Fuel 230 (2018) 410–417

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Full Length Article

A mechanistic study of CO oxidation over spinel MnFe2O4 surface during T

chemical-looping combustion
⁎
Feng Liu, Jing Liu , Yingju Yang, Xufeng Wang
State Key Laboratory of Coal Combustion, School of Energy and Power Engineering, Huazhong University of Science and Technology, Luoyu Road 1037, Wuhan 430074,
China

A R T I C LE I N FO A B S T R A C T

Keywords: Spinel MnFe2O4 is a potential oxygen carrier owing to its low cost, non-toxicity and good thermal stability during
Chemical-looping combustion the chemical-looping combustion (CLC) redox cycles. The reactivity of MnFe2O4 and the mechanism of CO
Spinel MnFe2O4 oxidation over MnFe2O4 surface were investigated by using the density functional theory (DFT) method. It is
CO adsorption found that CO chemisorbs preferably at the octahedral Fe3+ site with C-down orientation. Particularly, a Mn
CO oxidation
atomic layer lying on the top of Mn-terminated surface occupies some active O sites and weakens the surface
Density functional theory
activity. The adsorbed CO then reacts with a bridging surface O to generate a surface CO2 complex, revealing the
key intermediate for CO2 production. CO2 desorption ultimately takes place by surmounting an energy barrier.
Based upon the DFT-derived energetics, CO oxidation over the spinel MnFe2O4 surface is identified as a three-
step process involving CO adsorption, CO diffusion and CO2 desorption. The pathway analysis illustrates that the
surface O with three Fe3+ ligands shows superior reactivity than that with two Fe3+ and one Mn2+ ligands.
Further, it is noted that the consumption of lattice O primarily occurs around Fe sites, which indicates that Fe3+
can be easily reduced to Fe2+ accompanying with MnFe2O4 transformation to (Fe, Mn)O. These results are well
consistent with the experimental kinetics.

1. Introduction
Chemical-looping combustion (CLC) is a novel combustion tech-
nology that has been suggested as a better alternative for low cost CO2
capture [1,2]. It converts carbonaceous fuels efficiently while produ-
cing a relatively pure sequestration-ready CO2 stream without sig-
nificant energy penalty. In a CLC system, as shown in Fig. 1, metal oxide
is employed as oxygen carrier to transport oxygen from air reactor to
fuel reactor, which can avoid the direct contact between combustion air
and fuel. This arrangement also gives rise to a higher energy conversion
efficiency [3].
Oxygen carrier is the foundation of CLC and is identified as one of
the determining factors for successful operation of CLC. Up to now,
oxides of Fe, Mn, Cu, Co and Ni are feasible candidates to be used as
oxygen carriers. Fe-based oxides show a lot of positive properties such
as low cost, high mechanical strength and environmental friendliness.
However, the redox characteristics of this oxide are relatively weaker
than that of other metal oxides, especially for the CLC with methane or
coal. In addition, Fe-based oxides with thermodynamic limitation re-
sults in a low oxygen transport capacity, because only the transforma-
tion from Fe2O3 to Fe3O4 is applicable for CLC system to fully convert
fuels to CO2 and H2O [4]. Mn-based oxides are also inexpensive and
nontoxic. Moreover, it can be used in the chemical-looping with oxygen
uncoupling (CLOU) process for the solid fuel combustion because of its
oxygen release characteristic at high temperatures [5]. Nevertheless,
Mn-based oxygen carrier owns the disadvantages of low reactivity and
high tendency to react with support oxides [6–8]. Therefore, single
metal oxide of either Fe-based or Mn-based oxide with these dis-
advantages cannot sufficiently meet the criteria of oxygen carrier
during practical CLC application [9–14].
Recently, mixed Mn/Fe oxides combining the advantages of both
Fe- and Mn-based materials have been developed as the oxygen carriers
[15–18] and have received great attention for their better performance
due to the synergistic effects [19–21]. The reduction pathway of bi-
metallic Fe/Mn with CH4 and H2 was studied by Lambert et al. [15],
they found that the reduction of spinel (Fe, Mn)3O4 to (Fe, Mn)O is
rather fast. Further reduction to MnO and Fe0 could be observed when
H2 was used as a reducer. Azimi et al. [16] synthesized a series of mixed
Mn/Fe oxygen carriers with different Mn/Fe ratios, and found that the
particles with Mn content in the range from 25% to 33% exhibited the
best methane conversion at 950 °C. This is because the formation of
spinel phase of (Mn, Fe)3O4 enhances the chemical reactivity and

