-side surface containing sulfur impurities
of the BCCF membrane after 480 h of operation at 600 °C. e) Feed-side surface. f) Permeation-side surface containing silicon impurities of the BCCF
membrane after 477 h of operation at 600 °C. h) Top view and cross-section view of the porous SSC catalyst layer. The arrows mark BaSO4 grains.
g) Schematic graphs of the chemical potential of elemental sulfur/silicon and the transport of sulfate/silicate group across the membranes under
different atmospheres. Data from ref. [33] and ref. [34] are replotted in (a) and (b). c,d,h) Reproduced with permission.[33] Copyright 2013, Wiley-VCH.
e,f,g) Reproduced with permission.[34] Copyright 2015, Elsevier B.V.

long-term operation, the chemical potentials of the oxyanions
on both surfaces and in membrane bulk were equal, indicating
a net diffusion of oxyanions from the air side to the permea-
tion side; as a result, the content of impurities decreased to
near zero on the air side (Figure 4e–g).
At high temperatures, oxyanions migrate from the mem-
brane bulk to the two surfaces, but performance degrada-
tion was not observed for the MIEC perovskite membranes.
The results of the thermodynamic calculations reveal that
increasing the temperature inhibits the formation of sulfates.
At low temperatures, sulfates tend to form on surfaces, so sul-
fates accumulate on the membrane surfaces and result in a sig-
nificant decrease in the oxygen exchange rates, while at high
temperatures, the formation rate is slow, so no sulfate accumu-
lates and the membrane can keep stable oxygen permeation.[33]
For membranes containing silicon impurities, the stabiliza-
tion mechanism at high temperatures is attributed to the sin-
tering effect of the accumulated silicates on the membrane
surfaces.[34] The resultant large silicate particles occupy only a
small portion of the membrane surfaces, so they have a weak

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effect on the oxygen exchange rate on the gas–solid interfaces.
Thus, the different surface microstructures of the impurities
induced by the different operating temperatures govern the sta-
bility of the oxygen permeation.
The above interfacial degradation mechanism for perovskite
MIEC membranes with good phase stability indicates that a trace
amount of oxyanions moves out of the membrane bulk to the
surfaces controlling the permeation stability of the membranes.
According to the degradation mechanism, there are three possible
solutions to sustain the permeation flux at ILT. The first is the pre-
process control in which the oxyanion-containing impurities are
removed by purifying the starting chemical precursors in advance
and the process of membrane fabrication is strictly controlled
to avoid introducing oxyanion-containing impurities during the
preparation of the membranes. Unquestionably, this process
would sharply increase the cost of MIEC membranes. The second
solution is the in-process control in which the migration of oxy-
anions is blocked or slowed by changing the composition of the
MIEC membranes. However, the migration path or mechanism
of oxyanions in the perovskite lattice is still unclear. Therefore,
there is no clear direction for the development of the materials.
The third is the post process control in which the enriched oxy-
anion-containing impurities are removed from the membrane
surfaces to avoid the enrichment on the gas–solid interfaces.
We proposed a simple method to remove oxyanion-containing
impurities from the membrane surfaces by changing the surface
microstructures.[8,33,34] Porous layers with high catalytic activity
toward oxygen exchange reactions were coated on both sides of
the membranes, which cause the migration of oxyanions from the
membrane bulk into the porous layers; thus, the impurities accu-
mulate not on the surfaces but in the porous layers (Figure 4h).
SSC perovskite was used to create ≈10 µm thick porous layers on
the two surfaces of a BCCF membrane. The flux of the SSC-coated
BCCF membrane was only 5% lower than the initial value after
the 480 h on-stream process at 600 °C (Figure 4a). For the SSC-
coated BCFN and BZCF membranes, stable permeation fluxes
were observed during the 100 h operation at 600 °C (Figure 4b).
After the long-term operation, the postmortem analysis indicated
that the sulfur and silicon impurities migrated to the outer skin of
the SSC layers. Therefore, no elemental sulfur or silicon impuri-
ties remained on the surface of the membrane. The porous layers
had a much higher surface area than did the membrane surface,
so the enrichment of impurities did not significantly inhibit the
oxygen exchange reactions. The success in realizing stable fluxes
through the three perovskite MIEC membranes suggests that this
method may extensively work well for the MIEC membrane fami-
lies to prevent the permeation degradation at ILT. Therefore, the
third solution is the simplest and the most effective. However, a
slight reduction in the catalytic activity toward the oxygen reduc-
tion and evolution reactions is inevitable when the oxyanion-
containing impurities are enriched in the porous layers. There-
fore, there was a weak degradation (<5%) in the permeation flux
during the initial stage.[33,34]
3.2.2. Phase Transformation at the Perovskite GBs
BSCF is the most attractive material because of its high
ionic diffusion rate and high catalytic activity toward oxygen
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exchange reactions at ILT. The permeation flux is close to
1 mL cm−2 min−1 at 600 °C under an oxygen partial pres-
sure gradient of 21 kPa/2 kPa through a 0.5 mm thick BSCF
membrane. The permeation flux meets the frequently referred
threshold (>1 mL cm−2 min−1) for commercial applications.[41]
However, many studies have shown that the performance deg-
radation occurs on the BSCF membrane at ILT due to the com-
plex phase transformation. The 2H-type hexagonal perovskite
structure was formed after the sintered powder was treated for
240 h at 750 °C.[42] The real driving force of the phase transfor-
mation from the cubic to the hexagonal perovskite structure is
the oxidation of Co2+ with a high spin (HS) state to Co3+ with a
low spin (LS) state, which corresponds to a significant decrease
in the cationic radii from 0.0745 nm (Co2+, HS) to 0.0545 nm
(Co3+, LS).[43] Müller et al. observed that the content of the hex-
agonal phase increased slowly with the treating time. In addi-
tion to the hexagonal phase, plate-like regions were observed
when the BSCF was annealed at 700–900 °C.[44] The plate-like
regions contained three phases, i.e., the cubic perovskite phase,
hexagonal phase, and Ba3Co10O17 phase.[45] The Ba3Co10O17
phase comprised a periodic arrangement of two (111)-planes
of O octahedrons with a cubic stacking order and three planes
with a CdI2-type structure and two interface planes, as shown
in Figure 5a. The generation of plate-like regions is more rapid
than that of the hexagonal phase at the GBs of BSCF. Recently,
we found that the Ba3Co10O17 phase with a composition of
approximately Ba0.45Sr0.07Co1.6Fe0.18O2.8 was formed at the GBs
after the BSCF membrane was operated for 500 h at 600 °C
(Figure 5b,c), but we did not find the hexagonal phase.[10] The
Ba3Co10O17 phase is not stable at temperatures above 800 °C
and tends to decompose to Co3O4 or CoO (depending on the
temperature) and the 2H-type hexagonal phase.[46] Therefore,
the Ba3Co10O17 phase was observed only at ILT, while the Co3O4
(or CoO) phase and the 2H-type hexagonal phase were found
at 700–850 °C for the BSCF material. Müller et al. reported
that plate-like regions tend to form around the CoO grains.[45]
However, another possible explanation to this phenomenon is
the decomposition of the Ba3Co10O17 phase producing the CoO
impurities.
