Powder Technology 388 (2021) 474–484

Contents lists available at ScienceDirect

Powder Technology

journal homepage: www.elsevier.com/locate/powtec

Modulation of Fe-based oxygen carriers by low concentration doping

of Cu in chemical looping process: Reactivity and mechanism based
on experiments combined with DFT calculations
Nini Yuan, Hongcun Bai, Mei An, Jinpeng Zhang, Xiude Hu, Qingjie Guo 1,⁎
State Key Laboratory of High-efficiency Utilization of Coal and Green Chemical Engineering, College of Chemistry and Chemical Engineering, Ningxia University, Yinchuan 750021, China

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

Article history: Fe-based oxygen carriers (OCs) are currently the crucial material basis for chemical looping technology to realize
Received 21 January 2021 industrial applications. However, the relatively low reactivity of pure Fe-based OCs limits their extensive applica-
Received in revised form 8 April 2021 tions. One strategy to enhance reactivity in the chemical looping process is the introduction of another metallic
Accepted 9 April 2021
element by doping. This study prepared a series of Fe-based OCs (Cu2xFe2(1-x)O3) with low concentration doping
Available online 4 May 2021
of Cu. The reaction mechanism and reactivity modulation of Cu2xFe2(1-x)O3 OCs in the chemical looping process
Keywords:
were systematically investigated by means of experiments and density function theory (DFT) calculations. Acti-
Chemical looping vation energies for Cu2xFe2(1-x)O3 ranging between 72 and 37 kJ/mol were detected using H2 and the thermogra-
Oxygen carriers vimetric analyzer (TGA) test, indicating enhanced reactivity in the chemical looping process as compared with
Reaction mechanism that of pure Fe-based OCs of 84 kJ/mol. Thus, the low concentration doping of Cu can effectively improve the re-
Doping activity of Fe-based OCs. Furthermore, comprehensive DFT calculations upon the transition state indicated the re-
Density function theory calculations action energy barrier for Cu2xFe2(1-x)O3 with different doping concentration and configurations to be in the range
of 1.68–1.02 eV, lower than that of pure Fe2O3 of 2.30 eV. The Cu doping and the modulation of the reaction path-
ways are important reasons for the enhanced reactivity of Cu2xFe2(1-x)O3 OCs. Additionally, this study proposed a
lattice oxygen release mechanism of Cu2xFe2(1-x)O3 OCs during chemical looping combustion.
© 2021 Elsevier B.V. All rights reserved.

1. Introduction The design and preparation of high-efficiency OCs remains a popular

High-efficiency oxygen carriers (OCs) are currently a crucial mate-
rial basis for chemical looping technology (CLT) to realize industrial ap-
plications from laboratory-based studies. CLT [1,2] is a novel energy
conversion technology, and its application can realize the capture of
CO2 [3] as feedstock to produce high value-added chemicals. Metal ox-
ides are commonly employed as OCs [4,5] in CLT to transport lattice ox-
ygen though redox reactions. Meanwhile, heat is transferred between
an air reactor and a fuel reactor. CLT has the potential to realize the
clean and efficient utilization of fuels and the reduction of pollutant
emissions [6] without the need for an air-separating plant. The selection
of high-efficiency OCs is a key requirement for CLT. These OCs are char-
acterized by a high oxygen-carrying capacity, high reactivity, and stable
cycle performances. Therefore, the application of high-efficiency OCs
can clearly reduce the quantity of OCs and equipment load required
for the chemical looping system and can shorten the time required for
conversion of fuels in the reactor.
⁎ Corresponding author.
E-mail address: qingjie_guo@163.com (Q. Guo).
1
Present address No.489, Helanshan west road, Xixia district, Yinchuan, Ningxia, China.
research topic and is highly relevant in the CLT field. The extensive re-
search of OC materials for large-scale application of CLT is mainly fo-
cused on Fe-based OCs [4,7,8]. This can be ascribed to the abundant
reserves, superior mechanical properties and environmental-
friendliness of Fe-based OCs. However, the reactivity of Fe-based OCs
is relatively low compared with those of Ni-based and Cu-based OCs,
which limits their wide applications. Several studies have investigated
the design and preparation of Fe-based OCs as well as their reactivities
in the chemical looping process. For instance, Zhang et al. [9] studied
the chemical looping gasification characteristics of rice straw with
Fe2O3/Al2O3 OCs. The results of their study indicated that the addition
of inert Al2O3 improves the performance of Fe2O3 OC and the yield
rate of syngas. Kuo et al. [10] prepared Na-modified Fe-based OCs
using the conventional ceramic method and it was applied to chemical
looping gasification process. The results indicated that the reduction
rate of Fe-based OCs was enhanced by incorporation of Na. Additionally,
Guo et al. [11] investigated that Fe2O3/ATP OC prepared by sol-gel
method was applied to the chemical looping combustion of coal. Their
results showed that the addition of inert ATP optimized the pore struc-
ture of Fe-based OCs, increased their surface area, and improved the re-
activity and the conversion rate of coal. In an exploration of the

