Applied Energy xxx (2015) xxx–xxx

Contents lists available at ScienceDirect

Applied Energy
journal homepage: www.elsevier.com/locate/apenergy

Ca1xAxMnO3 (A = Sr and Ba) perovskite based oxygen carriers for

chemical looping with oxygen uncoupling (CLOU)
Nathan Galinsky a, Amit Mishra a, Jia Zhang b, Fanxing Li a,⇑
a
North Carolina State University, Campus Box 7905, Raleigh, NC 27695-7905, USA
b
Institute of High Performance Computing, 1 Fusionopolis Way, #16-16 Connexis, Singapore 138632, Singapore

h i g h l i g h t s

 Sr and Ba are doped into the CaMnO3 structure for enhanced phase stability and CLOU properties.
 Strontium dopant helps to prevent irreversible decomposition of the perovskite structure.
 Sr-doped oxygen carriers have CLOU capabilities at lower temperatures while being redox stable.
 Computational techniques, such as DFT, can potentially be used to guide oxygen carrier selection.

a r t i c l e i n f o a b s t r a c t

Article history: Operated under a cyclic redox mode with an oxygen carrier, the chemical looping with oxygen uncou-
Received 6 January 2015 pling (CLOU) process offers the potential to effectively combust solid fuels while capturing CO2.
Received in revised form 28 March 2015 Development of oxygen carriers capable of reversibly exchanging their active lattice oxygen (O2) with
Accepted 6 April 2015
gaseous oxygen (O2) under varying external oxygen partial pressure (PO2) is of key importance to
Available online xxxx
CLOU process performance. This article investigates the effect of A-site dopants on CaMnO3 based oxygen
carriers for CLOU. Both Sr and Ba are explored as potential dopants at various concentrations. Phase seg-
Keywords:
regations are observed with the addition of Ba dopant even at relatively low concentrations (5% A-site
Chemical looping
Oxygen uncoupling
doping). In contrast, stable solid solutions are formed with Sr dopant at a wide range of doping level.
Perovskite While CaMnO3 perovskite suffers from irreversible change into Ruddlesden–Popper (Ca2MnO4) and
Solid fuel spinel (CaMn2O4) phases under cyclic redox conditions, Sr doping is found to effectively stabilize the per-
ovskite structure. In-situ XRD studies indicate that the Sr doped CaMnO3 maintains a stable orthorhombic
perovskite structure under an inert environment (tested up to 1200 °C). The same oxygen carrier sample
exhibited high recyclability over 100 redox cycles at 850 °C. Besides being highly recyclable, Sr doped
CaMnO3 is found to be capable of releasing its lattice oxygen at a temperature significantly lower than
that for CaMnO3, rendering it a potentially effective oxygen carrier for solid fuel combustion and carbon
dioxide capture.
Ó 2015 Elsevier Ltd. All rights reserved.

1. Introduction
Climate change caused by anthropogenic carbon dioxide emis-
sions along with the ever increasing demand for energy requires
new power generation processes with lower carbon footprints. Of
the various carbon capture technologies under development,
chemical looping combustion (CLC) has emerged as a potentially
promising option [1,2]. The CLC processes utilize a solid oxygen
carrier to transfer oxygen from the air to the fuel. This is achieved
using interconnected fluidized bed or moving bed reactors [3–8]. In
⇑ Corresponding author. Tel.: +1 919 515 7328.
E-mail address: fli5@ncsu.edu (F. Li).
the first reactor, commonly termed the reducer/fuel reactor, the
oxidized form of the oxygen carrier is reacted with the fuel to form
carbon dioxide and water vapor. The oxygen depleted carrier is
then transported to a second reactor referred to as the oxidizer/
air reactor. Here, air is used to regenerate the oxygen depleted car-
rier while producing heat for power generation.
While most oxygen carriers are effective for gaseous fuel com-
bustion, they tend to be less active in converting solid fuels such
as biomass or coal due to mass transfer and kinetic limitations.
To enhance the combustion rate for solid fuels, two methods are
typically used. In the first method, solid fuel is gasified into syngas
by steam, carbon dioxide, or oxygen. The resulting syngas is then
reacted with the oxygen carrier at a faster rate than direct

http://dx.doi.org/10.1016/j.apenergy.2015.04.020
0306-2619/Ó 2015 Elsevier Ltd. All rights reserved.