⁎
Corresponding author.
E-mail address: liujing27@mail.hust.edu.cn (J. Liu).

https://doi.org/10.1016/j.fuel.2018.05.079
Received 2 April 2018; Received in revised form 13 May 2018; Accepted 15 May 2018
Available online 25 May 2018
0016-2361/ © 2018 Elsevier Ltd. All rights reserved.
F. Liu et al. Fuel 230 (2018) 410–417

was applied due to the magnetic properties of MnFe2O4. The general-

ized gradient approximation (GGA) with ultrasoft pseudopotentials
[34] was adopted to describe ion-electron interactions using Perdew-
Burke-Ernzerhof [35] (PBE) exchange-correlation, which has been
proved to be an appropriate functional for studying the spinel systems
[36,37]. The explicitly treated valence electrons were (3d54s2),
(3d64s2), (2s22p2), and (2s22p4) for Mn, Fe, C, and O atoms, respec-
tively. The kinetic energy cutoff for the plane-wave functions was set to
340 eV. The Monkhorst-Pack k-point sampling [38] was used in the
Brillouin zone with a 4 × 4 × 4 mesh for bulk optimization, and a
4 × 4 × 1 mesh for surface relaxation and CO adsorption. Self-con-
sistent field (SCF) calculations were converged until the energy differ-
ences between electronic iterations were smaller than 1.0 × 10−6 eV/
atom. Furthermore, the structural parameters and internal coordinates
were relaxed with the Broyden-Fletcher-Goldfarb-Shanno (BFGS)
method [39]. The energy, force and maximum displacement tolerances
were 1.0 × 10−5 eV/atom, 0.03 eV/Å and 0.001 Å, respectively.
The adsorption energy (Eads) can be calculated according to the
Fig. 1. Simplified schematic of coal gas fuelled chemical-looping combustion.
following expression:
The gray, white, red, and blue spheres represent C, H, O, and N atoms, re-
spectively. The purple, green and orange spheres represent different transition Eads = E (CO-MnFe2 O4 )−(ECO + EMnFe2O4 ) (1)
metal atoms.
where E(CO-MnFe2O4), ECO, and EMnFe2O4 represent the total energy of CO
molecule over MnFe2O4(1 0 0) surface system, CO molecule in the gas-
stability of the oxygen carrier during multiple CLC cycles. Similar re-
phase, and MnFe2O4(1 0 0) surface, respectively. Under this definition, a
sults were obtained by Larring et al. [17]. In many studies [20–22], the
more negative Eads value corresponds to a stronger interaction.
synergetic effects of mixed oxygen carriers were primarily ascribed to
In addition, to further understand CO oxidation mechanism, the
the formation of various new crystalline phases, such as spinels or
transition state (TS) structures are identified by using the complete
perovskites. Further, Wang et al. [23] prepared spinel MnFe2O4 using
LST/QST method [40]. The activation energy (Ea) is defined as follows:
sol-gel combustion synthesis method and suggested that MnFe2O4
showed superior reactivity with coal as compared to the single re- Ea = ETS−EIM (2)
ference oxides of Mn3O4 or Fe2O3. Hence, MnFe2O4 could be a potential
where ETS and EIM are the energies of transition state and intermediate
oxygen carrier candidate better than the corresponding single metal
(IM) state in each elementary reaction, respectively.
oxide applied in CLC process. Moreover, spinel MnFe2O4 is regarded as
a promising catalyst with good activity [24], which is beneficial to coal
gasification and gas reforming in fuel reactor. More importantly, spinel 3. Results and discussion
MnFe2O4 with good magnetic property can greatly facilitate the se-
paration of oxygen carrier from ash [25]. 3.1. Bulk optimization and surface relaxation
The knowledge of micro-interaction mechanism between fuel mo-
lecules and oxygen carriers is useful for understanding the relationship MnFe2O4 is an important spinel oxide, and it naturally crystallizes in
between structure and their properties, which will facilitate the design a mixed phase consisting of both normal and inverse spinel structures.
and optimization of efficient oxygen carriers. Although some experi- However, this compound is believed to be of primarily normal spinel
mental studies have been performed to study the reaction performance structure [41,42]. Accordingly, normal spinel MnFe2O4 is used as
of MnFe2O4 with various fuels [21,23], heretofore, there is no theore- substrate structure in this study. The unit cell of normal spinel MnFe2O4
tical research on CO molecule adsorption and oxidation mechanism is displayed in Fig. 2.
over MnFe2O4 surface in CLC process. Moreover, the quantitative To find the ground state of spinel MnFe2O4, the non-magnetic as
structure-activity relationship of spinel MnFe2O4 are still lacking, and well as two magnetic ↑↑ and ↑↓ configurations were taken into account.
the detailed interaction mechanism between spinel MnFe2O4 and CO The ↑ and ↓ represent up- and down-spin directions of Fe or Mn atoms,
molecule also await elucidation. respectively. The optimization results are listed in Table 1. The lowest
Theoretical methods, for instance, density functional theory (DFT)
can be utilized to understand variations in adsorption activity and to
explicate the surface chemical reactions in detail from one material to
another [26–28]. Importantly, DFT calculations are ideally suitable for
providing valuable information about the active sites of the structure
and the energy of the adsorbed species interacting with surface at an
atomic level [29–32], which can make complements to the experi-
mental studies. Herein, based on the periodic slab models and DFT
calculations, the detailed adsorption behavior of CO molecule over
MnFe2O4 surface is studied, and then the oxidation mechanism of CO
molecule over this surface is proposed through pathway analysis. To the
best of our knowledge, this is the first detailed theoretical study in-
volving CO adsorption and oxidation mechanism on MnFe2O4 surface.