From the above discussion, the BSCF phase transformation
is different from those of SrCoO3−δ, BaFeO3−δ, SrCo0.8Fe0.2O3−δ,
etc. For SrCoO3−δ and BaFeO3−δ, the phase transformation
from cubic to 2H hexagonal is a martensitic transformation
that occurs in the temperature range of 800–900 °C in air.[35]
This process is a diffusionless transformation with rapid rear-
rangement of atoms and thus has a very low thermal activation
energy and an extremely fast rate. However, the generation of
crystal nuclei requires the long-distance diffusion of the atoms
in the grain to reach the proper sites for the phase transforma-
tion of the BSCF, and then the crystal nuclei can grow to new
phases. Therefore, this process is a diffusion-controlled phase
transformation. New phases are frequently observed at GBs,
because GBs are active sites for the generation of crystal nuclei
due to their loose arrangement of atoms and their large amount
of defects.
A convenient method to stabilize the perovskite structure of
BSCF is the substitution of cations with high and stable oxidation
states. However, a low doping amount cannot completely stabilize
the perovskite structure, while a high doping amount leads to a
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Figure 5.  a) Structure of Ba3Co10O17. b) BSCF membrane after oxygen permeation for 500 h at 600 °C. “R” denotes the trigonal phase precipitated at the GBs.
c) Elemental mapping of the area marked in the red frame in (b). d) Time-dependent oxygen permeation through Zr-, Nb-, Y-, Ce-doped BSCF membranes
at 600 °C. e) Zr-doped BSCF membrane after operating for 432 h at 600 °C. f) GB of Y-doped BSCF with nanoparticles after the 500 h oxygen permeation
testing. g) GB of Y-doped BSCF without nanoparticles after the 500 h on-stream process. h) GBs of the as-prepared Ce-doped BSCF membrane. i) Time-
dependent bulk permeation resistances of the Ce-doped BSCF membrane at 600 °C. j) Oxygen permeation flux of the asymmetric Ce-doped BSCF mem-
brane. a) Reproduced with permission.[6] Copyright 2017, Springer Nature. b–j) Reproduced with permission.[10] Copyright 2015, American Chemical Society.

significant reduction in the oxygen permeability. In addition to the
lattice doping method to enhance the perovskite stability, a new
strategy was proposed to prevent a phase transformation in BSCF
by introducing nanoparticles at the GBs.[10] A thermodynamic
analysis indicated that the appearance of nanoparticles at the GBs
produces a Zener pinning pressure. Thus, after the introduction
of nanoparticles at the GBs, the grain boundary energy is
3γ Vm 3γ Vm f V sin2θ 3  1 f 
∆GGB = − + = − γ Vm  − V sin2θ  (7)
2Rg 2rNP 2  R g rNP  The maximum value of sin2θ appears at θ = π/4; there-
where γ is the grain boundary energy per unit area, Vm is
the molar volume of the material, Rg is the grain radius
of the material, fV is the volume fraction of the nanoparticles
in the material, rNP is the radius of the nanoparticles, and θ is
the angle between the grain boundary surface and the surface
at the point where the grain joins the nanoparticle (0 ≤ θ ≤ π/2).
In the above equation, the first term on the right side is the
inherent grain boundary energy, and the second term is the
Zener pinning energy. To prevent the phase transformation at
the GBs, the grain boundary energy must be larger than zero,
which gives the following relationship
f VRg
sin2θ ≥ 1 (8)
rNP
fore, for a fVRg/rNP greater than one, the grain boundary
energy is reduced to zero at equilibrium. Thus, the driving
force of the heterogeneous nucleation at GBs is reduced after
the introduction of nanoparticles at the GBs. The increase in
the volume fraction of nanoparticles results in an increase in
the particle size during the sintering at high temperatures.
In addition, the oxygen permeation flux is reduced when there is

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a high volume fraction of nanoparticles in membranes. The
grain size of BSCF membranes typically changes in the range
of 10–50 µm, and the increase in the Rg decreases the strength
and creep resistance of the ceramics.[6] Therefore, it is effective
to reduce the size of the nanoparticles to obtain fVRg/rNP ≥ 1.
A kinetic analysis indicates that the heterogeneous nuclea-
tion and new phase growth at GBs obey a stepwise growth
mechanism. As nanoparticles are introduced at the GBs, the
driving force of the step motion includes two parts, i.e., the
inherent grain boundary pressure and the Zener pinning pres-
sure. Thus, the motion velocity of the steps is
3γ km 3γ kmf V sin2θ 3γ km  1 f 
v= − =  − V sin2θ  (9)
2hR g 2hrNP 2h  R g rNP 
where h, k, and m are the height of the step, the distance
between the two steps, and the boundary migration mobility,
respectively. In the above equation, the first term on the right
side represents the inherent motion velocity of the steps, and
the second term represents the motion velocity inhibited by the
Zener pinning effect due to the introduction of nanoparticles
at the GBs. The inhibition of the step motion indicates that the
atomic net diffusion fluxes at the GBs are limited by the nano-
particles at the GBs; thus, there is no accumulation of cations
for the heterogeneous nucleation and new phase growth.
The above theory has been described by our group.[10] We
attempted to use four cations (Y3+, Zr4+, Nb5+, and Ce4+) with
different valence states and ionic radii to form nanoparticles
at the GBs of BSCF membranes. At the doping amount of
3 mol%, the Zr4+ and Nb5+ entered the BSCF lattice completely.
