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CuO promoted Mn2O3-based materials for solid

fuel combustion with inherent CO2 capture†
Cite this: J. Mater. Chem. A, 2015, 3,
10545
D. Hosseini,a Q. Imtiaz,a P. M. Abdala,a S. Yoon,b A. M. Kierzkowska,a A. Weidenkaffc
and C. R. Müller*a

Received 9th February 2015
Accepted 10th April 2015
DOI: 10.1039/c5ta01088h
www.rsc.org/MaterialsA
We experimentally demonstrate the promising redox and oxygen release characteristics of a novel
bimetallic Cu–Mn oxygen carrier for chemical-looping with oxygen uncoupling (CLOU) based CO2
capture. The new material was prepared via a co-precipitation technique and showed a higher oxygen
partial pressure than pure CuO and a higher oxygen carrying capacity than Mn2O3, thus, synergistically
combining the advantages of the individual metal oxides. The promising CLOU characteristics of the new
material were demonstrated further by combusting charcoal fully in a fluidized bed and producing a
pure stream of CO2.

Initially CLC was considered for gaseous fuels only.7

Introduction
According to the Intergovernmental Panel on Climate Change
(IPCC), the implementation of carbon dioxide capture and
storage (CCS) technologies could reduce the total global,
anthropogenic CO2 emissions by approximately 20%.1–3
However, the rst generation CO2 capture technology i.e. amine
scrubbing is possibly prohibitively expensive.4 Nonetheless,
emerging second and third-generation CCS technologies such
as calcium looping and chemical looping combustion (CLC)
have the potential to reduce substantially the costs of CO2
capture.5,7 In CLC oxygen is transferred from air to a hydro-
carbonaceous fuel via a solid oxygen carrier, typically a transi-
tion metal oxide (MexOy).6 In the so-called fuel reactor, the fuel
is oxidised and the oxygen carrier is reduced. The off-gas of the
fuel reactor comprises a mixture of CO2 and H2O (reaction (1)):
However, since coal is substantially more carbon dioxide
intensive than methane, substantial research efforts have been
directed towards the development of CLC schemes that allow
the use of solid fuels.
Here, one possible process option is the prior gasication of the
solid fuel to yield a synthesis gas.8,9 However, gasication is a
comparatively slow process since the main gasication products
act as poisons to the gasication reaction.10 An alternative strategy
is chemical-looping with oxygen uncoupling (CLOU).11 Here,
molecular oxygen is released from the lattice of an oxygen carrier.
The combustion reaction of the solid fuel with the molecular
oxygen released is very fast when compared to the gasication
reaction. Conceptually, CLOU is similar to the CLC process, but
involves three steps. In the rst step, molecular oxygen is released
via the decomposition of the oxygen carrier according to

CnH2m + (2n + m)MexOy / nCO2 + mH2O MexOy / MexO(y 2) + O2 (3)

+ (2n + m)MexO(y 1) (1)
Subsequently, the solid fuel reacts with the oxygen released
Aer the condensation of steam, a pure stream of CO2 is to produce, aer the condensation of steam, a pure stream of
obtained. To close the redox cycle, the reduced oxygen carrier is CO2:
re-oxidized with air (reaction (2)):
CnH2m + (n + m/2)O2 / nCO2 + mH2O (4)
MexO(y 2) + O2 / MexOy (2)
Finally, the oxygen carrier is transferred back to its initial
oxidation state by using air (reaction (2)). However, the addi-
a
tional requirement to release molecular oxygen at typical
Laboratory of Energy Science and Engineering, ETH Zürich, Leonhardstrasse 21, 8092,
Zürich, Switzerland. E-mail: muelchri@ethz.ch operating temperatures reduces the number of suitable oxygen
b