2. Computational details
Fig. 2. Crystal structure of the normal spinel MnFe2O4, Fe3+ atoms are in oc-
All calculations were performed using the plane-wave based DFT as tahedron while Mn2+ atoms in tetrahedron. The red, blue, and purple spheres
implemented in CASTEP package [33]. The spin-polarized calculation represent O, Fe, and Mn atoms, respectively.

411
F. Liu et al.
Table 1
The optimized cell parameters of bulk MnFe2O4.
Magnetic state a = b = c (Å) RFe−O (Å) RMn−O (Å) Relative energy (eV)
NM 8.125 1.958 1.892 15.44
↑↑ 8.291 1.953 2.016 2.59
↑↓ 8.553 2.071 1.973 0.00
Expt. 8.511 [43] 2.035 2.012 / △Z = Zrelaxed − Zpre-relax, where Zrelaxed and Zpre-relax are the z coordinates of
NM, ↑↑, and ↑↓ denote nonmagnetic, ferromagnetic, and anti-ferromagnetic
ordering, respectively.
RFe−O and RMn−O denote bond lengths of FeeO and MneO, respectively.
Zero relative energy denotes the lowest energy magnetic state (i.e. ↑↓).
energy structure with the lattice parameter of 8.553 Å is in a good
agreement with the experimental value of 8.511 Å [43], suggesting that
antiferromagnetic configuration (↑↓) is the magnetic ground state. This
result is also consistent with previous theoretical work [44]. Conse-
quently, this magnetic order (↑↓) is used in the following study. It is
worth noting that the FeeO and MneO bond lengths in optimized
MnFe2O4 are 2.071 Å and 1.973 Å, respectively. The FeeO and MneO
bonds in MnFe2O4 are thus shorter than the FeeO bonds in α-Fe2O3
(2.113 Å) [45] and MneO bonds in Mn2O3 (2.047 Å) [46], which im-
plies that spinel MnFe2O4 has higher thermal stability. It might be the
reason for the robust performance of MnFe2O4 at high temperatures
[16,17].
Spinel (1 0 0), the thermodynamically stable [47] and catalytically
active [24] low-index surface, is adopted in this study. Along the (1 0 0)
orientation of normal spinel MnFe2O4, the surface structure is com-
posed alternatively of a Mn atomic layer and an oxygen-bearing Fe
atomic layer, as shown in Fig. 3a. Accordingly, two modeled slabs
(named as Fe- and Mn-terminated surfaces) were built, as shown in
Fig. 3b and c. The Fe and Mn atoms, as well as O atoms with different
metal ligands are exposed upon both surfaces. Each surface was sepa-
rated by 12 Å-thick vacuum regions in the (1 0 0) orientation of surface,
preventing the interaction between any two successive slabs. Since the
forces acting on atoms near the surface are asymmetric, the surface
relaxation was taken into account to make the calculations more reli-
able. Considering the efficiency and precision, the 8-layer periodic slabs
with top four fully relaxed layers were used in the present work.
Table 2 shows the variations of surface displacement and energy for
these two slabs before and after surface relaxation. The results suggest
that the relaxed layers tend to move towards the bottom of bulk, which
is common in the solid surface. That is to say, surface relaxation causes
the slab layers more compact. From the view of energy, the relaxed
Fig. 3. Structure of MnFe2O4(1 0 0) orientation (a). The settings and possible adsorption sites of two cleaved surfaces: Fe-terminated surface (b) and Mn-terminated
surface (c). The blue, purple and red spheres represent Fe, Mn and O atoms, respectively.
412
Fuel 230 (2018) 410–417
Table 2
The variation of slab displacement and energy before and after relaxation.
△Z (Å) △E (kJ/mol)
Fe-terminated surface −0.121 −109.18
Mn-terminated surface −0.558 −98.24
surface atom before and after relaxation, respectively. A negative value means
the shrinkage along (1 0 0) direction.
△E = Erelaxed − Epre-relax, where Erelaxed and Epre-relax are total slab energies