Oxygen permeation experiments revealed that the BSCF mem-
branes doped with Zr4+ and Nb5+ showed degradation behavior
similar to that of the BSCF parent (Figure 5d). The surfaces of
all membranes were covered with the SSC porous catalyst layers
to eliminate the negative effects of the oxyanion-containing
impurities enriched from the membrane bulk to both the sur-
faces. The Ba3Co10O17 phase was still detectable at the GBs
after a 432 h oxygen permeation test of the Zr-doped sample
at 600 °C (Figure 5e). A higher doping amount of the Zr4+ and
Nb5+ would inhibit the phase transformation, and a significant
decrease in the oxygen permeability would be inevitable.
Y3+ partially entered the BSCF lattice and produced a
small amount of nanoparticles at the GBs (Figure 5f). The
degradation rate of the Y-doped BSCF was much slower than
that of the BSCF and the Zr- and Nb-doped BSCF, indicating
that the nanoparticles at the GBs effectively inhibited the
phase transformation (Figure 5d). Other researchers verified
that the BSCF stability can be enhanced by a slight Y-doping
in the B-site.[47] However, the amount of nanoparticles in the
sample was too low to fully inhibit the phase transforma-
tion. An analysis of the Y-doped sample after a 500 h test at
600 °C for the oxygen permeation revealed that the Ba3Co10O17
phase did not appear at the GBs where the nanoparticles were
inlayed (Figure 5f,g).
However, for the Ce-doped sample, the Ce4+ did not enter
the BSCF lattice but combined with the Ba2+ to form BaCeO3
nanoparticles at the GBs (Figure 5h). Even when the doping
amount was reduced to 0.1 mol%, the BaCeO3 nanoparticles
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were observable at the GBs. The oxygen permeation flux
was stable during a 500 h test, as shown in Figure 5c. No
Ba3Co10O17 phase appeared at the GBs, but many BaCeO3
nanoparticles were found at the GBs with sizes of 50–100 nm
and at crystal edges with sizes of 100–200 nm. The depend-
ence of the bulk diffusion resistance on time was determined
by using Zhu’s model to provide an analysis of the inhibition
of the phase transformation by the nanoparticles at the GBs.
The resistance to bulk diffusion remained constant at 600 °C
(Figure 5i). The volume fraction of the BaCeO3 nanoparticles
was 4%, and the average size of the nanoparticles was 100 nm.
The average size of the BSCF grains was 15 µm. Therefore, the
value of fVRg/rnp was 6, which was higher than the critical value
of 1. Therefore, the heterogeneous nucleation and Ba3Co10O17
phase growth can theoretically be inhibited. The zig-zag nature
of the GBs (Figure 5h) supports the stepwise-motion mecha-
nism, because the mobility of GBs close to nanoparticles is
more heavily reduced than that of GBs far from nanoparticles.
In contrast, smooth GBs were found in samples without nano-
particles at the GBs. An asymmetric Ce-doped BSCF membrane
with a 90 µm thick dense layer showed a high oxygen permea-
tion flux up to 5.2 mL cm−2 min−1 at 600 °C, indicating that it
is promising to use Ce-doped BSCF membranes for practical
oxygen production at ILT (Figure 5j).
4. Dual-Phase Membranes
Although the BaFe1−xMxO3−δ and other cobalt-free perovskite
membranes are stable in strong reducing environments, decom-
positions of the perovskite structure up to tens of microns deep
are inevitable after long-term operations in catalytic membrane
reactors. Kinetic demixing of cations for the perovskite oxides
is accelerated when they are exposed to a high oxygen partial
pressure gradient or atmospheres containing CO2 and steam.
Because the responses of the A- and B-site cations of perov-
skites to the surrounding atmospheres are different, i.e., the
A-site cations easily lose their lattices sites under the erosion
of CO2 and steam, while the B-site cations tend to be reduced
to metals or low-valent cations by reducing gases. In addition,
the diffusion rates of cations in the A- and B-sites through the
perovskite lattice are different, so the kinetic demixing is inevi-
table even though the perovskite material can sustain the ero-
sion of CO2 and steam.
Mazanec and Frye proposed a concept of “dual-phase” MIEC
membranes in a patent in 1990[48] that may solve the difficulty
encountered in “single-phase” membranes. In the DP mem-
branes, one phase is an oxygen ionic conductor and the other
phase is an electronic conductor (Figure  6a). The oxygen ionic
conductor is usually chosen from the fluorite-type oxides (such
as Y2O3 stabilized ZrO2 (YSZ) and CeO2 doped by rare earth
elements), which have high oxygen ionic conductivities and
structure stability but low electronic conductivities at elevated
temperatures. The development of DP materials experienced
three periods based on the type of electronic conductor. In
the first period, precious metals, such as Ag, Au, and Pt, were
adopted as the electronic conductors because they can maintain
their metallic states under redox atmospheres at elevated temper-
atures.[49] A volume fraction of no less than 30% is required for
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Figure 6.  a,b) DP membranes made of an electronic conducting phase and ionic conducting phase (a) and a mixed conducting phase and an ionic
conducting phase (b). c) Arrhenius plots of SDC–SSF and SDC–SSCr DP membranes with a thickness of 0.5 mm. c) Reproduced with permission.[51]
Copyright 2012, Elsevier B.V. d) Schematic illustration of the oxygen chemical potential drop and conductivity change across a MIEC membrane in a
POM reactor, where L represents the thickness of the membrane and σe is the electronic conductivity including p-type and n-type. e) Dependence of the
total conductivities on the oxygen partial pressure of SDC, SDC–SSAF and SDC–SSCF at 950 °C. d,e) Reproduced with permission.[57] Copyright 2016,
Elsevier B.V. f) Comparison of oxygen fluxes in oxygen permeation and POM reactions. Data in (f) are replotted from ref. [57].

the electronic conductor to form a continuous conducting net-
work across membranes. The oxygen permeation fluxes of the
DP membranes consisting of fluorite-type oxides and precious
metals were far lower than the threshold value for industrial
applications. Both the high material cost and the low perme-
ability discouraged the development of this type of materials. In
the second period, to decrease the material cost, electronic con-
ducting oxides were suggested to be substituted for the precious
metals in the DP membranes.[50] The electronic conducting
oxides included perovskite oxides (such as La1−xSrxMnO3 and
La1−xSrxCrO3), spinel oxides (NiFe2O4, MnFe2O4, etc.) and other
materials. These DP membranes had high stability and high
tolerance to CO2 but low oxygen permeability. The electronic
conducting phase, which had extremely low ionic conductivities,
occupying at least 30% of the membrane bulk volume blocked
the ionic transport in the membrane bulk, thus resulting in low
oxygen permeability. Therefore, in the third period, to enhance
the oxygen permeability of DP membranes, we proposed that
mixed ionic–electronic conductors be adopted to substitute for
the traditional electronic conductors in the DP membranes.