Please cite this article in press as: Galinsky N et al. Ca1xAxMnO3 (A = Sr and Ba) perovskite based oxygen carriers for chemical looping with oxygen uncou-
pling (CLOU). Appl Energy (2015), http://dx.doi.org/10.1016/j.apenergy.2015.04.020
2 N. Galinsky et al. / Applied Energy xxx (2015) xxx–xxx
solid–solid interactions [6–11]. A variety of oxygen carriers includ-
ing Fe [8,10,12–14], Mn [13,15], and Ni [16,17] based oxides have
been used in the conversion of solid fuels via such an in-situ
gasification approach. An even faster approach to combust solids
fuel is the so-called chemical looping with oxygen uncoupling
(CLOU) [3,18,19]. The CLOU process takes the advantage of oxygen
carriers with high equilibrium oxygen partial pressure (PO2). As a
result, solid fuels are combusted with gaseous oxygen released
from the oxygen carrier, resulting in significantly improved reac-
tion kinetics. Typical oxygen carriers that exhibit CLOU properties
include oxides and mixed oxides containing Cu, Mn, and/or Co
[18–30].
Despite possessing excellent oxygen uncoupling properties,
copper oxides face challenges including a low melting point of
the reduced Cu phase which can lead to agglomeration and deflu-
idization. Supports, such as MgAl2O4, SiO2, and Al2O3, have been
shown to help prevent sintering and defluidization while main-
taining the oxygen uncoupling properties of the copper oxide
[19,26–28]. Nevertheless, the relatively high cost of copper oxide
may limit its applications. Cobalt oxides, while potentially feasi-
ble, are typically avoided due to their low decomposition
temperature, toxicity, and negative environmental impact
[18,23]. Manganese oxides hold advantages over copper oxides
in terms of high availability and low cost. However, pure man-
ganese oxide is difficult to regenerate with air due to its high
equilibrium PO2. Formation of mixed oxide phases through the
addition of secondary metal oxides such as Fe, Ni, Mg, and Ca
to manganese oxides has been shown as an effective approach
to improve the regenerability and structural stability of Mn based
oxygen carriers [15,19,21–25,31–36].
More recently, perovskite structured oxygen carriers have
received increasing attentions as oxygen carriers for redox applica-
tions [23,31,33–54]. Typical perovskite takes the form of ABO3d,
where A is a large cation of either the alkali earth or rare earth
metal and B is a smaller transition metal cation [55]. As a support,
mixed ionic and electronic conductive (MIEC) perovskites such as
La1xSrxFeO3 (LSF) have shown to enhance the redox activity of
iron oxides by nearly two orders of magnitude [51–54].
Perovskite and perovskite supported iron oxide have also been
explored as redox catalysts for syngas generation and water-split-
ting [42,56]. In terms of CLOU applications, La containing per-
ovskite supports are reported to be effective to enhance the
oxygen donation properties of mixed Mn–Fe and Co–Fe oxides
[23]. Up to 8.8% decrease in initial decomposition temperature
was reported for perovskite supported mixed metal oxides. As a
standalone oxygen carrier, perovskites of the CaMnO3 family
are extensively studied for CLOU and CLC applications [20,29–
39,49,57–61]. While its oxygen uncoupling capacity is smaller than
copper oxides, CaMnO3, which can be synthesized from abundantly
available manganese ores and Ca precursors [29,60], has been
reported to be active for solid fuel conversions [29,31,34,36]. A
challenge to CaMnO3 is its lack of long term stability and activity
with fuels. Undoped CaMnO3 has been reported to undergo irrever-
sible phase change to CaMn2O4 and Ca2MnO4 phases, leading to
eventual deactivation of the oxygen carrier [19,20,32,58,59]. In
addition, CaMnO3 has been shown to deactivate in the presence
of sulfur, a common constituent of coal, through formation of
CaSO4 [32,36,59]. Prevention of irreversible phase transition has
been investigated by doping secondary metals into the A and
B-sites of the CaMnO3 parent material. The dopants can also be
used to increase the activity of the oxygen carrier. The most com-
mon elements used to stabilize the structure are Ti and Mg.
Pishahang et al. investigated Ca1yMn1xTixO3d oxygen carriers
under fixed bed conditions using syngas as the fuel [38]. The
authors reported that adding Ti and decreasing the Ca content
increased stability of the oxygen carrier. 95% conversion of the
Please cite this article in press as: Galinsky N et al. Ca1xAxMnO3 (A = Sr and Ba) perovskite based oxygen carriers for chemical looping with oxygen uncou-
pling (CLOU). Appl Energy (2015), http://dx.doi.org/10.1016/j.apenergy.2015.04.020
syngas was achieved with no observable coke formation. Rydèn
et al. studied a CaMn0.875Ti0.125O3d oxygen carrier for CLOU [35].
The oxygen carrier exhibited oxygen uncoupling at temperature
above 720 °C in a fluidized bed with a maximum oxygen uncou-
pling rate of 0.03 LN/min at 950 °C. The maximum oxygen concen-
tration was 4 vol.%. Besides the good uncoupling properties, the
oxygen carrier exhibited good redox activity and stability for
methane conversion. Kallen et al. used Mg doped CaMnO3 and
tested the oxygen carrier in a 10 kWth gas-fired CLC unit [37].
The synthesized oxygen carrier released oxygen at above 700 °C.
The oxygen carrier did not agglomerate for 120 h. at hot conditions
(including 55 h of reaction) and formation of fines (<45 lm) was
below 0.01%, indicating possible longevity in the particle’s lifetime.
Another study using Mg, Ti, and Fe dopants conducted by Hallberg
et al. shows good activity with methane and syngas while releasing
0.3–0.5% by weight gaseous oxygen at 900 °C [33]. A maximum
oxygen release of 1 wt.% was reported at 1000 °C. The authors
noted CaMn2O4 spinel formation after testing the oxygen carrier’s
CLOU properties in three cycles and activity for methane conver-
sion in a single cycle. Hallberg et al. also investigated the addition