before and after relaxation, respectively. A more negative value means a more
stable surface.
surfaces are more stable, which is in accordance with actual surface.
Based on these analyses, it can be concluded that the surface relaxation
made the substrate models more close to the actual surface. Therefore,
surface relaxation cannot be neglected, and is considered in all the
calculations for a more accurate result.
3.2. CO adsorption behavior on MnFe2O4(1 0 0) surface
In the fuel reactor, interaction between CO molecule and oxygen
carrier surface is the first step for lattice O consumption. Then the
oxygen vacancies arise, which will result in an oxygen diffusion from
sub-layers to the surface [48]. The deep reduction of metal oxides is
proposed to be controlled by oxygen diffusion [49], which means that
the oxygen diffusion step is a high-temperature process. In addition, the
formation of more desired oxygen vacancies can result in enhanced
reducibility [49], which means that the surface oxygen vacancies will
enhance the reactivity/migration of bulk lattice oxygen. Thus, we
mainly focus on the interaction mechanism between CO and MnFe2O4
surface.
The reactivity of oxygen carrier is largely connected to the presence
of active sites. As shown in Fig. 3b and c, these are eight distinguishable
adsorption sites at the two surfaces. To evaluate the reactivity of
MnFe2O4(1 0 0) surface, all possible adsorption sites on Fe- and Mn-
terminated surfaces have been examined with a CO molecular axis
perpendicular (C-down and O-down orientation) and parallel toward
the surface. CO molecule as a reactant is optimized with the bond
length of 1.153 Å, which is very close to experimental value of 1.128 Å
[50].
F. Liu et al.
Fig. 4. Adsorption energies and optimized structures of CO adsorption on the Fe-terminated surface. The bond lengths are in Å.
3.2.1. CO adsorption on Fe-terminated surface
As depicted in Fig. 3b, the coordinately unsaturated 5-fold Fe site
(Fe5c) and two types of 3-fold O site (O3c1 and O3c2), as well as the
coordinately saturated 4-fold Mn site (Mn4c) are exposed on the surface.
In detail, O3c1 only bonds with three Fe3+ atoms, and O3c2 bonds with
two Fe3+ and one Mn2+ atoms. CO molecule was found to strongly
interact with this surface with C-down orientation. The stable config-
urations with corresponding adsorption energies and structural para-
meters are given in Fig. 4. The stability of surface complex follows the
order of 1A > 1B > 1C.
In configuration 1A, CO adsorbs at the octahedral Fe5c site to form a
CeFe chemical bond with a distance of 1.761 Å. The CeO bond length
is elongated to 1.169 Å from 1.153 Å in gas-phase CO. This configura-
tion has the highest adsorption energy of −104.48 kJ/mol, suggesting
that octahedral Fe5c site has the strongest interaction with CO.
For 1B, the C atom of CO interacts with Fe5c and O3c1 atoms to form
CeFe and CeO bonds with the bond lengths are 2.021 Å and 1.273 Å,
respectively. Meanwhile, the CeO bond length in CO is stretched to
1.210 Å. The interaction between CO and O3c1 site results in the
breakage of two FeeO bonds (marked by dash lines in 1B) and the
formation of a new CeO bond generates a surface CO2 complex. The
adsorption energy of this interaction system is −95.44 kJ/mol, in-
dicating that O3c1 site is also active for CO adsorption. This config-
uration is very important and necessary for some kinds of reaction
process such as CO oxidation, Fischer-Tropsch synthesis, water gas
shift, and so forth.
Configuration 1C demonstrates the equilibrium structure describing
an interaction between CO and O3c2 site. The adsorption energy is