Therefore, the oxygen transport paths in the membrane bulk
were extended from those between the ionic conducting phase
grains to the whole membrane bulk (Figure 6b). The volume
fraction of the oxides for ionic transport equals unity because
the mixed conducting phase has a high ionic conductivity. The
DP membranes 75 wt%Ce0.85Sm0.15−25 wt%Sm0.6Sr0.4CrO3−δ
(SDC–SSCr) and 75 wt%Ce0.85Sm0.15−25 wt%Sm0.6Sr0.4FeO3−δ
(SDC–SSFe) were prepared and tested to determine the differ-
ence in oxygen permeability between the second and third types
of DP membranes (Figure 6c).[51] The DP membrane, SDC–SSF,
made of ionic conductors and mixed conductors, i.e., the third
type, has much higher oxygen permeability and lower per-
meation activation energy than those of the second type of DP
membranes consisting of ionic conductors and pure electronic
conducting oxides. After a series of studies reported by our
group,[51–57] considerable effort by other researchers was devoted
to developing the third type of DP membrane.[58–61]
4.1. Structure Design of DP Membrane Materials
The design theory of DP membranes is different from that
of the single-phase perovskite membranes introduced in
Section 3. Although many researchers have argued that the
ionic and electronic transport paths of DP membranes can be
separately designed according to their potential applications,
the interactions (such as chemical reaction, interdiffusion

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of elements, thermal expansion mismatch) between the two
phases do not occur in single-phase perovskite materials but
must be considered during the design of the DP membranes.
There are many types of ionic conductors, such as fluorite-type
(including zirconia-based, ceria-based, and bismuth-based),
perovskite-type, La2Mo2O9 series, Aurivillius-type, apatite-type,
pyrochlore-type, and many MIEC materials. The number of
pairwise combinations of the ionic conducting phase and the
MIEC phase is very large, even without considering the changes
in the ratios between the two phases and the element ratios in
each phase. Therefore, it is difficult to obtain a DP membrane
material with ideal performance. To quickly obtain materials
with the targeted performance, a design principle needs to be
constructed for the DP membrane according to the working
environment of the potential applications.
For a catalytic membrane reactor, the stability of the mem-
brane material under the reaction conditions is more important
than its oxygen permeability. Thus, the stabilities under both
oxidative and reductive environments are considered prior
to considering the permeability during the design of the DP
membrane. For example, three principles (i.e., the structural
stability under catalytic reaction conditions, the ionic and elec-
tronic conductivities under reaction conditions, and the chem-
ical compatibility between the two phases) should be consid-
ered for the selection of materials to devise a DP membrane
material for the syngas (H2+CO) production via the partial oxi-
dation of natural gas. Following the above three principles, the
selection of the ionic conductors and the MIECs is not difficult.
We have given a detailed description of the selection of the two
phases.[6,51] The resultant DP membranes have the composition
Ce1−xLnxO2−δ–Ln1−ySryFeO3−δ. The perovskite stability under
reducing conditions can be improved by doping appropriate
amounts of cations such as Al3+, Ga3+, Cr3+/4+, Mn3+/4+, Ti4+
and Zr4+ into the B-site. Ba2+ and Ca2+ cations may be appro-
priate doping cations for the perovskite phase, depending on
the systems of DP membranes being considered. Here, the
design of DP membranes is based on existing knowledge, while
more advanced strategies are expected with the development
of ionic conducting materials. As an example of the material
design, 75 wt%Ce0.85Sm0.15−25 wt%Sm0.6Sr0.4Al0.3Fe0.7O3−δ
(SDC–SSAF) exhibits a high oxygen permeation flux, which
is ≈10 times higher than those of traditional membranes.[6] A
1100 h on-stream process at 950 °C for syngas generation in
a SDC–SSAF membrane reactor showed that the oxygen per-
meation flux reached 4.2 mL cm−2 min−1, and the phase struc-
tures of the SDC–SSAF membrane surface remained intact
after the long-term on-stream.[52] Moreover, there were no ele-
ments enriched on the membrane surfaces. However, a stable
surface is not exhibited on perovskite MIEC membranes. The
DP structure increases the difficulty of the cationic transport
through the membrane bulk; thus, the special microstructure
can prevent the kinetic demixing of the MIEC phase under
the large gradient of the oxygen chemical potential. Elemental
strontium, with its large size, does not easily enter the ceria
lattice; thus, the transport of Sr from one perovskite grain to
another is difficult if there is a fluorite oxide grain between
the two perovskite grains. From a geometric point of view, the
diffusion paths are significantly prolonged for the strontium
element in the SDC–SSAF membrane. More importantly, the
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Zener pinning action induced by the ionic conducting phase in
the DP membrane protects the MIEC phase from decomposi-
tion. In addition, the creep rate of the materials is limited by
the DP structure.
4.2. Microstructural Effects
The effects of changes in compositions on the oxygen trans-
port properties of the ionic conductors and the use of MIEC
perovskite oxides as the electrodes of solid oxide fuel cells and
oxygen separation membranes have been widely studied. There
have been many reviews published that have provided good
summaries of elemental doping.[5,6] However, the DP system
is much more complicated than the single-phase system. Many
new phenomena were observed during the investigation of DP
membranes. Here, the microstructural effects on the oxygen
permeation through DP membranes are of concern.
For DP membranes, increases in the permeation fluxes with
time during the initial tens of hours of operation have been fre-
quently reported,[55,56,59,62] but this phenomenon rarely occurs
with perovskite MIEC membranes. Experiments have shown
that the increase in the permeation flux with time corresponds
to the oxygen exchange reactions at the gas–solid interfaces. For
a DP membrane, its surface microstructure changes from the
as-prepared state to the state being facile to oxygen exchange
during the oxygen permeation process. This microstructure
change is related to the redistribution of the two phases on
the surfaces at elevated temperatures. Not only does the
unsteady permeation disappear, but the flux can also be sta-
bilized at a higher value if both sides of the membrane are
coated with porous catalyst layers for oxygen activation. Cobalt-
containing perovskite oxides are usually used as the catalyst.