https://doi.org/10.1016/j.powtec.2021.04.022
0032-5910/© 2021 Elsevier B.V. All rights reserved.
N. Yuan, H. Bai, M. An et al.
performance of an Fe2SiO2 OC with a core-shell structure, Bhavan et al.
[12] demonstrated a decrease in reactivity due to the formation of
Fe2SiO4 and the loss of the core-shell structure during chemical looping
process. Although there have been significant efforts to investigate the
composition, structure, and preparation of Fe-based OCs, single-
component Fe-based OCs continue to face the challenges of low reactiv-
ity, rapid performance attenuation, and poor cycle performances during
the chemical looping process.
Mono-metallic OCs such as Fe2O3, CuO, NiO, and Mn2O3 show differ-
ent advantages and disadvantages. Composite Fe-based OCs are consid-
ered an alternative based on the complementary and synergistic effects
between binary metallic elements [13]. The purpose of the design and
preparation of the Ni\\Fe [14], Cu\\Fe [15], Ca\\Fe [16,17], and Mn\\Fe
[18] bimetallic OCs is to produce the composite Fe-based OCs with ex-
cellent comprehensive properties. For example, He et al. [19] prepared
a Ni\\Fe bimetallic OC, which displayed a higher gasification efficiency
for biomass due to the synergistic effects between Fe2O3 and NiO. How-
ever, the Ni\\Fe alloy has been detected in the reduced samples,
thereby changing the micro-morphology of the samples after 120 min
cyclic reactions and having a negative effect on lattice oxygen transport.
Jiang et al. [20] investigated the dose-response effects of the addition of
CuO on the structure and properties of Cu\\Fe OCs. The addition of CuO
resulted in the OCs becoming porous and increased their reactivity,
whereas Cu\\Fe OCs were sintered with the addition of 20 wt% CuO.
Shen et al. [21] explored the metal synergistic effects of an CuFe2O4
OC formed by mixing CuO and hematite. Their results indicated im-
provements to the reactivity of hematite and the physical stability of
CuO during the chemical looping process. Frick et al. [22] studied the
Cu\\Fe OCs by means of physical-chemical characterization, showing
that Cu\\Fe OCs of sufficient mechanical strength demonstrate high re-
activity with CO and CH4. Therefore, they were suitable for chemical
looping combustion. Fan et al. [23] recently reported that 1% Cu-doped
modified Fe-based OCs was applied to the conversion of CH4 to produce
syngas during chemical looping gasification. The rate of CH4 conversion
increased by 470% at 700 °C, and energy saving of ~35% when compared
to that at 1000 °C. As a result, the selection of Cu as a dopant withing low
concentration modified Fe-based OCs shows obvious advantages. Fur-
ther investigation of Cu\\Fe OCs is important to advancing this technol-
ogy. Of particular importance is the study of the micro-reaction
mechanism and modulation of the reactivities of Cu\\Fe OCs, which
only a few studies have reported on at the molecule/atom level.
The investigation of the micro-reaction mechanism of OCs during
the chemical looping process [17,24] is helpful to understand the asso-
ciated structure-activity relationship and to provide theoretical guid-
ance for the design and preparation of OC materials. Density function
theory (DFT) calculations are commonly used to provide valuable infor-
mation on the micro-reaction mechanism, the active sites of the OC sur-
face, and the adsorbability between OC and fuel molecules [18,24,25],
which is helpful to experimental studies [26,27]. For example, Liu
et al. [28] investigated the reactivity and reaction mechanism of CO
over the CuFe2O4 OC surface and pointed out that the reaction of
CuFe2O4 with CO was controlled by adsorption. Wang et al. [29] simi-
larly explored the solid-solid reaction of CuFe2O4 with C by the experi-
ments and DFT calculations. However, there have been few reports on
the modulation of reactivity of Fe-based OCs with low concentration
doping of Cu. In particular, few studies have reported on the compre-
hensive investigation of the micro-reaction mechanism and structure-
activity relationship based on DFT calculations.
The present study investigated the micro-reaction mechanism and
modulation of reactivity of Cu2xFe2(1-x)O3 OCs (x = 1, 2, 5 and 10%)
with H2 during chemical looping combustion based on experiments
and DFT calculations. In addition, the detailed lattice oxygen release
mechanism was explored and the composition, structure, element dis-
tribution, and micro-morphology of Cu2xFe2(1-x)O3 OCs were character-
ized by X-ray powder diffraction (XRD) and scanning electron
microscopy/energy dispersive X-ray spectroscopy (SEM-EDS) mapping.
475
Powder Technology 388 (2021) 474–484
The results of the present study are expected to be helpful for the
screening, design, and optimization of Fe-based OCs.
2. Experiment and computational method
2.1. Preparation of OCs
The Cu2xFe2(1-x)O3 OCs (x = 1, 2, 5 and 10%) were synthetized via
the co-precipitation method. Two kinds of nitrates (Cu(NO3)2·3H2O
and Fe(NO3)3·9H2O) were dissolved in deionized water based on n
(Cu2+)/n(Fe3+) = x/(1-x) to produce nitrate solution. The nitrate solu-
tion and the co-precipitation solution of 1 mol/L Na2CO3 were evenly
mixed using a peristaltic pump with the pH of the mixture maintained
in range of 9–10. The precipitation mixture was then stirred for half
an hour until completely precipitated, the supernatant was discarded,
and the material was washed repeatedly with deionized water until
neutral. Next, the material was vacuum filtered and transferred to an
oven to dry at 120 °C for 12 h. Finally, the material was calcined in a
muffle furnace at 900 °C for 3 h and then crushed and sieved using a
standard sieve to obtain particles with a diameter between 75 and
150 μm. The blank sample of Fe2O3 OC was prepared using the same
method. All reagents used were of analytical purity and were provided
by the Chinese Medicines Group Chemical Reagent Co. Ltd.
2.2. Characterization
2.2.1. XRD
The crystalline phases of OCs were characterized by X-ray diffraction
techniques (XRD, a Bruker D8 Advance A25) with a Cu target. The in-
strument voltage, amperage, and scan rate were set to 40 kV, 40 mA,
and 2°/min from 5° to 85°, respectively.
2.2.2. SEM-EDX
Scanning electron microscopy (SEM, ZEISS EVO18, Germany)
coupled with an energy dispersive X-ray system (EDX) mapping were
used to analyze the micro-morphology and element distribution of
OCs. The instrument accelerated voltage and resolution were set to
10 kV and 1 μm, respectively.
2.3. Reactivity test
A thermogravimetric analyzer (TGA, Netzsch STA 449F3, Germany)
was used to determine the conversion rate and lattice oxygen release
rate of OCs at various temperatures. H2 is an important gas component
that reacts with OCs during the chemical looping process. During the re-
activity tests, reducing gas containing 20 vol% H2 balanced Ar was used
for the evaluation of the reactivity of OCs at a gas flow rate of 200 mL/
min. The flow rate of the Ar protection gas was 20 mL/min and the
heating rate was 10 °C/min.
2.4. Model and computational method
DFT calculations were performed on the BAND module of the
Amsterdam Density Functional (ADF) code [30–32]. In comparison
with the plane-wave method adopted in the literature [23,33–35], the
basis set of the BAND module of the ADF code is the linear combination
of atomic orbitals (LCAO) and Slater-type orbitals (STOs). This repre-
sents an efficient and accurate approach for processing the system of
solids and periodic materials at an atom scale [36]. The DZP and TZP
basis sets were tested, with the former providing accurate results for
the optimization of geometry, the calculation of reaction heat, and the
reaction mechanism investigated in the current study. The reaction
mechanism of OCs and H2 was calculated by means of the exchange-
correlation function proposed by Perdew, Burke and Ernzerhof (PBE)
and a double-ζ plus polarization basis set DZP which approximates
the equivalent basis set 6-31G*, which was implemented in ADF code.
N. Yuan, H. Bai, M. An et al.
A similar level of calculation was successfully used by Bai et al. [37,38] to
process solid and periodic materials. The Nudged Elastic Band method
(NEB) [25,39] was used to determine the transition state. The NEB
method has been used in past studies to investigate the surface reaction
mechanism of the periodic slab model [25]. The detailed calculations, in-
cluding SCF convergence, force, displacement, and k-point sampling in
the first Brillouin zone were set as normal in the ADF program.
As shown in Fig. 1, the α-Fe2O3 (001) surface with single iron-layer
(Fe-O3-Fe…termination) is the most stable and common among natu-
rally grown crystals [24,33,35,40], and was adopted to construct the
model of periodic slab. In the calculations, the super-cell model with 2
× 2 units contained 9 layer atoms. The setting of a 20 Å-thick vacuum
layer eliminated inter-slab-layer interactions. In addition, there was suf-
ficient space for the relaxation of adsorption molecules. The bottom four
layer atoms were fixed, whereas the remaining five layer atoms were
allowed to relax, constituting the slab model of Fe2O3. As shown in
Fig. 1(c), the single Fe atom of the Fe2O3 model surface was replaced
by a Cu atom, following which the Cu-Fe2O3 model was generated. Fur-
thermore, the models with multiple substituted Cu atoms, primarily lo-
cated the first, second, and third Fe atom layer of the surface and
subsurface presented in the Fig. 1(b), were considered in the calcula-
tions and labeled as nCu-Fe2O3 (n = 1, 2, 3 denotes the number of
substituted Cu atoms). The calculated lattice parameters were a = b
= 5.038 Å and c = 13.750 Å, which is in good agreement with experi-
mental (a = b = 5.035 Å, c = 13.747 Å) and theoretical (a = b =
5.035 Å, c = 13.74 Å) values [23]. The spin-polarization test was con-
ducted for the system of the Cu-Fe2O3 reaction with H2. The reaction en-
ergy barriers were 1.69 eV and 1.68 eV for the top sites of the Cu atoms
with and without spin-polarization, respectively. Therefore, the basis
set DZP without self-polarization was adopted for all calculations,
which satisfied the basic calculation requirements for the current study.
3. Results and discussion
3.1. DFT calculations
3.1.1. Structure analysis of OCs
The structures of OCs were investigated by the quantum chemistry
method. Fig. 1 shows the introduction of the Cu atom into the Fe2O3 struc-
ture taking the Cu-Fe2O3 model as an example. Partial Fe―O and partial
Fe―Fe bonds with lengths of 1.754 Å and 3.150 Å respectively for the
Fe2O3 model were replaced by Cu―O bonds and Cu―Fe bonds with
lengths of 1.882 Å and 3.190 Å, respectively. The increases in bond length
were as expected. In contrast to the Fe2O3 model, the structure of Cu-
Fe2O3 not only contained an Cu atom, but also showed changes to the
Fig. 1. Models of OCs: (a) primitive cell of α-Fe2O3; (b) α-Fe2O3 (001) surface; (c) Cu-Fe2O3 OC.
476
Powder Technology 388 (2021) 474–484
chemical environment around Fe atoms, including changes to the type
of bond and an increase in the bond length. In addition, the changes to
the structural characteristics of nCu-Fe2O3 models (n = 2 and 3) were
similar to those of the Cu-Fe2O3 structure. The DFT calculations confirmed
obvious changes to the structure of Fe2O3 OC due to Cu doping.
3.1.2. Adsorbability of H2 on the surface of OCs
The present study explored the active sites of Cu2xFe2(1-x)O3 and the
stable adsorption configurations of H2 molecules on the surface of OCs
based on the investigation of the adsorbability of H2 molecules on the
surface of OCs at different sites. In addition, the effects of the number
and position of substituted Cu atoms on the adsorbability of H2 mole-
cules were studied. As shown in Table 1 and Fig. 4, the present study ex-
plored a total of 30 adsorption models of H2 molecules on the surfaces of
nCu-Fe2O3, including three, six, nine, and twelve models for the surfaces
of Fe2O3, Cu-Fe2O3, 2Cu-Fe2O3, and 3Cu-Fe2O3, respectively.
The adsorbability of the surface of nCu-Fe2O3 was explored by focus-
ing on the adsorption energy (ΔEads) and adsorption distance (D). D
represents the distance of a H2 molecule adsorbed on the OC surfaces.
ΔEads is defined as below:


ΔEads ¼ EðOCþH2 Þ − EOC þ EH2 (1)
In Eq. (1), E(OC+H2), EH2 and EOC represent the total energies of H2
molecule adsorbed over the surface of OCs, the H2 molecule, and OCs,
respectively. Under this definition, the value of ΔEads is inversely related
to the strength of interaction between H2 molecules and OCs.
As shown in Table 1, Eq. (1) was used to calculated the ΔEads of H2
molecule adsorbed over the surface of nCu-Fe2O3. The absolute values
of ΔEads were all less than 0.2 eV. No new formations of chemical
bonds were observed. As shown in Fig. S1–S10 (from R-1 to R-30)
within the electronic supporting information (ESI), the process was
characterized by physical adsorption. As shown in Fig. 2, taking the
Fe2O3 OC as an example, the ΔEads of the top, bridge, and hollow sites
of the Fe atoms were − 0.13, −0.01, and − 0.07 eV, respectively,
whereas the adsorption distances corresponded to 2.150, 1.910, and
1.780 Å, respectively. As shown in Fig. 2(c), these results indicated
that the strongest interactions between the H2 molecules and the
Fe2O3 OC occurred at the top site of the Fe atom. This site had the
smallest adsorption energy and the largest adsorption distance. This
site also represented the configuration with the highest stability, similar
to that of H2 adsorbed on the surface of iron oxide reported in literature
[24,33,35,40]. As shown in Table 1, the adsorbability and adsorption
configurations of the H2 molecule on the surface of Cu-Fe2O3 were sim-
ilar to that of Fe2O3. The configurations of H2 molecules vertically
N. Yuan, H. Bai, M. An et al. Powder Technology 388 (2021) 474–484