−66.87 kJ/mol, which reveals that the interaction between CO and
O3c2 site is relatively weak. The different CO adsorption behaviors at
O3c1 and O3c2 sites may be due to the reason that the O3c2 coordinated
to Mn2+ is hard to be abstracted.
3.2.2. CO adsorption on Mn-terminated surface
As illustrated in Fig. 3c, Mn-terminated surface can be viewed as Mn
adatom deposition on the Fe-terminated surface, causing the occupa-
tion of the active O3c1 site (named as O4c in this surface). Consequently,
the coordinately unsaturated 5-fold Fe site (Fe5c′), 2-fold Mn site (Mn2c)
and 3-fold O site (O3c2′), as well as the coordinately saturated 4-fold O
site (O4c) are exposed on this surface. After CO adsorption, three stable
configurations are obtained. The corresponding adsorption energies
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Fuel 230 (2018) 410–417
and geometric parameters are displayed in Fig. 5. Similarly, C-down
orientation is more favorable than O-down one for the active sites.
Adsorption energies show the order of 2A > 2B > 2C, the octahedral
Fe3+ site in 2A remains the most active site. However, CO adsorption
on Mn-terminated surface is weaker than that on Fe-terminated surface.
This may be associated with the fact that the existence of Mn atoms on
the top layer lowers the surface activity.
For configuration 2A, CO binding on the Fe5c′ top is still the
strongest adsorption structure. The corresponding adsorption energy is
−79.21 kJ/mol, and the equilibrium distance of a newly formed CeFe
bond is 1.734 Å. Moreover, the CeO bond distance of CO is lengthened
to 1.175 Å.
Configuration 2B indicates that the tetrahedral Mn2c atom is also
active for CO adsorption with an adsorption energy of −63.50 kJ/mol.
The newly formed CeMn bond length is 1.985 Å, and the CeO bond
distance in CO is elongated to 1.167 Å. However, the existence of sur-
face Mn atoms blocks some active O sites preventing the formation of
CO2 complex, which is undesirable for CO oxidation by lattice O.
In configuration 2C, CO molecule adsorbs on the bridge site of Fe5c′
and O3c2′ to generate CeFe and CeO bonds with corresponding bond
distances are 1.964 Å and 1.331 Å, respectively. The bond length of CO
is stretched to 1.228 Å. Compared with configuration 1C, the adsorp-
tion energy for this configuration decreases to −52.73 kJ/mol.
3.2.3. Electronic interaction between CO and surface
The density of states (DOS) of a system describes the number of
states at each energy level that are available to be occupied by electrons
[51–53]. To elucidate CO bonding nature at MnFe2O4(1 0 0) surface,
two representative partial densities of states (PDOS) for CO adsorption
at the Fe5c site and the bridge site of Fe5c and O5c are provided, as
shown in Fig. 6.
For comparison, the DOS of free CO and CO2 molecules are also
provided, as shown in Fig. 6a−d. The electronic states of the CO related
to the primary 4σ, 1π, 5σ and 2π∗ orbitals are located at about −5.0,
−2.5, 0 and 7.0 eV. The gap between the highest occupied molecular
orbital (HOMO, 5σ) and the lowest unoccupied molecular orbital
(LUMO, 2π∗) in CO is about 7 eV, which is consistent with the experi-
mental value [54]. Compared the DOS of free CO with the DOS of C and
O atoms, it shows that the components of the 5σ and 2π∗ orbitals are
mainly from the C atom orbitals. This can explain why the CO is ad-
sorbed on this surface with the C-down orientation. Moreover, the DOS
Fig. 5. Adsorption energies and optimized
structures of CO adsorption on the Mn-termi-
nated surface. The position change of Mn atom is
displayed in upper-right corner of each config-
uration. The bond lengths are in Å.
F. Liu et al. Fuel 230 (2018) 410–417