Ostensibly, the function of the porous catalyst layer coated
on DP membranes is similar to that coated on perovskite
membranes operated at ILT, but the stabilization mechanisms
are different. When the porous layer is coated on a DP mem-
brane, it speeds up the oxygen exchange reactions, and thus
the changes in the surface microstructure have little effect on
the total permeation resistance of the DP membrane. However,
when the porous layer is coated on a perovskite membrane,
it mainly acts as a sponge to accommodate the impurities
enriched from the membrane bulk.
DP membranes have many new and unique microstructural
characteristics, such as the grain size ratio of the two phases,
grain distribution in the bulk and on the surfaces and the GBs
between the two phases. Oxygen exchange and bulk transport
are sensitive to these microstructural characteristics, which
depend on the preparation method, sintering temperature, ele-
mental composition, etc. The effects of the powder synthesis
method on the microstructures, chemical composition, crystal
lattice defects, ionic and electronic conductivity, and oxygen
permeability of perovskite MIEC membranes have been well-
studied in the past 20 years. For DP membranes, the factors that
affect perovskite materials also exist in DP materials to some
extent. We compared four methods to prepare the powders
of DP membranes and found that the distributions of the two
phases in the membranes are different.[63] The DP membrane
derived from a one-pot method (i.e., mixing all the chemical
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precursors together to prepare the composite powder) has
the most homogeneous distribution of the two phases, while
the DP membrane derived from the traditional method (i.e.,
mixing the two powders to prepare the composite powder)
shows an inhomogeneous distribution of the two phases. The
oxygen permeation flux is closely related to the distribution
of the two phases, since the more homogeneous distribution
of the two phases results in more active sites for the oxygen
exchange reaction. However, when the volume fraction of the
MIEC phase is lower than the percolation threshold (≈30 vol%),
the inhomogeneous distribution of the two phases improves
the oxygen permeation flux if the surfaces are covered with
MIEC porous catalytic layers to speed up the oxygen reduction
and evolution reactions. The inhomogeneous distribution can
increase the possibility of the formation of an electronic con-
ducting network across the DP membrane. An extreme case
of the inhomogeneous distribution of the two phases is when
an electrolyte membrane outside or inside is short-circuited by
a wire.[64] Compared with a DP membrane containing an Fe-
based MIEC phase, a DP membrane containing a Co-based
MIEC phase needs a larger volume fraction of the MIEC phase,
since the Co-based MIEC phase acts as a sintering promoter to
cause the rapid growth of the grains to a large size. The large
MIEC grains have a lower probability of forming a continuous
conducting network than do small grains at the same volume
fraction. Therefore, an excessively high sintering temperature
disrupts the electronic conducting network if the volume frac-
tion of the MIEC phase is not high enough.[65,66] In addition, an
over high sintering temperature induces the accumulation of
ionic conducting phases on the surfaces of DP membranes.[65]
There are many factors that determine the oxygen permeability
of DP membranes, and some factors interact with each other,
so it is difficult to study the actions of each factor separately.
The microstructure effects of DP membranes are very compli-
cated; therefore, there is no standard explanation for the micro-
structure effects, and a case-by-case analysis is needed.
Several DP membranes consisting of ceria-based ionic con-
ductors and Fe-based perovskite-type mixed conductors were
employed for the production of syngas,[54,55,57,58,61,67] and no
degradation of phase structure was observed, indicating good
structural and permeation stability under redox environments.
However, the oxygen permeation fluxes through 0.5 mm thick
DP membranes were all ≈4 mL cm−2 min−1 at 950 °C for syngas
production, although the DP membranes had different compo-
sitions in both phases.[52,54,55,61] We found that the extremely low
electronic conductivity in the central region of the membrane
bulk limited the ambipolar diffusion of the oxygen ions and
electrons (Figure 6d), thus increasing the bulk diffusion resist-
ance. In a relatively high oxygen partial pressure system (>10−10
atm) MIEC materials exhibit a p-type electronic conduction,
while in a relatively low oxygen partial pressure system (<10−15
atm), they exhibit n-type electronic conduction. However, in the
intermediate-low oxygen partial pressure range, i.e., 10−10–10−15
atm, they usually have a minimum value corresponding to a
p–n transfer.[57,68] Therefore, the oxygen permeation flux can
be increased by enhancing the electronic conductivity in the
intermediate-low oxygen partial pressure range for syngas
production in MIEC membrane reactors. Elemental Cr was
used to replace the elemental Al in SDC–SSAF to form the
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SDC–SSCF DP membrane.[57] The Cr-substitution led to a great
improvement of the electronic conductivity in the oxygen par-
tial pressure range of 10−2–10−15 atm, as shown in Figure 6d. A
high oxygen permeation flux of up to 7.8 mL cm−2 min−1 was
achieved at 950 °C for the syngas generation, which is nearly
two times that of the SDC–SSAF under the same conditions,
although the SDC–SSCF exhibited a lower oxygen permeation
flux than did the SDC–SSAF under an oxygen partial pressure
gradient of 0.21 atm/0.005 atm (Figure 6f).
5. Catalytic Membrane Reactors
Partial oxidation of methane and methane coupling are two
widely investigated reactions in MIEC membrane reactors. In
these membrane reactors, one side is fed with air and the other
side is fed with methane. Many reviews have given comprehen-
sive summaries of the two reactions.[5,6,69] With improvements
in the stabilities of membrane materials, new membrane reac-
tors in which both sides of the MIEC membranes are exposed
to strong reducing atmospheres have been reported in recent
years. The thermodynamic limited reactions, for instance
hydrogen production from water splitting[70–72] and CO2 reduc-
tion to CO,[73] can be promoted by coupling with a thermody-
namic spontaneous reaction in MIEC membrane reactors.