of both Ti and Mg in a 300 W fluidized bed system using natural
gas as the fuel [61]. The designed oxygen carriers showed higher
conversion of the fuel than Ni oxides while showing little attrition,
however, it was determined that the spent particles contained a
noticeable amount of the spinel CaMn2O4 phase. Pour et al.
examined different oxygen carriers created by combining cheap
manganese ores with Ca(OH)2 [29]. While the primary phase was
CaMnO3d, the manganese ores also contained Al, Fe, K, Ti, Mg,
etc. in small quantities. In reaction with methane, ores containing
high concentrations of Al showed poor performance due to spinel
formation between Al and Mn. The best performing oxygen carrier
made from a South African manganese ore, which was mainly com-
posed of Fe, Si, Ca, Mg, and Mn, had an oxygen capacity of 1.5 wt.%
in methane. Oxygen uncoupling capacity was between 0.37 and
0.68 wt.% for the various oxygen carriers investigated.
Although extensive studies on B-site dopants were performed,
limited studies using A-site dopants have been conducted.
Arjmand et al. investigated CaxLa1xMnyM1yO3d (M = Mg, Ti, Fe,
or Cu) oxygen carriers for CLOU properties between 900 and
1000 °C in a laboratory scale fluidized bed [31]. The authors
characterized the oxygen carriers’ capability to release oxygen by
measuring oxygen concentration in the product gas stream during
the uncoupling step. It was determined that pure CaMnO3 had the
highest oxygen release capability (0.7% after 360 s). La-doped
CaMnO3 had a lower oxygen concentration of 0.5% after 360 s.
Doping of both A and B-sites caused even further decrease in
oxygen release except for copper doping which exhibited higher
oxygen concentration than CaMnO3. However, copper caused the
perovskite materials to defluidize when fuel was added. The
authors did detect small amounts of spinel CaMn2O4 although its
effect on the oxygen carrier performance was not documented.
To summarize, further studies on the effect of A-site substitution
using low cost alkali earth metals are desired in order to obtain a
more informed strategy to develop oxygen carriers with lower cost
and improved CLOU performance.
This article investigates the effect of A-site dopants on
CaMnO3 based oxygen carriers for CLOU applications. Both Sr
and Ba are explored as potential dopants at various concentra-
tions. The impacts of A-site dopants on phase stability, oxygen
release properties, redox stability, and reactivity of the
Ca1xAxMnO3 (A = Sr and Ba) based oxygen carriers are investi-
gated using an in-situ X-ray diffraction (XRD) instrument, a
thermogravimetric analyzer (TGA), and a fluidized bed reactor.
It is determined that Sr dopant can enhance the stability of
the perovskite structure while providing facile oxygen release
for solid fuel conversions.
 N. Galinsky et al. / Applied Energy xxx (2015) xxx–xxx
2. Experimental
2.1. Oxygen carrier synthesis
Mixed oxides with a general formula of Ca1xAxMnO3 (A = Ba or
Sr and x = 0, 0.05, 0.25, 0.5, 0.75, and 1) are prepared using a citric
acid sol–gel method. General procedure for the sol–gel samples
includes dispersion of cation precursors Ca(NO3)24H2O (Sigma–
Aldrich), Ba(NO3)2 (Sigma Aldrich), Sr(NO3)2 (ACS Reagent, Noah),
and Mn(NO3)24H2O (Sigma Aldrich) in distilled water followed
by addition of citric acid. In the synthesis procedure used, citric
acid (Sigma Aldrich) is added to the solution in a molar ratio of
2.5:1 (citric acid: total cations) as a chelating agent. After a short
time, ethylene glycol (Sigma Aldrich) is used as a gel promoter in
a molar ratio of 1.5:1 (ethylene glycol: citric acid) at a temperature
of 80 °C. After most of the water is boiled out, the sol–gel sample is
dried in a vacuum oven for 12 h to remove any extra moisture. The
dried sample is then annealed in air at 1200 °C for 12 h. The result-
ing powder is crushed and sieved to under 75 lm particle size.
A solid state reaction (SSR) method is used to scale up the
synthesis process. The SSR method procedure requires powder pre-
paration, followed by pelletization, and annealing/solid state reac-
tion. Preparation of a Ca0.75Sr0.25MnO3 oxygen carrier was
conducted by mixing calculated amounts of CaCO3 (P99.0%,
Sigma–Aldrich), SrCO3 (99.0%, Noah), and Mn3O4 (99.0%, Noah)
precursors for 12 h in a planetary ball mill (XBM4X, Columbia
International) at a rotation speed of 250 rpm. The mixture is then
pressed into 3=4 00 pellets by a hydraulic press (YLJ-15T, MTI
Corporation) at a pressure of 20 MPa and sintered in a high tem-
perature furnace (GSL-1500-X50, MTI Corporation) at 1200 °C for
12 h. After annealing, the particles are fractured and sieved into a
range of 90–250 lm.
2.2. Oxygen uncoupling experiments
Initial oxygen uncoupling properties of the oxygen carriers are
characterized in a TGA. Two primary experiments are conducted
in the TGA: (1) temperature programmable desorption TPD experi-
ments using inert helium (5.0, Airgas) up to 1000 °C at a ramp of
20 °C/min and (2) isothermal experiments between 650 and
950 °C. Isothermal experiments are conducted at various tempera-
tures to determine the oxygen uncoupling capabilities at low to
high temperatures. At each temperature, 5 cycles of switching
between pure inert and 10% O2 (Extra Dry, Airgas) balanced with
a mixture of argon (5.0, Airgas) and helium are conducted for short
term recyclability of the oxygen carrier. Best performing oxygen
carriers are also tested for 100 cycles at 850 °C to demonstrate
the oxygen uncoupling performance of the perovskite oxygen car-
riers over the long term.
2.3. Fluidized bed experiments
A laboratory-scale fluidized-bed reactor is used for solid fuel
conversion experiment (Fig. S1). The quartz fluidized-bed reactor
has an outer diameter of 25.4 mm. The reactor is heated through
external heating from a tube furnace (MTI OTF-1200X-S-VT).
Temperature is measured inside the reactor with an Inconel
(Type K) thermocouple to set the temperature of the reactor to