10
8 (a) 1 2 *
Free CO
6 3 4
4
5
2
0
6 (b) DOS of C in free CO
4
2
Density of states (electrons/eV)

0
6 (c) DOS of O in free CO
4
2
0
12 (d) 3 2
9 Free CO2 u 1 g u

6
1 u
3
0
8
(e) Adsorbed CO 1
6
4 2 *
4 Fe5c - 3d 5
2
0
6
(f) 3 O5c - s
Adsorbed CO 1 u 1
4 u g 2 u O5c - p
Fe5c - 3d
2 CO2 Complex
0
-20 -15 -10 -5 0 5 10
Energy (eV)
Fig. 6. Total DOS of the free CO (a), DOS of the C atom in free CO (b), DOS of the O atom in free CO (c), total DOS of the free CO2 (d), as well as PDOS of the CO
adsorbed at Fe5c site (e) and at the bridge site of Fe5c and O3c1 (f). The vertical dash lines indicate the Fermi level at 0 eV.

of free CO2 evidently shows the positions of three HOMOs 1πu, 3σu, and
1πg, and the LUMO 2πu.
Fig. 6e reveals the PDOS for CO adsorption at the Fe5c site. As
compared with free CO, all the energy of the electronic states of ad-
sorbed CO shifts toward lower energy level, suggesting a stable ad-
sorption. The 5σ orbitals shift downward and merge into 1π orbitals.
Moreover, CO 2π∗ splits into two orbitals, and the orbitals below the
Fermi level have a stronger hybridization with 3d states of Fe than the
orbitals above the Fermi level. The 2π∗ orbitals become almost empty,
which indicates that the 3d states of Fe atom will not donate electrons
back to the 2π∗. This electron interaction system is consistent with Hu
et al.’s orbital mixing model [55].
Fig. 6f presents the PDOS of CO adsorption at the bridge site of Fe5c
and O5c. The 2π∗ orbitals of CO also splits into two orbitals. On the
contrary, the orbitals above the Fermi level have a stronger hy-
bridization with Fe 3d states than that below the Fermi level. This
bonding mode is less stable than the that CO on Fe5c site. Hence, the
bond distance of CeFe in this configuration is longer than that in
configuration 1A. Moreover, the adsorbed CO orbitals hybridize with
O5c 2p in the range from −9 to 3 eV, generating a new energy level
corresponding to the CO2 1πg at approximately −3 eV.
The electronic interaction analysis shows that there is a chemical
binding of CO molecule to the MnFe2O4(1 0 0) surface, which agrees
well with above discussion. Dong et al. [56] studied the activity of α-
Fe2O3 by DFT calculations, they found that CO could only adsorb atop
Fe site on the low-index (0001) surface with an adsorption energy of
51.4 kJ/mol. Therefore, the low-index MnFe2O4 surface exhibits higher
activity than the low-index α-Fe2O3 surface.
3.3. CO oxidation mechanism by lattice oxygen
On both surfaces, octahedral Fe3+ atoms serve as active centers,
from where CO can react with the coordinately unsaturated bridging O
atom to form a surface CO2 complex, such as 1B, 1C and 2C. It is shown
in other studies that the CO2 complex is a crucial intermediate (IM) to
CO2 by combining the CO and lattice O [48,56,57]. Herein, the for-
mation of CO2 over spinel MnFe2O4(1 0 0) is proposed based on the
above discussion. The reaction pathways and energy profiles of CO
oxidation over Fe- and Mn-terminated surfaces are schematically illu-
strated in Figs. 7 and 8, respectively. The free CO molecule and
MnFe2O4 surface are regarded as the initial state (IS). The optimized
CO2 molecule and corresponding O-defective surface is accepted as the
final state (FS).
As shown in Fig. 7, there are two pathways for CO oxidation over
Fe-terminated surface due to the difference in oxygen activity. Each
pathway includes three elementary reactions: CO adsorption, CO dif-
fusion and CO2 desorption. CO chemisorbs at atop Fe5c site is the first
step (IS → 1A) for both pathways, and this step is exothermic by
104.48 kJ/mol.
In Path1, the adsorbed CO then glides to the neighboring O3c1 atom
through TS1 to form a CO2 complex (second step: 1A → TS1 → 1B), and
the desorption of CO2 is the third step (1B → TS2 → FS1). The second
step is an endothermic reaction with an activation energy of 90.19 kJ/
mol and a reaction heat of 9.04 kJ/mol. Meanwhile, the CeFe bond
length is elongated from 1.761 Å in 1A to 1.843 Å in TS1 (see Fig. 7).
CO2 desorption through TS2 shows a rather low activation energy of
13.21 kJ/mol, implying that this step is kinetically favorable. This
process is exothermic process with the energy of 37.11 kJ/mol. In TS2,
the CeFe distance is further lengthened to 2.654 Å, and newly