Laboratory for Energy Conversion Materials, Empa-Swiss Federal Laboratories for carriers for CLOU. An appropriate oxygen carrier for CLOU must
Materials Science and Technology, Ueberlandstrasse 129, 8600, Dübendorf, possess the following characteristics: (i) a high oxygen carrying
Switzerland capacity, (ii) sufficiently high oxygen partial pressure at typical
operating temperatures (800–1100  C), (iii) thermal stability and
c
Institute for Materials Science, University of Stuttgart, Heisenbergstrasse 3, 70569,
Stuttgart, Germany
(iv) fast decomposition kinetics. In addition, resistance to
† Electronic supplementary information (ESI) available. See DOI:
10.1039/c5ta01088h
attrition and agglomeration, cost and environmental impact

This journal is © The Royal Society of Chemistry 2015 J. Mater. Chem. A, 2015, 3, 10545–10550 | 10545
 View Article Online

Journal of Materials Chemistry A Paper

In this work we report the development of bimetallic copper–

manganese oxygen carriers for CLOU with the aim to overcome
the drawbacks of the individual metal oxides. The inuence of
the ratio of Cu to Mn on the cyclic redox performance and oxygen
uncoupling capacity was systematically studied over multiple
cycles. The oxygen carriers were characterized in detail to quan-
tify the synergistic effect of combining Cu and Mn, i.e. the release
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of a large quantity of molecular oxygen at a comparatively low

temperature. We also demonstrate the excellent CLOU capability
of the novel materials under practically relevant conditions, i.e. in
a uidized bed at 800  C using a solid fuel viz. charcoal (Fig. S1†).
The details of the synthesis procedure, the characterization tools
Fig. 1 Equilibrium oxygen partial pressure as a function of tempera-
used and the experimental set-up of the chemical-looping
ture, (——) Mn2O3, (C) CuMn2O4, (———) CuO and (.) CuAl2O4. The experiments are provided in ESI.†
thermodynamic data for the pure metal oxides, i.e. CuO and Mn2O3,
CuMn2O4 and CuAl2O4 were taken from Barin and Knacke,23 Schenck
and Kurzen24 and Jacob and Alcock25 respectively. Results and discussion
X-ray diffraction (XRD) measurements were performed to
determine the composition of the calcined oxygen carriers
have to be considered. With regard to equilibrium thermody-
(Fig. S2†). In all oxygen carriers that contained both Cu and Mn,
namics CuO and Mn2O3 are arguably the most attractive oxygen
a spinel phase (CuMn2O4) was observed. Depending on the
carriers for CLOU.12 However, both materials have some draw-
mass ratio of Cu to Mn, also CuO or Mn3O4 were identied. For
backs. In the case of pure CuO, sintering and a comparatively
example, the X-ray diffractograms of 75Cu–25Mn and 50Cu–
low oxygen partial pressure at temperatures below 900  C
50Mn revealed the presence of CuO and CuMn2O4. The oxygen
(Fig. 1) are the main disadvantages. The Mn2O3/Mn3O4 system
carrier with a ratio of CuO to Mn2O3 of 25 : 75 wt% contained
has a low oxygen carrying capacity when compared to CuO/
Mn3O4 and CuMn2O4.
Cu2O (0.03 g O2/g for Mn2O3 versus 0.1 g O2/g for CuO),12 but, on
The surface morphology of the calcined oxygen carriers was
the other hand, a comparatively high partial pressure of O2.
characterized by scanning electron microscopy (SEM, Fig. 2). Pure
A successful strategy to reduce particle growth and agglom-
CuO (Fig. 2(A)) is irregularly shaped with very few faceted surfaces.
eration due to sintering has been the stabilization of the active
On the other hand, pure Mn2O3 (Fig. 2(F)) is composed of
metal by a high Tammann temperature support such as Al2O3,
agglomerated nanoparticles with an average size of 230  30 nm.