Balachandran et al. proposed new MIEC membrane reactors,
in which the hydrogen generation via water decomposition was
combined with syngas production via the partial oxidation of
methane,[70] and the membrane reactor was experimentally ver-
ified by Jiang et al. using a perovskite hollow fiber membrane
reactor.[71] The combination of the selective oxidation of ethane
to ethylene with the water decomposition reaction was also con-
ducted in the hollow fiber membrane reactor.[72] Recently, our
group proposed two reaction–separation–reaction processes in
MIEC membrane reactors for coproducing two types of syngas
and hydrogen separation.[74,75]
5.1. Coproduction of Two Types of Syngas
Ammonia, one of the most widely produced chemicals in
the world, is synthesized via the classical Haber–Bosch pro-
cess, in which six main steps (i.e., steam reforming, air
reforming, water–gas shifting at high and low temperatures,
CO2 separation and methanation) are performed to produce
ammonia synthesis gas (ASG, H2/N2  = 3) in which natural
gas is used as the feed. A large amount of CO2, i.e., ≈400 mil-
lion metric tons annually, is discharged from the ammonia
synthesis industry. More than 80% of the energy consump-
tion of the entire ammonia synthesis process is contributed
by the long-route ASG production process. Therefore, new
processes for ammonia synthesis have attracted the attention
of many researchers. On the other hand, three main steps
(i.e., steam reforming, air separation, and mixed reforming)
are involved in the production of liquid fuel synthesis gas
(LFSG, H2/CO = 2), and >60% of the energy consumption and
investment in the gas-to-liquid process is contributed by the
three steps. The air separation step contributes a large por-
tion of the energy consumption (30–40%). However, these
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two multistep and high-energy-consumption processes can
be united in one MIEC membrane reactor for coproducing
ASG and LFSG with natural gas, water, and air in one step
(Figure 7a).
To carry out the process, air and steam in an appropriate
ratio are introduced into one side (side I) of the membrane
reactor, and natural gas is introduced into the other side
(side II). At elevated temperatures, the oxygen species in the air
and steam are driven by the oxygen chemical potential gradient
across the membrane from side I to side II where they react
with natural gas to produce LFSG. The electrical neutrality of
the whole process is achieved by the transfer of electrons from
side II to side I. After the oxygen in the air and steam is con-
sumed by the MIEC membrane, ASG with a H2/N2 ratio of 3:1
after drying is produced on side I. Thus, the resultant mixture
is ready for ammonia synthesis. The syngas produced on side
II with a H2/CO ratio of 2 is suitable for liquid fuel synthesis.
The highly intensified process has many advantages, as illus-
trated in Figure 7b. The greatest advantages of the catalytic
membrane reactor are its simple process (i.e., the nine steps
being shortened to one step) and its high energy efficiency.
Membrane reactors containing BCF perovskite membranes and
SDC–SSAF DP membranes were employed to illustrate the fea-
sibility of the process.[67,74] Considering the high stability but
low permeability of SDC–SSAF compared to BCF, the SDC–
SSAF was fabricated into asymmetric membranes with a dense
layer of 40 µm. Ru/SDC was used as the catalyst coating on
the surface with a thickness of 20 µm and was infiltrated into
the porous support layer (Figure 7c,d). High production rates of
the two types of syngas as well as high CO selectivity and CH4
conversion were obtained in the asymmetric DP membrane
reactor (Figure 7e). The membrane reactor was stable during
the steady operation (Figure 7f). The conversion of the water
decomposition to hydrogen was up to 55% at a H2O/CH4 ratio
of 1.25 (Figure 7g) and corresponded to an energy savings
larger than 60% compared to the current industrial processes
for the two types of syngas production. The success in the stable
operation of membrane reactors indicates that the new concept
for coproducing two types of syngas in membrane reactors is
promising and may trigger innovations in the natural gas and
chemical industries.
5.2. MIEC Membranes for Hydrogen Separation
Hydrogen is a high-quality, clean and sustainable energy car-
rier. Its production, separation, storage, and utilization have
been widely investigated in the past 20 years. CO, CO2, N2, and
H2S are the common impurities in the as-produced hydrogen.
These impurities should be removed before hydrogen is sup-
plied to protonic exchange membrane fuel cells and used for
the fabrication of semiconductors and solar energy cells. The
current technologies are limited by their low separation selec-
tivity (for the pressure swing adsorption and polymer mem-
brane separation technologies) or high price and low stability
(for Pd-based membranes).
In the previous investigations of water splitting in
MIEC membrane reactors, if the driving force of the water
decomposition reaction is provided by the hydrogen oxidation
reaction, the whole process does not seem to warrant further

Figure 7.  a) One-step production of the two types of synthesis gas for ammonia (H2/N2 = 3:1) and liquid fuel (H2/CO = 2:1) synthesis from water,
air, and natural gas in a membrane reactor. b) Merits of the membrane reactor compared with those of the industrial processes. a,b) Reproduced with
permission.[74] Copyright 2016, Wiley-VCH. c,d) Top-view (c) and cross-sectional view (d) scanning electron microscopy (SEM) images of the asym-
metric SDC–SSAF membrane. e) Effects of temperature on the performance of the membrane reactor. f) Stable operation of the membrane reactor at
900 °C. g) Energy saving in the membrane reactor. d–g) Reproduced with permission.[67] Copyright 2019, Elsevier Ltd.

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Figure 8.  a) Oxygen-permeable membrane for hydrogen separation; b,c) cross-sectional view of the asymmetric SDC–SSAF DP membranes with both
sides coated with Ru catalysts before (b) and after (c) the long-term operation. d) The dependence of the H2 separation rate and the corresponding PO2
for both sides on temperature. e) Stable operation for the hydrogen separation. f) Effect of the H2S concentration on the hydrogen separation rate. The
concentration of H2 to side I is 50% for the H2S concentration of 0–100 ppm and is 99.98% for the H2S concentration of 200 ppm. a–f) Reproduced
with permission.[75] Copyright 2017, Royal Society of Chemistry.

study.[70,71] However, the process using low-purity hydrogen to
produce high-purity hydrogen can be operated as a process of
hydrogen separation if steam is fed to side I while a low-purity
hydrogen source is introduced into side II (Figure  8a).[75] The
high-purity hydrogen is obtained by cooling and drying the
effluent gas of side I. In this process, when a hydrogen mol-
ecule is produced via the water-splitting reaction on side I,
there is a hydrogen molecule consumed simultaneously on side
II. The net chemical reaction is zero in the whole process, but
a mass exchange is achieved between the two sides. The fed
hydrogen has a low purity while the obtained hydrogen has a
high purity; thus it is a process of hydrogen separation with the
help of steam. In theory, the selectivity of the hydrogen separa-
tion is up to 100%, because only oxygen is allowed to permeate
through the dense MIEC membranes.
The hydrogen separation process was achieved on DP
membranes with both surfaces covered with Ru or Ni cata-
lysts to speed up the water-splitting and hydrogen oxidation
reactions (Figure 8b,c).[75] At 950 °C, the hydrogen separation
rate was as high as 16 mL cm−2 min−1 (Figure 8d), which is
100–1000 times higher than those of mixed electronic–pro-
tonic conducting (MEPC) ceramic membranes. This high flux
is on the same level as those of Pd composite membranes.