Table 1
Adsorption distance (D), adsorption energy (ΔEads), reaction energy barrier (ΔEbarrier) and reaction heat (ΔEreaction) of H2 molecules on the surface of nCu-Fe2O3 oxygen carriers.

Models D④/Å ΔEads/eV ΔEbarrier/eV ΔEreaction/eV

Fe2O3-H2-top-Fe① 2.150 −0.13 2.30 −0.29

Fe2O3-H2-bridge-Fe 1.910 −0.01 2.47 −0.13
Fe2O3-H2-hollow-Fe 1.780 −0.07 2.64 −0.71

(Cu-Fe2O3)-H2-top-Cu② 2.140 −0.03 1.68 −0.34

(Cu-Fe2O3)-H2-bridge-Cu 1.870 −0.02 2.04 −0.36
(Cu-Fe2O3)-H2-hollow-Cu 1.530 −0.01 2.36 −0.43

(Cu-Fe2O3)-H2-top-Fe 2.180 −0.11 1.81 −0.36

(Cu-Fe2O3)-H2-bridge-Fe 1.920 −0.10 2.42 −0.46
(Cu-Fe2O3)-H2-hollow-Fe 1.700 −0.02 2.26 −0.60

(2Cu-Fe2O3)-1-adjoin-H2-top-Cu 2.086 −0.05 1.30 −0.32

(2Cu-Fe2O3)-1-adjoin-H2-bridge-Cu 1.565 −0.04 2.10 −0.28
(2Cu-Fe2O3)-1-adjoin-H2-hollow-Cu 1.568 −0.03 2.07 −0.32

(2Cu-Fe2O3)-1-diagonal-H2-top-Cu 2.118 −0.05 1.28 −0.55

(2Cu-Fe2O3)-1-diagonal-H2-bridge-Cu 1.438 −0.03 2.49 −0.55
(2Cu-Fe2O3)-1-diagonal-H2-hollow-Cu 1.531 −0.04 2.45 −0.56

(2Cu-Fe2O3)-1–2-H2-top-Cu 2.082 −0.07 1.29 −1.07

(2Cu-Fe2O3)-1–2-H2-bridge-Cu 1.760 −0.03 2.50 −1.09
(2Cu-Fe2O3)-1–2-H2-hollow-Cu 1.695 −0.06 2.32 −1.06

(3Cu-Fe2O3)-1-H2-top-Cu 2.057 −0.03 1.07 −0.48

(3Cu-Fe2O3)-1-H2-bridge-Cu 1.431 −0.01 1.28 −0.52
(3Cu-Fe2O3)-1-H2-hollow-Cu 1.557 −0.02 1.27 −0.48

(3Cu-Fe2O3)-1–2-H2-top-Cu 2.038 −0.04 1.02 −1.12

(3Cu-Fe2O3)-1–2-H2-bridge-Cu 1.657 −0.03 1.22 −1.12
(3Cu-Fe2O3)-1–2-H2-hollow-Cu 1.491 −0.03 1.42 −1.12

(3Cu-Fe2O3)-2–1-H2-top-Cu 2.058 −0.07 1.03 −0.58

(3Cu-Fe2O3)-2–1-H2-bridge-Cu 1.607 −0.04 1.71 −0.65
(3Cu-Fe2O3)-2–1-H2-hollow-Cu 1.592 −0.06 1.66 −0.60