TiO2, SiO2, MgO or ZrO2.13–17 Additionally, to further improve
As seen in Fig. 2(B–E), the surface of CuMn2O4 containing oxygen
the performance of the oxygen carriers the use of bimetallic
carriers is composed of cuboidal or polyhedral structures. The
materials has been proposed.18 For example, Azad et al.19
sharpness of the edges of the polyhedron seems to be highest for
studied the oxygen uncoupling characteristics of CuxMn3 xO4
the Mn- and Cu richest materials. Furthermore, the surface
(0.1 # x # 2.5) in a uidized bed (temperature range 800–850  C)
morphology of 34Cu–66Mn, i.e. the oxygen carrier that is almost
using CH4 as a fuel. The oxygen carriers were prepared by
pure CuMn2O4, was found to be similar to that of CuO. These
physically mixing the metal oxides, followed by extrusion. The
observations indicate that the surface morphology of the spinel
materials developed showed a high reactivity with CH4 and,
phase is affected by excess CuO or Mn3O4. In general, the micro-
irrespective of the value of x, no agglomeration was observed.
graphs of Cu containing materials show a comparatively dense
However, the cyclic stability of the new materials was not
assessed. In a subsequent study, Mohammad Pour et al.20
reported the CLOU properties of Cu–Mn oxides prepared by
freeze granulation. The synthesized oxygen carriers released O2
at 750  C. However, again the cyclic stability of the materials was
not investigated. Generally, physical synthesis methods such as
mechanical mixing or freeze granulation do not allow the mix-
ing of the active components on a molecular or atomic level,
thus typically resulting in materials that show poor resistance
towards sintering when tested over repeated redox cycles.17 On
the other hand, wet-chemical synthesis approaches such as co-
precipitation could improve the level of mixing between the
active compound(s) and the support. For example, Imtiaz
et al.21,22 reported the synthesis of MgAl2O4- or Al2O3-stabilized,
Cu-rich oxygen carriers by using a co-precipitation technique.
The oxygen carriers developed possessed excellent mechanical Fig. 2SEM images of the calcined oxygen carriers: (A) CuO, (B) 75Cu–
25Mn, (C) 50Cu–50Mn, (D) 34Cu–66Mn, (E) 25Cu–75Mn, (F) Mn2O3.
properties and a stable redox performance over multiple cycles.
The scale bar is 2 mm.

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Paper
surface structure with very little porosity. This is possibly due to
rapid grain growth at high calcination temperatures (900  C).
H2-temperature programmed reduction (TPR) experiments
were carried out to investigate the effect of the ratio of Cu to Mn
on the reducibility of the materials (Fig. 3). The quantities of H2
consumed, as calculated from the H2-TPR experiments, are
summarized in Table S1.† Pure CuO has a broad, single H2
consumption peak centred at 335  C. On the other hand, the
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reduction of Mn2O3 occurred in two main steps: rst Mn2O3 is
reduced to Mn3O4 at 370  C followed by the reduction of
Mn3O4 to MnO at 455  C. This two-step reduction mechanism
is in good agreement with a previous report.26 The XRD
measurements of reduced Mn2O3 conrms the presence of
MnO. Furthermore, the total quantity of H2 consumed was
12.3 mmol g 1 and 6.25 mmol g 1 for CuO and Mn2O3,
respectively. These values are very close to the theoretically
expected values of, respectively, 12.5 mmol g 1 and 6.3 mmol
g 1. From Fig. 3 it is clear that in the bimetallic oxygen carriers
the reduction characteristics of the pure phases were altered.
Importantly, the reduction of the bimetallic oxygen carriers
started at signicantly lower temperatures when compared to
the pure CuO and pure Mn2O3 phases. This observation could
be explained by the fact that CuMn2O4 contains Mn4+ which is
reduced at a lower temperature than Mn3+.27,28 Deconvolution of
the overlapping peaks in the H2-TPR proles of the bimetallic
oxygen carriers revealed the presence of two reduction steps.
Reduction at the lower temperature (290  C) is attributed to
the reduction of Cu2+. On the other hand, the peak at 320  C is
due to the reduction of Mn3+ and Mn4+ to Mn2+. XRD
measurements of the reduced bimetallic materials revealed
only the presence of metallic copper and MnO (Fig. S3†). Fig. 3
also conrms that an increasing Mn content in the bimetallic
oxygen carriers shis the reduction temperature of manganese
oxide to lower temperatures. Furthermore, the H2 consumption
Fig. 3 H2-TPR profiles of the calcined oxygen carriers.