414
F. Liu et al.
Fig. 7. The reaction pathways and energy profiles for CO oxidation over the Fe-terminated surface. The bond lengths are in Å.
generated CO2 molecule breaks away from the surface. A gaseous CO2
and an oxygen-defect Fe-terminated surface are finally obtained in FS1.
The entire CO oxidation process via this pathway is strongly exo-
thermic, and the reaction between the adsorbed CO and surface O3c1
atom through TS1 is identified to be the rate-determining step.
In Path2, the formation of surface CO2 complex through the reaction
between the adsorbed CO and neighboring O3c2 atom is the second step
(1A → TS3 → 1C), and CO2 desorption is the third step (1C → TS4 →
FS2). The second step takes place through a similar TS (TS3) in Path1
(TS1), which is also an endothermic process with the activation energy
of 90.99 kJ/mol and an increased reaction energy of 37.61 kJ/mol. In
TS3, the bond length of CeFe is elongated from 1.761 Å in 1C to
1.809 Å. However, the CO2 desorption through TS4 in third step is an
endothermic process with an activation energy of 84.65 kJ/mol and a
reaction heat of 22.18 kJ/mol. The CeFe distance in TS4 is elongated to
2.654 Å resulting in the breakaway of CO2 molecule. The entire reaction
process via this pathway is visibly less exothermic, and the CO diffusion
step is also regarded as the rate-determining step.
As shown in Fig. 8, CO oxidation on the Mn-terminated surface also
Fig. 8. The reaction pathways and energy profiles for CO oxidation over the Mn-terminated surface. The bond lengths are in Å.
415
Fuel 230 (2018) 410–417
goes through three steps: CO adsorption (IS → 2A), CO diffusion (2A →
TS1′ → 2C) and CO2 desorption (2C → TS2′ → FS2). CO adsorption is
the first step, and this process is exothermic by 79.21 kJ/mol. The
second step through TS1′ is an endothermic process which presents a
relatively higher activation energy of 107.76 kJ/mol. The CO2 deso-
rption requires the activation energy of 120.61 kJ/mol. It is obvious
that the activation energy of CO2 desorption is higher than that of CO
diffusion. Therefore, CO2 desorption is identified as the rate-limiting
step.
Despite each pathway for CO oxidation on both surfaces includes
CO adsorption, CO diffusion and CO2 desorption, the energies vary
differently. It can be seen that CO oxidation on Mn-terminated surface
is more energetically demanding as compared with on Fe-terminated
surface. There are two major reasons for this distinction. The first is
ascribed to the different reactivity of surface O (Path1 vs Path2). The
second is due to the steric hindrance of Mn atoms on Mn-terminated
surface (Path2 vs Path3): i) Mn atoms occupy a part of O sites which are
active on the Fe-terminated surface. Thus, the appearance of Mn atomic
layer on the top surface results in a decrease of oxygen transport
F. Liu et al.
capacity, in good agreement with the experiments [58,59]. ii) as CO
adsorption on other sites, the distorted Mn position results in surface
reconstruction which will hamper CO diffusion and CO2 desorption
process. On the other hand, the consumption of lattice O mainly takes
place around the Fe3+ atoms, indicating that the reduction of MnFe2O4