(3Cu-Fe2O3)-1–2-3③-H2-top-Cu 2.064 −0.05 1.06 −1.03

(3Cu-Fe2O3)-1–2-3-H2-bridge-Cu 1.701 −0.03 1.22 −1.05
(3Cu-Fe2O3)-1–2-3-H2-hollow-Cu 1.709 −0.04 1.28 −1.03

Note:
① Fe2O3-H2-top (bridge/hollow)-Fe represents the adsorption and reaction of H2 molecules at the Fe-top (bridge/hollow) sites on the Fe2O3 surface.
② (Cu-Fe2O3)-H2-top (bridge/hollow)-Fe(Cu) represents the adsorption and reaction of H2 molecules at the Fe(Cu)-top (bridge/hollow) sites on the Cu-Fe2O3 surface.
③ 1,2,3 represents 1-Fe layer, 2-Fe layer and 3-Fe layer for nCu-Fe2O3 models, as shown in Fig. 1.
④ D represents the shortest distance of H2 molecule stable adsorbed on the OC surface.

Fig. 2. The stable adsorption configurations of the H2 molecule on Fe2O3 OC surface at different sites: (a) the top, bridge and hollow sites of Fe atom for Fe2O3 OC surface marked in yellow;
(b) the hollow site of Fe atom for over view; (c) the top site of Fe atom for side view; (d) the bridge site of Fe atom for side view.