850 °C. A 3.75 mm ID stainless steel tube is used for solid fuel
injection into the reactor. A gas mixing panel is used to send the
desired ratio of gases from both the bottom of the reactor for flu-
idization and through the smaller stainless steel tube for solid fuel
injection. For maintaining fluidization, flow rates of 1080 and
1200 mL/min (at S.T.P) are used for solid fuel conversion (inert
environment) and oxidation cycles, respectively. The flow rates
Please cite this article in press as: Galinsky N et al. Ca1xAxMnO3 (A = Sr and Ba) perovskite based oxygen carriers for chemical looping with oxygen uncou-
pling (CLOU). Appl Energy (2015), http://dx.doi.org/10.1016/j.apenergy.2015.04.020
3
correspond to 6–7 times the calculated minimum fluidization
velocity, Umf, of the synthesized oxygen carrier. Prior to experi-
ments, the reactor bed is loaded with 16 mesh silicon carbide
(Kramer Industries) at the bottom of the reactor. The SiC particles
act as a gas preheater and distributor. The SiC layer also supports
the oxygen carrier bed. After the SiC layer is placed, approximately
15 g of the oxygen carrier is placed into the reactor.
For redox reactions of solid fuel, bituminous coal (Asbury Inc.) is
converted into devolatized coal char through heating in the reactor
at 800 °C in a N2 environment. Injection of the coal char is con-
ducted in a pulse mode by loading from the top of the reactor
through the small stainless steel tube and is pulsed into the bottom
of the oxygen carrier layer of the reactor bed using N2. 10 redox
cycles are tested using the fluidized bed reactor conducting two
experiments in those 10 cycles. During cycles 1, 3, 5, and 10 solid
fuel conversion is tested. Cycles 2, 4, and 6–9 are examining the
oxygen uncoupling properties. Exhaust gas concentrations are
measured using a quadrupole mass spectrometer (MKS Cirrus 2)
and a near-IR based gas analyzer (Emerson X-Stream).
2.4. Sample characterizations
Phase identification of the oxygen carriers is conducted using
X-ray powder diffraction. Powdered samples are prepared and
tested using a Rigaku SmartLab X-ray diffractometer with Cu Ka
(k = 0.1542 nm) radiation operating at 40 kV and 44 mA. A scan-
ning range of 20–80° (2h) with a step size of 0.1° holding for
3.5 s at each step is used to generate the XRD patterns. To examine
phase properties during TPD experiments, in-situ X-ray diffraction
was conducted using an Empyrean PANalytical XRD using a similar
Cu Ka radiation operating at 45 kV and 40 mA. A 2h range of 20–80
is used at a ramp rate of 0.1° holding each step for 0.1 s. A TPD
experiment is conducted in the in-situ XRD by heating the sample
at 5 °C/min in pure argon. XRD scans are conducted the entire
length of the ramp to 1200 °C.
2.5. DFT calculations
Density functional theory (DFT) calculations are conducted to
interpret the oxygen uncoupling behavior of cubic CaMnO3 and
hexagonal BaMnO3. The calculations are performed using the
Vienna ab initio simulation package (VASP) [62,63] in which a
plane-wave basis set is used. The electron–ion interaction is mod-
eled by the projector-augmented wave (PAW) method [64,65]. The
Perdew–Burke–Enzerhoff (PBE) form of the generalized-gradient
approximation (GGA) is used for the exchange and correlation
functional [66]. The plane-wave cutoff energy is set to 425 eV. To
calculate the O vacancy (OV) formation energy, 1  2  2 and
2  2  2 supercells are chosen for BaMnO3 and CaMnO3 systems,
respectively. A 4  2  2 C-centered k-mesh and a 4  4  4
Monkhost–Pack k-mesh are used to the BaMnO3 and CaMnO3
supercells, respectively. In our calculations, both the ferromagnetic
(FM) and the antiferromagnetic (AFM) order are used for consid-
ered perovskite structures. Here, A-type AFM and G-type AFM spin
configurations are adopted by BaMnO3 and CaMnO3, respectively.
In this work, removal of one O atom from the perfect structure is
done to create a defect. The formation energy of the O vacancy is
defined as
1
EOV ¼ EAMnO3d þ EO2  EAMnO3
2
where EAMnO3d is the total energy of the perovskite supercells with
one O vacancy (A = Ba, Ca and d = 0.125), EO2 is the energy of the iso-
lated O2 molecules in the spin-polarized triplet state, and EAMnO3
corresponds to the energy of the perfect AMnO3.
4 N. Galinsky et al. / Applied Energy xxx (2015) xxx–xxx
3. Results and discussions
3.1. Motivation for dopant addition
Previous studies indicate that CaMnO3 undergoes an irreversi-
ble phase transition into CaMn2O4d and Ca2MnO4 under redox
conditions [58]. Since perovskites can accommodate significant
amount of oxygen vacancies, the decomposition would occur in
two steps. In the first step, manganese undergoes reduction from
a 4 + valence state (CaMnO3) to 3 + (CaMnO2.5) with the perovskite
structure maintained. Further reduction of Mn will result in the
formation of new phases:
6CaMnO2:5 $ 2CaMn2 O4d þ 2Ca2 MnO4 þ ðd  0:5ÞO2
ðReaction1Þ
One potential approach to avoid such an undesired transition is
to add dopants that enhance the stability of the perovskite phase.
By inspection of the Goldschmidt or bond-valence model (BVM)
tolerance factor, it is possible to project dopant effect on the struc-
tural stability of perovskites semi-empirically. The Goldschmidt
tolerance factor is defined in Eq. (1) [67]:
rA þ rO
t ¼ pffiffiffi
2ðr B þ r O Þ
where rA, rB, and rO are the ionic radii of the A-site ion, B-site ion,
and oxygen ion. BVM tolerance factor replaces the summations of
effective ionic radii in Eq. (1) with ideal A–O and B–O bond dis-
tances [68]. Based on the report by Dabrowski et al. [69], CaMnO3
has a tolerance factor of 0.985. While this value is within the suit-
able range to form stable cubic perovskites (0.9 6 t < 1), further
increase of the tolerance factor towards an ideal value of 1 for cubic
perovskite can potentially enhance the stability of the oxygen
vacant Ca1xAxMnO2.5 perovskite. It is apparent from Eq. (1) that