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decreases with an increasing Mn content. The total H2
consumption of bimetallic Cu–Mn is higher than the theoreti-
cally expected value, most likely due to the presence of Mn4+ in
the spinel as conrmed subsequently by X-ray absorption
spectroscopy. The theoretical H2 consumption was calculated
using the given Cu to Mn ratio and assuming a reduction of
Mn2O3 to MnO and CuO to Cu.
To investigate the oxidation states of Cu and Mn in the spinel
system, near edge X-ray absorption spectroscopy (XANES)
studies were performed at the Cu and Mn K-edges. In order to
study the Cu oxidation state in the spinel, an oxygen carrier
without CuO phase was selected. Similarly, for the Mn oxidation
state an oxygen carrier without excess of Mn3O4 phase was
chosen. This is based on the information extracted from the
XRD data shown in Fig. S2.† Fig. 4 (Top) shows the Cu K-edge
XANES spectra of 25Cu–75Mn and the references CuO and
Cu2O. The edge position of the spinel is close to CuO, indicating
an oxidation state close to Cu2+. Fig. 4 (Bottom) shows the Mn K-
edge XANES spectra of 50Cu–50Mn and the references MnO,
Mn3O4, Mn2O3 and MnO2. The edge in the bimetallic sample
lies between those of MnO2 and Mn2O3, suggesting an average
valence state between Mn3+ and Mn4+ in the oxygen carrier.
To study the effect of the ratio of Cu to Mn on the decom-
position characteristics, temperature programmed decomposi-
tion (TPD) experiments were performed. In Fig. 5, the
normalized mass loss is plotted as a function of temperature.
Fig. 5 shows that pure CuO decomposes in a single step (in the
temperature range 770–970  C) to Cu2O. The single step
decomposition of Mn2O3 to Mn3O4 occurred, as expected from
equilibrium thermodynamics, at much lower temperatures, viz.
in the temperature range 730–850  C. Furthermore, the TPD
Fig. 4 Top: Cu K-edge XANES data of 25Cu–75Mn, CuO and Cu2O.
Bottom: Mn K-edge XANES of 50Cu–50Mn, MnO2 and Mn2O3.
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Fig. 5 TPD profiles of the calcined oxygen carriers in N2: (a) Mn2O3, (b)
25Cu–75Mn, (c) 34Cu–66Mn, (d) 50Cu–50Mn, (e) 75Cu–25Mn, (f) CuO.
experiments also reveal a single-step decomposition mecha-
nism for 25Cu–75Mn and 34Cu–66Mn according to:
3CuMn2O4 / 3CuMnO2 + Mn3O4 + O2 (5)
As conrmed by XRD (Fig. S2†), 25Cu–75Mn contains
CuMn2O4 spinel and Mn3O4. It should be noted that the
conditions used in the TPD experiments do not allow the
decomposition of Mn3O4 to MnO. Thus, a single decomposition
step is observed for CuMn2O4 (decomposition to CuMnO2).
Increasing the CuO content above 50 wt% in the oxygen carrier
resulted in a two-step decomposition mechanism (Fig. 5). XRD
measurements of partially and fully decomposed 50Cu–50Mn
and 75Cu–25Mn conrm that in the rst step CuMn2O4 is
decomposed to CuMnO2 and in the second step excess CuO
decomposes to Cu2O. Thus, the overall decomposition reaction
for Cu-rich oxygen carriers can be written as:
CuMn2O4 + 3CuO / 2CuMnO2 + Cu2O + O2 (6)
As shown in the inset of Fig. 5 the decomposition of the
bimetallic oxygen carriers started at 650  C. Thus, the
decomposition of the bimetallic oxygen carriers occurs at a
lower temperature when compared to the pure oxides, i.e. CuO
and Mn2O3. Importantly, combining the oxides of Mn and Cu
also increased the quantity of oxygen released compared to pure
Mn2O3. Hence, the new bimetallic materials possess very
promising CLOU characteristics. The oxygen release capacity
and the decomposition temperature of the synthesized oxygen
carriers are summarized in Table 1.