477
N. Yuan, H. Bai, M. An et al.
adsorbed on the top sites of metal atoms of the surface of Cu-Fe2O3
showed higher stability and preferentially adsorbed forms. The metal
atoms represented the active sites of the surface of the Cu-Fe2O3 OC.
As shown in Table 1 and Fig. S4–S10 (from R-4 to R-30) of the ESI,
the adsorbability of H2 adsorbed on the Cu atoms of the surface of
nCu-Fe2O3 (n = 2 and 3) was investigated. The H2 adsorbed on the
top sites of Cu atoms on the surface of nCu-Fe2O3 showed a smaller
ΔEads and more most distant D in comparison with those of the bridge
and hollow sites, which were sites of higher stability and preferential
adsorption. This result indicated that the number and position of
substituted Cu atoms had little effect on the adsorbability of H2 over
Cu atom sites for the surface of nCu-Fe2O3.
The above results showed that the metal atoms of the surface of
nCu-Fe2O3 were active sites and that H2 molecules were vertically
adsorbed on the top sites of metal atoms through physical adsorption,
representing the primarily stable adsorption configurations.
3.1.3. H2 oxidation on the surface of OCs
The present study examined the reaction of H2 on the surface of
Cu2xFe2(1-x)O3 OCs during chemical looping combustion. The NEB
method was used to determine the transition states (TS) based on the
calculation conditions outlined in Section 2.4. The first step was the de-
termination of the reaction start and end points. As shown in Fig. S1–
S10 (from R-1 to R-30) of the ESI, by regarding the start point of the re-
action (R) to be the stable adsorption configurations of H2 molecules on
the surface of nCu-Fe2O3, the H\\H bond of H2 molecules was not dis-
connected and the system had the lowest energy. As shown in Fig. S1–
S10 (from P-1 to P-30) of the ESI, the stable configurations of the pro-
duced H2O molecules desorbed from the OC surfaces were taken as
the reaction (P) end point. The NEB method was used to generate five
different images between the start and end points. The images with
the highest energy were considered as being in a transition state (TS),
and their energies were used to calculate the energy barrier.
The reaction energy barrier (ΔEbarrier) was calculated to further un-
derstand the micro-reaction process of Cu2xFe2(1-x)O3 OCs with H2:
ΔEbarrier ¼ ETS −ER (2)
In Eq. (2), as shown in Fig. S1–S10 (from TS-1 to TS-30) of the ESI, ETS
is the total energy of the transition state determined through NEB
method and ER is the overall energy of the reactant. Under this defini-
tion, the value of ΔEbarrier is inversely related to the ease at which the re-
action occurs and the reactivity of the OCs.
As shown in Fig. S1–S10 of the ESI, the present study explored the re-
action of H2 on the different adsorption sites of the surface of nCu-Fe2O3.
First, as shown in Table 1 and Fig. S1 of the ESI, the reaction of the Fe
atom sites on the surface of Fe2O3 was considered. The ΔEbarrier of the re-
actions of H2 on the top, bridge, and hollow sites of the Fe atom sites
were 2.30, 2.47, and 2.64 eV, respectively. The ΔEbarrier of the reaction
of H2 on the Fe atom top site was the lowest, indicating that the top
site of the Fe atom was the most prone to chemical reactions and was as-
sociated the optimal reaction pathway. This reaction pathway is Path 1
and is consistent with adsorbability of H2 on the surface of Fe2O3.
Table 1 and Fig. S2–S3 of the ESI show the ΔEbarrier of the Fe and Cu
atoms sites of the surface of Cu-Fe2O3. The lowest energy barrier values
at the Fe atom top site and Cu atom top site were 1.81 eV and 1.68 eV,
respectively. These also constituted the optimal reaction pathways for
the top site metal atoms of the surface of Cu-Fe2O3, namely Path 2 and
Path 3. Fig. 3 shows the structures of reactant (R), transition state (TS),
and product (P) in the three optimal reaction pathways.
As shown in Fig. 3, the ΔEbarrier of Fe2O3 reacted with H2 decrease from
2.30 eV to 1.68 eV of Cu-top site and 1.81 eV of Fe-top site for Cu-Fe2O3
surface. The decrease in the reaction energy barrier facilitated the reac-
tion between Cu-Fe2O3 and H2. In addition, in contrast to Path 2 and
Path 3 of the surface of Cu-Fe2O3, the ΔEbarrier of the Cu atom sites were
lower than those of the Fe atom sites. This result indicated the reaction
478
Powder Technology 388 (2021) 474–484
at the Cu atom sites preferentially occurred after adsorption following
the reaction at Fe atom sites. More importantly, the reaction pathways
of Cu-Fe2O3 with H2 differed from those of Fe2O3 and H2 due to Cu doping.
The reaction primarily originally occurred at the Fe atom sites for the one-
component Fe-based OC, whereas that for the Cu-Fe2O3 OC was at the Cu
atom sites followed by the Fe atom sites. The reaction energy barriers of
the surface of Cu-Fe2O3 were lower than those of the one-component
Fe-based OCs due to Cu doping. In addition, obvious synergistic effects
of Cu-Fe were evident [13,20]. Analysis of the micro-reaction mechanism
demonstrated that the enhancement of the reactivity of Cu-Fe2O3 was
mainly due to the existence of atomic-scale Cu doping defects.
Fig. 3 shows the optimal reaction pathways. Within the reactant
(R)-transition state (TS)-product (P) process, the H\\H bond of the H2
molecule first stretches and disconnects. Taking Path 1 as an example,
H—H:0.751 → 1.204 → 1.590 Å. At the same time, the O atom of the sur-
face of Fe2O3, representing the nearest to adsorption sites of H2 molecule,
gradually move up. In addition, the Fe\\O bond continuously stretches
and disconnects, path 1, Fe—O:1.832 → 2.081 → 2.580 Å. Subsequently,
it reacts with 2H atoms to form H2O: Path1, H—O:3.410 → 1.941 →
0.990 Å. Finally, the H2O molecule desorbs from the surface of the OC.
The oxidation processes of H2 on the surfaces of Fe2O3 and Cu-Fe2O3
were similar. The H\\H bonds of the H2 molecule and metal‑oxygen
bonds (Fe/Cu—O) of the surface of the OC disconnected to form H2O. Fi-
nally, H2O desorbs from the surface of the OC. As shown in Fig. 3, the
main differences related to bond type and bond length between the
structure of reactant, transition state, and product. This result could be at-
tributed to the different structures of OCs as described in Section 3.1.1.
3.1.4. Effects of the number and position of substituted Cu atoms on the re-
activity of OCs
The present study investigated the micro-reaction mechanisms of
Cu-Fe2O3, 2Cu-Fe2O3, and 3Cu-Fe2O3 with H2, respectively to explore
the effects of the number and position of substituted Cu atoms on the re-
activity of OCs. A reaction-mechanism analysis of Cu-Fe2O3 with H2
showed that the Cu atoms represented the surface activity sites and
the optimal reaction sites in contrast to the Fe atoms. Therefore, as
shown in Table 1 and Fig. S1–S10 of the ESI, the focus was mainly on
the reaction of Cu atom sites on the surface of nCu-Fe2O3.
The 2Cu-Fe2O3 models with different Cu positions include three
kinds of configurations. As shown in Fig. S4–S6 of the ESI, the top,
bridge, and hollow sites of Cu atoms for each of the 2Cu-Fe2O3 models
were considered. Similar to the Cu-Fe2O3 model, the top sites of Cu
atoms showed the lowest ΔEbarrier and represented the optimal reaction
pathways. The ΔEbarrier was ~1.3 eV, indicating that the substituted po-
sition of Cu atoms had little effect on the reaction energy barriers for
2Cu-Fe2O3 models. As shown in Fig. 4, compared to ΔEbarrier(Fe2O3) =
2.30 eV, the ΔEbarrier of 2Cu-Fe2O3 surface decreased by ~1.0 eV. There-
fore, the reactivity of 2Cu-Fe2O3 was enhanced.
As shown in Table 1 and Fig. S7–S10 of the ESI, similar to that pre-
sented for the 2Cu-Fe2O3 model, the present study investigated the reac-
tion mechanism of 3Cu-Fe2O3 with H2. The lowest ΔEbarrier of ~1.0 eV
occurred at the top sites of Cu atoms rather than at the bridge and hollow
sites. Similarly, the positions of substituted Cu atoms had little effect on
the reaction energy barrier for the 3Cu-Fe2O3 models. As shown in Fig. 4,
the ΔEbarrier decreased by ~1.3 eV as compared to ΔEbarrier(Fe2O3) = 2.30
eV. As a result, the Cu atoms sites of the 3Cu-Fe2O3 surface exhibited a
superior reactivity compared to Fe2O3, Cu-Fe2O3, and 2Cu-Fe2O3.
The above results indicated that the ΔEbarrier of H2 on the Cu atom
sites of the surface of nCu-Fe2O3 gradually decreased and the reactivity
gradually enhanced as the number of substituted Cu atoms increased.
The oxidation of H2 molecules at the Cu atom sites of 3Cu-Fe2O3 oc-
curred more readily. There were significant changes to the structure of
the Fe2O3 OC when multiple Fe atoms (≤ 3 atoms) of the surface of
Fe2O3 were replaced by Cu atoms. As shown in Section 3.1.1, these
changes included the introduction of active sites of Cu atoms in addition
N. Yuan, H. Bai, M. An et al. Powder Technology 388 (2021) 474–484

3.0
Path 1 Path 2 Path 3

2.5
2.30
H

2.0 R-1
Relative energy/eV

1.81
P-1
1.68
1.5
1.850
R-4
1.0 TS-1 P-4

0.5 R-7
TS-4
P-7

0.0 0.00
TS-7 -0.29
-0.36
-0.5 -0.34
R TS P
Reavtion coordinate

Fig. 3. The energy barrier diagram of OCs reaction with H2: Path 1: on Fe atom top sites of Fe2O3 surface; Path 2: on Fe atom top sites of Cu-Fe2O3 surface; Path 3: on Cu atom top sites of Cu-
Fe2O3 surface.