larger A-site dopants such as Ba and Sr should render such an effect.
It is also noted that the ionic radius of Ba2+ (1.61 angstrom) is sig-
nificantly larger than Mn3+ (0.58 angstrom under low spin) and
Ca2+ (1.34 angstrom). Therefore, significant doping of Ba will lead
to a tolerance factor larger than 1, resulting in a hexagonal per-
ovskite structure.
Effect of A-site dopant on stability of CaMnO3 perovskite family
can also preliminarily be understood from DFT calculations. The
BaMnO3/CaMnO3 structures have different magnetic ordering pat-
terns over different temperature ranges. Table 1 shows the oxygen
vacancy formation energies for BaMnO3 and CaMnO3 in both FM
and AFM states. It can be seen that O vacancy is easier form in
CaMnO3 (EOv ¼ 1:20 eV and 2.28 eV, respectively) than in
BaMnO3 (EOv ¼ 2:79 eV and 3.18 eV, respectively) regardless of
the magnetic state adopted. We found that both CaMnO3 and
BaMnO3 with AFM ordering need more energy to release oxygen
than the corresponding one with FM ordering. Indeed, the AFM
ordered state can only be remained at a relatively low temperature
(below the Néel temperature). The computational results implies
that the structural stability coupled with the oxygen donation
capability can potentially be changed by substituting Ca in the A-
site with larger cations such as Sr or Ba. In addition, the doping
effect is likely to be correlated to the experimental temperature.
Since Sr has an ionic radius slightly larger than Ca but smaller than
Table 1
Oxygen vacancy (OV) formation energy of BaMnO3 and CaMnO3 under FM (ferromag-
netic) and AFM (antiferromagetic) orders.
EOV , FM (eV) EOV AFM (eV)
BaMnO3 2.79 3.18
CaMnO3 1.20 2.28
Please cite this article in press as: Galinsky N et al. Ca1xAxMnO3 (A = Sr and Ba) perovskite based oxygen carriers for chemical looping with oxygen uncou-
pling (CLOU). Appl Energy (2015), http://dx.doi.org/10.1016/j.apenergy.2015.04.020
Ba, one could anticipate Sr addition to CaxA1xMnO3 causing simi-
lar effects as Ba addition, but to a lesser extent. Although stability
of the perovskite can only be accurately estimated by comparing
the relative stability of original and decomposed phases, vacancy
formation energy calculations together with semi-empirical analy-
sis give important clues to the selection of potentially effective
dopants (like Sr and Ba) for the CaMnO3 parent structure.
3.2. Thermal stability of CaMnO3
Although previous studies revealed irreversible decomposition
of CaMnO3 to Ruddlesden–Popper and spinel phases, the
decomposition was observed under extended redox cycles at rela-
tively low temperatures (<1000 °C) [31]. An alternative approach
that can conveniently quantify phase stability of perovskites with-
out undergoing extended redox cycles would be desirable for effi-
cient screening of perovskite based oxygen carriers. In the current
study, temperature programmed desorption (TPD) and in-situ XRD
are used to determine the stability of perovskites as well as their
initial oxygen uncoupling temperature and rate of oxygen uncou-
pling. Fig. 1 shows the TPD and in-situ XRD results. The sample
weight loss profile in TPD indicates an initial decomposition tem-
perature at approximately 800 °C followed with significant release
ð1Þ
of lattice oxygen. This is corroborated by the in-situ XRD spectra,
which exhibit significant increase in lattice parameter (decreasing
2h angles) at above 800 °C. When heated above 1000 °C, the
CaMnO3 phase decomposes into undesired Ca2MnO4 and
CaMn2O4 structures as evidenced by the peaks formed at or near
29.5, 33, 34.5, 37.7, 39, 40.4, 43.2, and etc. 2h angles.
3.3. Effect of A-site dopants on oxygen uncoupling properties
Perovskite samples with various dopant amounts are tested
using TPD to observe initial oxygen release temperature and total
amount of oxygen released. Differential thermal gravimetry
(DTG) curves of selected samples are shown in Fig. 2. The area
under the DTG curves is the total weight loss exhibited by the oxy-
gen carriers. As can be seen, CaMnO3 exhibits a significant
decomposition peak at around 800 °C. A similar feature is also
observed for Ca0.95Ba0.05MnO3. Both Sr and Ba dopant affect the ini-
tial decomposition temperature, oxygen release rate, and total oxy-
gen release of Ca1xAxMnO3. Both pure SrMnO3 and BaMnO3 are
more stable than CaMnO3 and, as a result, release less total oxygen.
BaMnO3 offers about 7 times less total oxygen release and SrMnO3
offers about 3.5 times less oxygen compared to pure CaMnO3.
When Sr and Ba are doped to the A-site, properties of both oxides
can be observed. Ba and Sr doped samples tend to decompose at
significantly lower temperatures (<700 °C) than Ca based per-
ovskites. When Ba is doped, the trend is apparent to shift between
pure CaMnO3 and pure BaMnO3. While 0.05 Ba doping does not
significantly affect the properties of oxygen uncoupling, increasing
the dopant amount to 0.25 can shift the initial reduction tempera-
ture by approximately 200 °C. Total oxygen release for
Ca0.75Ba0.25MnO3 is 3 wt.% during the TPD experiment. This is only
slightly lower than the 3.7 wt.% oxygen release by pure CaMnO3.
The rate of oxygen release in the high temperature ranges
(>750 °C), however, is significantly slower for Ca0.75Ba0.25MnO3.
Another intriguing property is the significant weight loss observed
at low temperatures (<600 °C) in which almost 0.5 wt.% of the sam-
ple is released in the form of oxygen (Fig. 2a). Further doping of Ba
onto the perovskite follows a trend to reduce total oxygen release
and oxygen donation rate in the high temperature range. Sr-doped
samples follow a trend similar to that exhibited by the Ba-doped
samples. Rates of oxygen release at high temperatures are slightly
faster than the Ba-doped samples, although still slower than pure
CaMnO3. Doping up to 0.25 Sr does not significantly affect the total
 N. Galinsky et al. / Applied Energy xxx (2015) xxx–xxx 5