The hydrogen separation rate was 1.7 mL cm−2 min−1 even
at a temperature as low as 600 °C, indicating it is possible to
extend the running temperature to ILT for hydrogen separa-
tion using asymmetric DP membranes. Although the defects
in the membrane and sealing are inevitable, the hydrogen
separation factor was achieved on the order of 103–104. The
performances of the dual-phase membrane reactors were
stable for hydrogen separation when 50% H2/N2 and 90%
H2O/He were used as the feed gases (Figure 8e). Although
the low-purity hydrogen source contained impurities such
as CO2[53] and H2S (Figure 8f),[75] the dual-phase membrane
reactors were stable for hydrogen separation. However, Pd-
based membranes and MEPC membranes are sensitive to
the poisoning of H2S.[76] Therefore, hydrogen separation
using DP membranes is feasible in principle. The mem-
brane thickness and porous supports have a strong influ-
ence on the ambipolar diffusion resistance in the membrane
bulk and on gaseous reactions at the gas–solid interfaces.
These effects were observed on the MIEC DP membranes
for hydrogen separation. Concentration polarization induced
by the thick porous support of the asymmetric membranes
was not observed compared with membranes with the same
thickness of the dense layer but different structural types.[77]
However, the concentration polarization has been verified on
asymmetric membranes for oxygen separation from air.[23,78]
This abnormal phenomenon is caused by the diffusion rate of
the hydrogen molecules being faster than that of the oxygen
molecules. The hydrogen separation rate is jointly controlled
by the bulk diffusion and interfacial reactions compared with
membranes with the same structure types but different thick-
nesses of the dense layer.
The concept of using oxygen-permeable MIEC membranes
for hydrogen separation is different from the traditional con-
cept of membrane separation. In the traditional approach, there
are two mechanisms for the separation of a target molecule,

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i.e., permeation and rejection. However, in the new method, the
hydrogen separation is realized via a reaction–separation–reac-
tion process. This special separation concept may be extended
to other systems in the future.
6. Technological Development of MIEC
Membranes for Pure Oxygen Production
and Catalytic Membrane Reactors
In the past 20 years, APCI has led the technological develop-
ment of MIEC membranes for pure oxygen production. APCI
began research and development in 1989 and focused on
the development of planar ceramic wafers (Figure  9a) with a
composition of LnxA1−xCo1−y−zFeyCuzO3−δ (where Ln and A
are selected from the lanthanide block and the alkaline earth
elements, respectively).[6,31,79] In 2006, a 5 ton-per-day (TPD)
subscale engineering prototype containing six independent
modules was successfully operated over 1000 days to produce
oxygen with a purity >99% (Figure 9b).[79] Next, full size MIEC
modules with an oxygen production capability of ≈1 TPD in
the pressure vessel were tested under a variety of operating
conditions. However, the oxygen permeation flux of a mem-
brane module containing 12 wafers decreased by ≈10% after
operating for 15 000 h. The degradation was attributed to the
ceramic creep leading to the deformation of the microchannels
under elevated pressure and temperatures (Figure 9c,d).[31] A
transient liquid phase method was invented by APCI to seal
the MIEC membranes. The ceramic sealant has the same or
similar chemical composition as the MIEC membrane; thus,
there is no chemical and thermal incompatibility between the
sealant and the membrane. The innovative sealing technology
is the key to the APCI’s success in planar MIEC membranes.
The APCI and its partners were motivated by the success of the
5 TPD prototype to construct a 100–150 TPD intermediate-scale
test unit. However, no further news on the intermediate-scale
test unit has been released to date.
Different from APCI using the planer membranes, the
Institut für Keramische Technologien und Systeme (IKTS) of
Fraunhofer in Germany built a membrane module with BSCF
capillaries (Φ 3 mm) with an oxygen production capability of
0.38 TPD in 2017 (Figure 9e,f).[24] With the advanced design
of heat exchange between the inlet and outlet air, rubber was

Figure 9.  a) Construction steps of the commercial modules. b) Subscale engineering prototype capable of testing up to six 144-wafer ITM Oxygen
modules. a,b) Reproduced with permission.[79] Copyright 2009, Springer. c) 12-wafer module after testing for over 15 000 h. d) Example of deformation
and decreased cross-sectional area of the channels due to creep. c,d) Reproduced with permission.[31] Copyright 2016, Elsevier B.V. e) BSCF capability
prepared by IKTS. f) Pilot plant for the production of 10 m3 (STP) O2 h−1. e,f) Adapted with permission.[24] Copyright 2018, ICIM.

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successfully used to seal the capillaries with a long-lasting seal.
The module design scale-up to the oxygen production capa-
bility of hundreds of tons per day needs further verification.
IKTS evaluated the total energy demands for oxygen separation
including the heat needed to keep the modules at elevated tem-
perature and the energy requirement for gas compression, and
found that the energy costs can be reduced to 18.39 or 14.01
Euro ton−1 oxygen if the gas combustion or waste heat is used
to heat the modules. The energy costs is only 54% and 41% that
of cryogenic separation technology.
Praxair Inc. focuses on developing MIEC membrane reac-
tors for natural gas conversion to syngas.[80] Tubular dual-phase
membranes with a dense layer thickness of 20–30 µm were
used to construct the membrane reactors. An innovative design
of an integrated reactor was proposed that contained membrane
reactors and steam reformers. The membrane tubes were par-
allelly arranged in a panel, and the steam reformer tubes were
arranged in another panel. Then, the membrane tube panels and
the steam reformer panels were alternately installed in a vessel.
The natural gas and steam were fed into the steam reformer
tubes and then into the membrane tubes. Air was fed outside the
membrane tubes and steam reformer tubes. This design allows
for the thermal exchange between the steam reformer tubes
(endothermic) and the membrane tubes (exothermic). This
integrated reactor combines the primary steam methane per-
former, secondary autothermal reformer, and air separation unit
together. Compared with the traditional reactors, the integrated
reactor is expected to decrease CO2 emissions by 29% and the
capital investment by 18% while increasing the net income >30%
for a 3000 ton day−1 methanol plant. Six-panel arrays, containing
216 membrane tubes, with a capability of up to 190 Nm3 h−1
syngas were tested for 44 weeks without failure during >100
start-up/shut-down cycles. Praxair Inc. reported the achieve-
ment of commercial ceramic performance targets for permea-
tion flux, strength, creep life, degradation, and sealing. A project
was started in 2019 to build an integrated reactor with a capa-
bility of up to 9940 Nm3 h−1 syngas for a methanol plant.