Equilibrium thermodynamic calculations show that the
equilibrium O2 partial pressure of CuMn2O4 is higher than that
of CuO (Fig. 1). In order to determine the equilibrium O2 partial
pressure of the different bimetallic oxygen carriers, the
decomposition reaction was conducted in a packed bed reactor
in a N2 atmosphere. Fig. S4† plots the O2 partial pressure at 800  C
for the synthesized bimetallic oxygen carriers, pure Mn3O4 and
the state-of-the-art reference material CuAl (the CuAl oxygen
carrier contained 70 wt% CuO and 30 wt% Al2O3). Under the
conditions studied here, Mn3O4 could not be decomposed to
MnO. From Fig. 1 it is expected that at 800  C CuO has a very low
10548 | J. Mater. Chem. A, 2015, 3, 10545–10550
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Table 1 Quantity of oxygen released and the decomposition
temperature as determined from the acquired TPD profiles
Decomposition
temperature
range ( C)
Oxygen release capacity
Oxygen carrier Starta Endb (g O2/g oxygen carrier)
CuO 785 970 0.097
75Cu–25Mn 660 950 0.085
50Cu–50Mn 630 995 0.064
34Cu–66Mn 665 1025 0.051
25Cu–75Mn 655 1010 0.045
Mn2O3 720 930 0.034
a
Dened as a 1% weight change. b Dened as a 98% weight change.
oxygen partial pressure. This is conrmed by the low oxygen
partial pressure of CuAl (Fig. S4†). All bimetallic oxygen carriers
showed very high O2 partial pressures that substantially excee-
ded the values of the references CuAl and Mn3O4.
The cyclic oxygen uncoupling capacity of the bimetallic oxygen
carriers was evaluated in a TGA at 850  C. The oxygen carriers
were subjected to ten CLOU cycles. The amount of O2 released is
plotted in Fig. S5(a).† The oxygen carrier 75Cu–25Mn possessed a
high but continuously decreasing O2 carrying capacity. This
observation could be explained by a decreasing decomposition
rate with cycle number. Fig. S5(b)† shows that within the xed
decomposition time chosen (75 min), 75Cu–25Mn decomposes
completely in the 2nd CLOU cycle, but incompletely in the 10th
CLOU cycle. The decreasing decomposition rate is most likely
due to sintering and agglomeration decreasing the effective
surface area and porosity of the material (Fig. S5(c)†). Similarly,
50Cu–50Mn also showed a gradual, albeit much slower, decay in
the oxygen uncoupling capacity with cycle number. For Cu-rich
oxygen carriers, the decay in the cyclic oxygen release was found
to decrease with decreasing CuO content. This is in agreement
with the TPD measurements (Fig. 5), which show that the oxygen
carriers with a lower CuO content possess faster apparent
decomposition rates. The CLOU performance of 34Cu–66Mn
showed a 12% decrease in the quantity of oxygen released as
determined over the ten cycle experiment. On the other hand,
25Cu–75Mn possessed a stable oxygen release capacity over the
10 CLOU cycles tested. The experimentally determined cyclic
oxygen release, viz. 1.4 mmol g 1 oxygen carrier was close to its
theoretically expected value of 1.53 mmol g 1 oxygen carrier.
To assess the attrition resistance of the oxygen carriers
synthesized, additional CLOU experiments were performed in a
uidised bed at 850  C and 950  C. The decomposition reaction
was performed in a N2 atmosphere, whereas a mixture of 10.5
vol% O2 and 89.5 vol% N2 was used for re-oxidation. Fig. 6 plots
the cyclic O2 release of the bimetallic oxygen carriers at 850 and
950  C. The oxygen carrier 75Cu–25Mn shows a low cyclic O2
release at 850  C. This is due to the fact that the CuO–Cu2O
couple has a low equilibrium oxygen partial pressure at 850  C.