Fig. 1. (a) TPD of the pure CaMnO3 at 5 °C/min to 1000 °C in pure helium environment. Sample weight: 20 mg; gas flow rate: 100 mL/min. He (grade 5.0). (b) In-situ XRD of
the same oxygen carrier at 5 °C/min to 1200 °C in argon. Gas flow rate: 50 mL/min Ar (grade 5.0).

Fig. 2. Normalized differential thermal gravimetric (DTG) curves of (a) Ba-doped and (b) Sr-doped CaMnO3 ramped to 1000 °C at a rate of 20 °C/min in a pure helium
atmosphere. Sample weight: 20 mg; gas flow rate: 100 mL/min. He (5.0 grade).

oxygen released. Initial temperature for oxygen release; on the
other hand, is lowered. For instance, Ca0.75Sr0.25MnO3 exhibits sig-
nificant weight loss in two distinct temperature regions, i.e. 300–
450 °C and >600 °C. The low temperature oxygen release could
be associated with chemisorbed oxygen in the lattice structure.
Fig. 3 summarizes the total oxygen release and initial decomposi-
tion temperature for several representative perovskite samples.
3.4. Structural and stability studies
Effectiveness of dopant addition largely relies on the compati-
bility of the dopant and its parent structure. Ideally, the dopant
should be fully incorporated into the host structure to form a
homogeneous solid state solution. Fig. 4 illustrates the XRD pat-
terns for the oxygen carriers for Ba and Sr doped CaMnO3 at a range