7. Conclusions and Perspectives
In this paper, the designs of the microstructure and gas–solid
interfaces of MIEC oxygen-permeable membranes to improve the
permeability and stability were summarized. The understanding
of the permeation mechanism with the help of a modeling anal-
ysis is important for the development of membrane materials,
oxygen exchange catalysts, and the degradation mechanism. The
enrichment of impurities from the membrane bulk to the surface
decreases the oxygen exchange rate on the gas–solid interfaces,
while the new phase appearing at the grain boundaries blocks the
ambipolar diffusion. Thus, the degradation of MIEC membranes
at intermediate-low temperatures is closely related to the changes
in the gas–solid interfaces and bulk microstructures. Accordingly,
the strategies to overcome the degradation are focused on the
designs of interfaces and bulk microstructures. The microstruc-
tural and interfacial effects are more pronounced in dual-phase
membranes due to the complicated chemical and physical rela-
tionships between the two phases. We have obtained high-per-
formance dual-phase membranes through the comprehensive
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design of dual-phase materials by considering the critical factors
such as phase composition, phase ratio, phase distribution, grain
size, and gas–solid interfaces. Based on the perfect membranes,
newly catalytic membrane reactors were developed for reaction–
separation–reaction coupling to produce two types of synthesis
gas in one step and to use the oxygen-permeable membranes
for hydrogen separation. In the common membrane separation
process, the separation of the target molecules is realized via
permeation or rejection by the membranes; however, hydrogen
separation with oxygen-permeable membranes is realized via a
coupling process of reaction–separation–reaction. In the future,
the development of MIEC oxygen-permeable membranes should
be focused on the following points:
1) Membrane materials. It is possible to explore the operating
temperatures of dual-phase membranes for intermediate-
low temperatures by optimizing the microstructures and
preparation methods. The processes of oxygen separation
and reaction–separation coupling have more potential to be
commercialized using dual-phase membranes since they
have higher stability than do single-phase perovskite mem-
branes at similar permeabilities. The recent development of
dual-phase membrane materials is focused on the change of
the electronic conducting phase. The ceria-based ionic con-
ductors are the most often used ionic conducting phase in
dual-phase membranes, but the remarkable chemical expan-
sion of ceria due to the reduction of Ce4+ to Ce3+ increases
the breakage risk of membrane reactors. Zirconia-based ionic
conductors may be good alternatives due to their high stabil-
ity. However, it is challenging to develop a mixed conduct-
ing phase with good chemical compatibility with zirconia.
The microstructures and interfaces (including gas–solid and
solid–solid interfaces) may play important roles in the per-
meability of the zirconia-based dual-phase membranes.
2) Permeation model and simulation. The mechanisms of
oxygen exchange at the gas–solid interfaces are not fully
understood. The dependence of the permeation resistances,
including the resistances on both the interfaces and the bulk,
on the oxygen partial pressure is not known. Thus, the cur-
rent models cannot provide an accurate analysis of the oxygen
permeation process. The applicability of models to different
materials and processes needs to be explored in detail to avoid
misleading conclusions. Little research has been carried out
on the simulation of catalytic membrane reactors. The rate-
determining step of membrane reactors is rarely discussed in
the literature. The challenge is that all the current models for
oxygen permeation are not suitable for membrane reactors,
because the conditions of the gas–solid interfacial reactions
and bulk transport process do not meet the assumptions of
the permeation models. In addition, little effort has been put
into simulating the membrane modules to understand the
mass transport in the membranes and modules; thus, the
current stage of the design of membrane modules is guided
by experiments with a low efficiency.
3) Reaction–separation coupling. There is a need to explore new
reaction–separation coupling processes in MIEC oxygen-per-
meable membrane reactors. Decreasing the operating tem-
perature from the high-temperature range (800–1000 °C) to the
intermediate-low temperature range (350–700 °C) would allow
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many oxygen-related catalytic reactions in the MIEC oxygen-
permeable membrane reactors, while the challenges of the
permeation flux of membranes and activity of catalysts would
increase sharply. Because it is different from traditional hetero-
geneous catalysis, the transport of oxygen ions and electrons
from the membrane bulk to the catalysts warrants further study.
Common catalyst supports, such as alumina, silica, and zeo-
lites, which cannot transport oxygen ions and electrons simulta-
neously, are not effective for membrane reactors. In the past 20
years, research has focused on the development of membrane
materials and new reaction–separation coupling processes, but
few studies have been conducted on catalyst development for
membrane reactors. The experiences and knowledge from solid
oxide cells are useful for the development of customized cata-
lysts for MIEC oxygen-permeable membrane reactors.
4) Technologies. Tape-casting technology is the most frequently
used approach for the fabrication of flat asymmetric mem-
branes. However, the tubular shape is ideal for a MIEC oxygen-
permeable reactor operating at a high pressure. Pores and cracks
are difficult to avoid if the tubular asymmetric membranes
are prepared via a traditional dip-coating method. Therefore,
new methods are needed for the highly effective preparation
of tubular asymmetric membranes. Membrane sealing has
not been adequately developed in the past 20 years. Sealants
such as glass, ceramics, and metals have been reported in the
literature; however, their reliabilities need to be carefully evalu-
ated under operating conditions. Sealing membranes with rub-
ber gaskets as they come out of the high-temperature zone is
easily accomplished; however, its feasibility at the industrial
scale needs carefully to be evaluated when scale, energy con-
sumption, costs, and lifetime are all considered. In addition,
the MIEC membrane process and the economic outlook are
competitive but have yet to be verified by a practical case.
Acknowledgements
The authors appreciate the financial supports from the National Natural
Science Foundation of China (91545202 and U1508203), the Strategic
Priority Research Program of the Chinese Academy of Sciences (CAS)
(Grant No. XDB17000000), grants of Dalian National Laboratory for
Clean Energy (DNL) (DNL180203 and DICP&QIBEBT UN201708), and
the Youth Innovation Promotion Association of CAS.
Conflict of Interest
The authors declare no conflict of interest.
Keywords
interfaces, membrane reactors, microstructure, mixed ionic–electronic
conductors, oxygen permeation
Received: April 22, 2019
Revised: June 11, 2019
Published online:
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