Thus, the O2 released is predominantly due to the decomposi-
tion of the spinel phase that is, however, only present in a
comparatively small quantity in 75Cu–25Mn. Furthermore,
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Fig. 6 Cyclic CLOU characteristics of the oxygen carriers synthesized
as determined in a fluidised bed at (a) 850  C and (b) 950  C. The
theoretically expected values for Mn3O4, 25Cu–75Mn, 34Cu–66Mn,
50Cu–50Mn, 75Cu–25Mn, CuO and CuAl are 0, 1.53, 1.67, 2.1, 2.6, 3.14
and 2.20 mmol g 1, respectively.
75Cu–25Mn exhibits a high, but continuously decreasing
oxygen release at 950  C. The decreasing quantity of oxygen
released is due to sintering and/or agglomeration. At 850  C
50Cu–50Mn also shows a continuously decreasing oxygen
release over the rst 10 cycles. Despite its stable oxygen release
over the second 10 cycles, 50Cu–50Mn shows again a decrease
over the last 5 cycles.
To understand better the origin of the decreasing oxygen
release, oxidised 50Cu–50Mn that has undergone 25 redox
cycles was analysed further by SEM (Fig. S6†). The sintering of
individual particles can be clearly observed. On the other hand,
50Cu–50Mn possessed a stable O2 release when tested at 950  C.
However, the quantity of oxygen released was 60% lower than
the theoretically expected value of 2.1 mmol g 1 oxygen carrier.
A possible explanation for the low oxygen release capacity is a
rapid decrease in surface area owing to sintering under the
operating conditions studied here (uidised bed at 950  C). A
similar observation was made for 34Cu–66Mn (Fig. 6(b)). The
oxygen carrier 34Cu–66Mn releases only 18% of the theoreti-
cally expected quantity of 1.67 mmol g 1 oxygen carrier at 950  C.
At 850  C, the quantity of O2 released by 34Cu–66Mn continu-
ously decreased with cycle number owing to sintering and
agglomeration. For Al2O3-stabilised Cu (CuAl), the quantity of
O2 released started to decrease aer 15 cycles. Under the
conditions studied, the decomposition of CuAl2O4 is not fully
reversible22 resulting in a lower quantity of oxygen released than
the theoretically expected value of 2.2 mmol g 1. A very stable
cyclic oxygen release, and close to the theoretically expected
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Journal of Materials Chemistry A
value of 1.53 mmol g 1, was observed for 25Cu–75Mn (both at
850  C and 950  C). The oxygen carrier 25Cu–75Mn contains
CuMn2O4 and excess Mn3O4. Furthermore, no agglomeration
was observed during the 25-cycle experiment. A size analysis of
cycled 25Cu–75Mn (1 g) detected only a small quantity (15 mg)
of particles with dp < 300 mm, indicative a high attrition resis-
tance of the material. The stable O2 release of 25Cu–75Mn is
attributed to the presence of excess Mn3O4 (subsequently
conrmed via in situ XRD) which has a high Tammann
temperature (644  C) when compared to Mn2O3 (334  C) and
CuO (526  C). Thus, excess Mn3O4 in 25Cu–75Mn effectively
stabilized CuMn2O4 against sintering and agglomeration.
To investigate the phase changes occurring during decom-
position and re-oxidation, in situ XRD measurements were
performed over three CLOU cycles at 850  C. The X-ray dif-
fractograms of Mn-rich (25Cu–75Mn) and Cu-rich (50Cu–50Mn)
oxygen carriers are given in Fig. 7(a) and (b), respectively. Fig. 7
shows that independent of the Cu to Mn ratio, the spinel
CuMn2O4 decomposed to CuMnO2. In situ XRD also conrms
that the excess phase in 50Cu–50Mn, i.e. CuO, is reversibly
decomposed to Cu2O (Fig. 5(b)), whereas in 25Cu–75Mn
(Fig. 7(a)) the excess phase, i.e. Mn3O4, is not decomposed
under the conditions studied here. The stable CLOU charac-
teristics of 25Cu–75Mn are attributed to the presence of high
Tammann temperature Mn3O4 in both the decomposed and
oxidized oxygen carriers.