Please cite this article in press as: Galinsky N et al. Ca1xAxMnO3 (A = Sr and Ba) perovskite based oxygen carriers for chemical looping with oxygen uncou-
pling (CLOU). Appl Energy (2015), http://dx.doi.org/10.1016/j.apenergy.2015.04.020
6 N. Galinsky et al. / Applied Energy xxx (2015) xxx–xxx

Fig. 3. Total oxygen release and initial decomposition temperature comparisons between CaMnO3 and Sr- and Ba-doped synthesized oxygen carriers. Sample weight: 20 mg;
gas flow rate: 100 mL/min. He (5.0 grade).

Fig. 4. XRD of various doped CaMnO3 with (a) Sr doping and (b) Ba doping. Phases: (d) SrMnO3, (x) CaMnO3, (N) BaMnO3, and (H) Mn3O4.

of x = 0 to x = 1. As can be seen, Ba cannot be fully incorporated into
the CaMnO3 structure in most cases. Even at small dopant levels
(x < 0.1), a secondary hexagonal BaMnO3 phase can be identified.
When doped further, ternary phases, such as Mn oxides, are
observed until A-site is fully occupied by Ba. Sr-doped CaMnO3,
on the other hand, forms a relatively homogenous solid-solution.
Sr doping up to x = 0.25 exhibits complete incorporation of Sr into
CaMnO3 while shifting the structure from cubic to orthorhombic.
At x = 0.5, co-existence of SrMnO3 and CaMnO3 structures are
observed. At higher doping levels (>0.5), a single orthorhombic
SrMnO3 phase is observed.
The primary motivation for dopant addition is to stabilize the
CaMnO3 structure and prevent the formation of stable spinel
phases at high temperatures. Fig. 5 investigates the in-situ XRD
of the Sr- and Ba-doped CaMnO3. For the Sr-doped sample, the
structure of the perovskite phase is maintained even at a high tem-
perature of 1200 °C. To compare, CaMnO3 is decomposed at
1000 °C. Significant shift of 2h angles, which are indicative of oxy-
gen release, begins at approximately 600 °C. This is consistent with
TPD observations. Ca1xBaxMnO3 sample with a low dopant level
(x = 0.05) was chosen for in-situ XRD due to the difficulty to incor-
porate Ba into the CaMnO3 host structure. As shown in Fig. 5, the
Ba-doped sample, similar to CaMnO3, exhibited phase
decomposition at 1000 °C. It is therefore concluded that Sr is likely
to be a more suitable dopant for CaMnO3, since it readily incorpo-
rates into the host structure and helps to enhance the stability of
the perovskite phase. Ba-doped samples, on the other hand, do
not exhibit the desired CLOU properties. This may have resulted
from the significant differences in ionic sizes between Ba2+ and
Ca2+, which can lead to large lattice distortions and stresses.
3.5. Redox testing
CLOU performance of an oxygen carrier can be characterized by
its oxygen donation properties under cyclic redox conditions. In
order to determine the oxygen donation properties of the reference
(CaMnO3) and Sr doped (Ca0.75Sr0.25MnO3) oxygen carrier samples,
short-term isothermal redox experiments are carried out at 650 °C,
750 °C, 850 °C, and 950 °C. The results are summarized in Fig. 6.
As can be seen, undoped CaMnO3 does not observe any notice-
able weight loss at 650 °C. Once the temperature reaches 850 °C,
significant oxygen release is observed. When the temperature is
increased even further, the oxygen carrier exhibits even higher
oxygen donation.
When doping Sr and Ba into CaMnO3, different phenomena are
observed. When Ba is doped, there is no indication that the

Please cite this article in press as: Galinsky N et al. Ca1xAxMnO3 (A = Sr and Ba) perovskite based oxygen carriers for chemical looping with oxygen uncou-
pling (CLOU). Appl Energy (2015), http://dx.doi.org/10.1016/j.apenergy.2015.04.020
 N. Galinsky et al. / Applied Energy xxx (2015) xxx–xxx 7

Fig. 5. In-situ XRD of the (a) Ca0.75Sr0.25MnO3 and (b) Ca0.95Ba0.05MnO3 in argon at a ramping rate of 5 °C/min to 1200 °C. Gas flow rate: 50 mL/min Ar (grade 5.0).

material is being reoxidized to any extent at any temperature using

10% O2. From XRD of the reduced sample, the formation of spinel
CaMn2O4 phase is observed. This may indicate that Ba could be dis-
torting the structure to promote the decomposition of the cubic
CaMnO3 phase. In-situ XRD (Fig. 5b) also corroborates the
formation of spinel and reduced perovskite phases at a lower tem-
perature than pure CaMnO3. When Sr is doped into the CaMnO3
structure, it promotes oxygen donation at a much lower tempera-
ture while still being able to reoxidize. While at 650 °C, 0.1 wt.%
oxygen release is observed. Once the material is heated to 850 and
950 °C, total oxygen release becomes more significant. In pure
CaMnO3, near complete oxidation using 10% oxygen is achieved.
However, Sr-doped CaMnO3 is only able to restore roughly 99%
of the initial weight. Each sample was cycled 5 times at each tem-
perature and no change in performance was observed.
In chemical looping schemes, long term cycling is important
due to the need to replenish the solid oxygen carriers over time.
Fig. 7 examines the Sr-doped perovskite at 850 °C for 100
uncoupling cycles. Over 100 cycles, the material has no observable Fig. 6. Isothermal weight loss at temperatures between 650 and 950 °C. Sample
weight: 30 mg. Flow rates: reduction step: 30 mL/min He (5.0 grade) and 60 mL/
deactivation and is very stable throughout all 100 cycles. After 100
min Ar (5.0 grade). Oxidation step: additional 10 mL/min O2 (extra dry grade) added
cycles are performed, oxygen release is still observed at lower to aforementioned gas stream.