occurs in stepwise of Fe3+ → Fe2+ → Fe0. The reduction of MnO → Mn
at CLC temperature levels is not observed [1], confirming that the Fe3+
atom possesses a higher activity than the Mn2+ atom. The lattice O
covered by Mn2+ atom can hardly be extracted out. This result is also
well consistent with the experimental kinetics [15,16,60].
From the above discussion, it is clear that CO oxidation by lattice O
located at MnFe2O4 surface is governed by the Mars van Krevelen
mechanism: CO first adsorbs at a surface octahedral Fe site, it then
glides to a bridge-O atom, generating a surface CO2 complex with a bent
equilibrium geometry which still bonds to the octahedral Fe site, CO2
desorption finally occurs by surmounting an energy barrier. In parti-
cular, the presence of Mn2+ atoms on the top of MnFe2O4 surface are
unfavorable for CO oxidation. Further, it should be noted that H2 would
also be present in the CLC process, and it may have the synergistic effect
for CO adsorption and oxidation. Therefore, more fundamental work is
necessary for comprehending the synergistic effects of H2 on CO ad-
sorption and oxidation over MnFe2O4 surface.
4. Conclusions
The periodic slab model and density functional theory methods
were used to investigate the CO adsorption and oxidation mechanism
over spinel MnFe2O4(1 0 0) surface during the chemical-looping com-
bustion. All the possible active sites over both Fe- and Mn-terminated
surfaces were properly examined. The results indicate that CO adsorbs
preferably on MnFe2O4 surface through the C-down orientation, and the
surface octahedral Fe3+ atoms on both surfaces are the most active sites
for CO chemisorption. In the case of CO adsorbed atop Fe site, the
electronic analysis of binding mechanism shows that the electron in-
teraction between CO and Fe atom abides by the orbital mixing model.
On the other hand, the coordinately unsaturated surface O atoms ex-
posed on both surfaces are active for combining CO to form the CO2
complex, which is a key intermediate for CO oxidation. In particular,
the surface O atom with three Fe3+ ligands shows higher activity than
that with two Fe3+ and a Mn2+ ligands. According to the DFT-derived
energetics, CO oxidation on MnFe2O4 surface is a three-step process
governed by Mars-van Krevelen mechanism. Specifically, CO oxidation
over Fe-terminated surface is found to be an exothermic process con-
trolled by CO diffusion with an activation energy of 90.19 kJ/mol. It
becomes endothermic controlled by CO2 desorption with a higher ac-
tivation energy (120.61 kJ/mol) due to the steric hindrance of a Mn
atomic layer on Mn-terminated surface. Besides, it should be noticed
that the consumed lattice O is mainly bonded with Fe3+ resulting in the
reduction to Fe2+. This study provides valuable information about the
reactivity of MnFe2O4 and the nature of CO oxidation over spinel
MnFe2O4 surface at an atomic level.
Acknowledgements
This work was supported by the National Natural Science
Foundation of China (51676079, 51661145010), and the Foundation of
State Key Laboratory of Coal Combustion (FSKLCCB1701).
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