Based on the TGA and uidised bed experiments, 25Cu–
75Mn was chosen as the most promising oxygen carrier to be
assessed further in a CLOU experiment using a solid fuel. In a
uidized bed, 10 CLOU cycles using charcoal as a fuel were
performed at 800  C. The concentration proles of O2 and CO2
in the off-gas of the uidized bed are plotted in Fig. 8. Fig. 8(a)
convincingly demonstrates that 25Cu–75Mn fully combusts the
charcoal added. Indeed, no CO2 could be detected in the re-
oxidation step which conrms that the fuel was completely
burnt by the molecular oxygen released by the oxygen carrier.
During combustion the concentration of CO was below the
detection limit of the analyser (0.01 vol% CO). The decompo-
sition kinetics were fast, as demonstrated by the fact that the
combustion was completed within 5 min. Furthermore, no
agglomeration was observed aer the 10-cycle experiment. On
the other hand, Fig. 8(b) shows that the charcoal added to a bed
Fig. 7 In situ XRD of (a) 25Cu–75Mn and (b) 50Cu–50Mn: (-)
CuMn2O4, (:) CuMnO2, (C) Mn3O4, (B) CuO, (+) Cu2O. The blue line
and red line correspond to air and N2, respectively.
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Fig. 8 The gas composition of the off-gas leaving the fluidized bed.
Charcoal (50 mg) was used as the solid fuel and (a) 25Cu–75Mn or (b)
CuAl were used as the oxygen carrier at 800  C: (—) O2, (—) CO2.
of CuAl was not fully burnt, not even aer 10 min. This is
conrmed by the detection of CO2 in the re-oxidation step.
Conclusions
In this study bimetallic Cu–Mn oxygen carries were synthesized
via a co-precipitation technique. Using XANES we could conrm
experimentally the presence of Cu2+ and Mn4+ in the spinel
system. TPD and H2-TPR conrm that the bimetallic oxygen
carriers possess improved decomposition and redox character-
istics when compared to the individual metal oxides. However,
cyclic CLOU experiments revealed that Cu-rich oxygen carriers
have a high but continuously decreasing oxygen release due to
the slow (and decreasing) decomposition kinetics of CuO. On the
other hand, the formation of a spinel markedly enhanced the O2
equilibrium partial pressure at 800  C when compared to pure
CuO. Fluidised bed experiments revealed a cyclically stable
oxygen release over 25 cycles for 25Cu–75Mn, an oxygen carrier
that contains CuMn2O4 and Mn3O4. Finally, it was demonstrated
that the best bimetallic oxygen carrier synthesized (25Cu–75Mn)
is able to fully oxy-combust a solid fuel at 800  C over 10 CLOU
cycles. The oxygen carrier 25Cu–75Mn possessed a high resis-
tance to agglomeration, a high oxygen carrying capacity, a high
solid fuel conversion rate and a high cyclic oxygen release over
multiple cycles when compared to the individual metal oxides.
These favorable characteristics make the newly developed
bimetallic Cu–Mn oxygen carrier a promising material for CLOU.
Acknowledgements
We are grateful to the Swiss national science foundation (SNF)
for nancial support (Project IZERZ0_141976/1). We also thank
Mrs Lydia Zender for her help with the XRD analysis, and
Scientic Center for Optical and Electron Microscopy (ScopeM)
at ETH Zurich for providing access to and training on scanning
electron microscopes. The Swiss–Norwegian Beamline (ESRF,
Grenoble, France) is gratefully acknowledged for the provision
of beamtime at the synchrotron.
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