Please cite this article in press as: Galinsky N et al. Ca1xAxMnO3 (A = Sr and Ba) perovskite based oxygen carriers for chemical looping with oxygen uncou-
pling (CLOU). Appl Energy (2015), http://dx.doi.org/10.1016/j.apenergy.2015.04.020
8 N. Galinsky et al. / Applied Energy xxx (2015) xxx–xxx
Fig. 7. 100 Cycles at 850 °C Ca0.75Sr0.25MnO3 oxygen carrier. Sample weight: 50 mg.
Gas flow rates: reduction step: 30 mL/min He (5.0 grade) and 60 mL/min Ar (5.0
grade). Oxidation step: additional 10 mL/min O2 (extra dry grade) added to
aforementioned inert gas.
temperatures 650 °C and 750 °C. The oxygen capacity and rate of
oxygen release at these lower temperatures are comparable to
what was observed in Fig. 6. XRD analysis shows a small amount
of SrMnO3 appearing after the 100 cycles (see Fig. S2). However,
no spinel or Ruddlesden–Popper phases were identified.
Initial coal char reactions were conducted in a TGA. Coal char
was well mixed with the oxygen carrier and placed in the TGA
and heated to 250 °C to remove any moisture. The TGA is then
heated to 950 °C in helium and the reaction is allowed to proceed
to completion. Fig. 8 examines the results of pure CaMnO3 versus a
Sr-doped sample. The Sr-doped oxygen carrier has an initial reac-
tion temperature of approximately 100 °C lower compared to the
undoped CaMnO3 oxygen carrier. Besides the lower reaction tem-
perature, the Sr-doped has a higher activity in reaching full conver-
sion of solid char.
Fluidized bed results are shown in Fig. 9. Examination of the
solid char cycles of the Ca0.75Sr0.25MnO3 reveals nearly 100% con-
version of the coal char in every cycle. This is confirmed through
no observable CO2 during the oxidation step (see Fig. S3). Further
comparison of the CO2 to CO selectivity reveals around 90%
Fig. 8. Char combustion using TGA of pure and Sr-doped CaMnO3. Heating in inert
to 250 °C for drying, then heated at a rate of 20 °C/min in helium to 950 °C. Sample
weight: 20 mg for the oxygen carrier and 0.2 mg of coal char. Gas flow rates:
100 mL/min He (5.0 grade).
Please cite this article in press as: Galinsky N et al. Ca1xAxMnO3 (A = Sr and Ba) perovskite based oxygen carriers for chemical looping with oxygen uncou-
pling (CLOU). Appl Energy (2015), http://dx.doi.org/10.1016/j.apenergy.2015.04.020
Fig. 9. Char conversion and CO2 selectivity of the Ca0.75Sr0.25MnO3 oxygen carrier in
a fluidized bed reactor. Sample weight: 17 g. Ca0.75Sr0.25MnO3 and 10 mg of char
temperature: 850 °C gas flow rates: nitrogen: 800 mL/min (grade 5.0) and helium
(grade 5.0): 280 mL/min (char reduction) and oxygen (extra dry grade): 120 mL/
min (during oxidation only).
selectivity during every cycle. The fluidized bed results confirm
the viability of the Ca0.75Sr0.25MnO3 oxygen carrier in CLOU
applications.
4. Conclusions
The present study investigates the redox properties of doped
CaMnO3 as oxygen carriers for CLOU processes. The effects of A-site
substitution with Sr and Ba dopants on structural stability, oxygen
carrying capacity, and oxygen donation temperature of the oxygen
carriers are investigated. The A-site dopants are chosen through
both a semi-empirical approach and DFT calculations for oxygen
vacancy formation energy. Ba addition to the CaMnO3 structure
is found to be ineffective due to the inability of Ba to incorporate
into the CaMnO3 structure. Sr, on the other hand, is found to form
homogeneous solid solutions with the CaMnO3 host structure.
Sr-doped samples are also found to be effective in preventing irre-
versible decomposition of the parent perovskite structure to the
Ruddlesden–Popper (Ca2MnO4) and spinel (CaMn2O4) phases.
Excellent stability is observed for Sr doped sample
(Ca0.75Sr0.25MnO3) through various conditions including heating
to 1200 °C, 100 isothermal redox cycles, and reaction with solid
fuels. Besides the increased stability of the structure, Sr-doped oxy-
gen carriers exhibit noticeable oxygen release at significantly
lower temperature than that observed for pure CaMnO3. Due to
its various advantages compared to undoped CaMnO3, Sr-doped
CaMnO3 oxygen carrier offers a potentially viable option for solid
fuel conversion in CLC schemes.
Acknowledgements
Funding supports from the U.S. Department of Energy (Award
Number FE001247) and Illinois Clean Coal Institute (Award
Number 14/5C-2) are greatly appreciated. We acknowledge the
use of the Analytical Instrumentation Facility (AIF) at North
Carolina State University, which is supported by the State of
North Carolina and the National Science Foundation. We would
also like to acknowledge Feng He for his help in setting up some
of the experiments.
 N. Galinsky et al. / Applied Energy xxx (2015) xxx–xxx
Appendix A. Supplementary material
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.apenergy.2015.
04.020.
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