to those of Fe atoms, new chemical bonds, and an increase in bond

length. This was beneficial to H2 oxidation on the surface of nCu-Fe2O3. ΔEreaction ¼ Ep −ER (3)

In Eq. (3), Ep is the total energy of the produced H2O molecules

3.1.5. Reaction heat of OCs with H2
The reaction heat of OCs with fuels in the reactor can be used to pro-
vide the thermal equilibrium required for the chemical looping system,
thereby reducing the required external heat supply and improving the
economy of the chemical looping process. Hence, there is value in ex-
ploring the change in heat occurring during reactions of OCs with H2.
The reaction heat (ΔEreaction) was calculated to investigate the
change in heat of the Cu2xFe2(1-x)O3 reaction with H2:
desorbed from the OC surfaces. A negative ΔEreaction value indicates an
exothermic reaction, whereas a positive ΔEreaction value indicates an en-
dothermic reaction.
As shown in Table 1, all ΔEreaction values of the reaction of nCu-Fe2O3
with H2 were negative, indicating that the reaction was exothermic,
thereby supplying heat during the chemical looping process. Further-
more, the reaction heat increased from 0.29 eV for Fe2O3 to the maxi-
mum 1.12 eV for nCu-Fe2O3 as the number of Cu atoms increased for

3
Fe2O3 Cu-Fe2O3 2Cu-Fe2O3 3Cu-Fe2O3
Fe sites Fe sites Cu sites Cu sites Cu sites
2.30
∆Ebarrier/eV

2
1.81

1.68

1.30

1.29
1.28

1.07

1.06
1.03
1.02

1
1 1 2 1 2 3 1 2 3 4
The number of the stable adsorption configrations of H2 molecule on nCu-Fe2O3 surface

top bridge hollow

Fig. 4. The energy barrier of different reaction sites for nCu-Fe2O3 OCs reacted with H2, respectively.

479
N. Yuan, H. Bai, M. An et al.
nCu-Fe2O3. Therefore, Cu doping can modulate the heat produced
through the reaction between Fe2O3 OC and H2 during the chemical
looping process.
3.2. Experimental analysis
3.2.1. Characterization of OCs
As shown in Fig. 5, the XRD was used to characterize the composition
and crystal structure of Cu2xFe2(1-x)O3 OCs. As shown in Fig. 5(a), all the
characteristic diffraction peaks of Fe2O3 were present for both
the fresh Fe2O3 and Cu2xFe2(1-x)O3 OC samples. This indicated that
the Cu2xFe2(1-x)O3 OCs were converted to Fe2O3 after calcination at
high temperature. No other impurity phase was evident. Furthermore,
the doped Cu atoms completely entered the Fe2O3 lattice to replace
the equivalent number of Fe atoms [23]. As shown in Fig. 5(b), all lattice
oxygen removed from Fe2O3 OC was converted to metallic Fe, whereas
the Cu2xFe2(1-x)O3 OCs were reduced to metallic Cu and Fe.
As shown in Fig. 6, the element distribution of the surface of the
Cu2xFe2(1-x)O3 OCs was characterized through SEM-EDX mapping. The
O, Cu, and Fe elements of the surfaces of Cu2xFe2(1-x)O3 (x = 10%) OCs
were uniformly distributed with no local accumulation and agglomera-
tion. This result indicated that a low concentration of Cu doping in the
Fe2O3 lattice could be realized through the co-precipitation method. In
addition, the elements of the surfaces of the Cu2xFe2(1-x)O3 OCs were
uniformly distributed. In particular, the original crystalline structure of
Fe2O3 was maintained. Agglomeration and sintering did not readily
occur due to the amount and distributed forms of the Cu element
[20,41].
As shown in Fig. 7, the morphologies of the Cu2xFe2(1-x)O3 (x = 10%)
OCs before and after the release of lattice oxygen were characterized by
SEM. Fig. 7(a)(c) shows an increase in the particle diameter of the re-
duced Fe2O3 OC. The shapes of particles were more obvious and gaps/
pores also appeared. The results shown in Fig. 7(b)(d) indicated in-
creases in the particle diameter, pore size, and number of gaps of the re-
duced Cu2xFe2(1-x)O3 OCs. In addition, the number of pores increased
when the lattice oxygen was removed at 900 °C. Moreover, no agglom-
eration and sintering was evident, which was due to the amount and
distribution forms of the Cu element and the method of preparing the
OCs [20]. Overall, doping using Cu under a low concentration changed
the structure of the Fe2O3 OC and optimized its micro-morphology.
This was beneficial to the rapid release of lattice oxygen during the
chemical looping process.
3.2.2. Analysis of the reactivity of Cu2xFe2(1-x)O3 OCs
The conversion rate (Ct) was calculated by the TGA experiments to
explore the reactivity of Cu2xFe2(1-x)O3 OCs. The sample weight wt at a
given time t was converted to the Ct of OC as follows:
(a) Fresh * * Fe2O3
* *
* * *
Cu0.2Fe O
1.8 3
**
Intensity(a.u)
Cu0.10Fe O
1.90 3
Cu0.04Fe O
1.96 3
Cu0.02Fe O
1.98 3
Fe2O3
10 20 30 40 50 60 70
2θ (°)
Fig. 5. XRD patters of Cu2xFe2(1-x)O3 OCs: (a) Fresh; (b) Reduced.
Powder Technology 388 (2021) 474–484
wi −wt
Ct ¼  100% (4)
wi −wx
In Eq. (4), wi and wx represents the initial weight of the sample and
the weight of the reduced OC, respectively. The rate of release of lattice
oxygen can be determined by the relationship between Ct and t. Finally,
the Arrhenius equation was used to calculate the apparent activation
energy, Ea.
Fig. 8 shows the Ct-t curves of the reaction between the Cu2xFe2(1-x)
O3 OCs and H2. The value of Ct of the OC at unit time was positively re-
lated to the rate of release of lattice oxygen and the reactivity of the
OC. As shown in Fig. 8(a), the Ct of the Cu2xFe2(1-x)O3 OCs (x = 10%)
gradually increased with increasing temperature from 700 °C to 900
°C. As shown in Fig. S-11 of the ESI, the trend of the conversion rate of
the Cu2xFe2(1-x)O3 OCs was the same as that of the Fe2O3. This result in-
dicated that the increase in temperature was beneficial to the rapid re-
lease of lattice oxygen of the Cu2xFe2(1-x)O3 OCs. More importantly, as
shown in Fig. 8(b), the Ct and rate of release of lattice oxygen of the
Cu2xFe2(1-x)O3 OCs exceeded those of Fe2O3 at the same temperature.
The relationship of Ct and rate of release of lattice oxygen of the
Cu2xFe2(1-x)O3 OCs at 700 °C was:
Cu0.20Fe1.80O3>Cu0.10Fe1.90O3>Cu0.04Fe1.96O3>Cu0.02Fe1.98O3>Fe2O3.
This result could be attributed to the Cu component increasing the
reactivity of Cu-Fe OCs [42,43]. In addition, the Ct and rate of release of
lattice oxygen of the Cu2xFe2(1-x)O3 OCs gradually increased with in-
creasing Cu content under a constant temperature. A low content of
Cu inhibited agglomeration and sintering during the chemical looping
process [20]. Therefore, it was concluded that the use of Cu2xFe2(1-x)O3
OCs is more suitable for the chemical looping process due to a higher
conversion rate and a rapid lattice oxygen release rate.
As shown in Fig. 9, the Ea of the reaction between the Cu2xFe2(1-x)O3
OCs and H2 was calculated based on Ct-t curves and the Arrhenius equa-
tion. The Ea represents the energy required for the occurrence of the
chemical reaction, with the value of Ea inversely related to the ease at
which the chemical reaction occurs. Ea values of 83.9, 72.3, 66.0, 41.1,
and 37.0 kJ/mol corresponded with molar ratios of Cu doping of 0, 1,
2, 5, and 10%, respectively. This result indicated that the reactivities of
Cu2xFe2(1-x)O3 OCs gradually increased with an increase doped Cu.
Low concentration Cu doping effectively improved the reactivity of
the Fe2O3 OC. The reactivity of the Cu2xFe2(1-x)O3 OCs gradually in-
creased with increasing Cu content. More importantly, the concentra-
tion of doped Cu modulated the Ea and reactivity of the Fe2O3 OC,
consistent with the analysis of the mechanism of the reaction between
Cu2xFe2(1-x)O3 OCs and H2 shown in Section 3.1. As shown in
Section 3.1.3, this result explained the microscopic nature of reactivity
enhancement of Cu2xFe2(1-x)O3 OCs.
(b) Reduced * Fe k Cu
*
Cu0.2Fe O
1.8 3 k * *
Intensity(a.u)
Cu0.10Fe O
1.90 3
Cu0.04Fe O
1.96 3
Cu0.02Fe O
1.98 3
Fe2O3
80 10 20 30 40 50 60 70 80
2θ (°)
480
N. Yuan, H. Bai, M. An et al. Powder Technology 388 (2021) 474–484

Fig. 6. The SEM-Mapping images of the O, Cu and Fe elements distribution for Cu2xFe2(1-x)O3 OCs (x = 10%).

Fig. 7. SEM images of oxygen carrier: (a) Fresh Fe2O3; (b) Reduced Fe2O3 at 900 °C; (c) Fresh Cu2xFe2(1-x)O3 (x = 10%); (d) Reduced Cu2xFe2(1-x)O3 (x = 10%), at 900 °C.

481
N. Yuan, H. Bai, M. An et al. Powder Technology 388 (2021) 474–484

100 100
(a) (b) 700 ℃

Particle Conversion/%
Particle Conversion/%
80 80

60
Fe2O3
60
700 ℃ 1% Cu-Fe2O3
40 750 ℃ 40 2% Cu-Fe2O3
800 ℃
850 ℃
5% Cu-Fe2O3
20 900 ℃ 20 10% Cu-Fe2O3

0 0
0 10 20 30 40 50 0 10 20 30 40 50
Reaction Time /min Reaction Time /min

Fig. 8. The conversion rate curves of OCs at different temperature: (a) Cu0.20Fe1.80O; (b) at 700 °C, Cu2xFe2(1-x)O3 (x = 0, 1, 2, 5 and 10%).

2.5 3.3. Mechanism insights

The lattice oxygen release process of Cu2xFe2(1-x)O3 OCs can be di-

2.0
vided into different stages based on the TG and DTG curves shown in
Fig. 10. Fig. 10 (a) shows that the process of lattice oxygen release of
1.5 the Fe2O3 OC was divided into three stages. By combining with the re-
sults of XRD characterization shown in Fig. 5, the lattice oxygen release
ln (k)

process of Fe2O3 OC was:

1.0 Fe2O3 Ea=83.9 kJ/mol
Cu0.02Fe1.98O3 Ea=72.3 kJ/mol I:Fe2O3 → Fe3O4；II:Fe3O4 → FeO；III:FeO → Fe.

0.5 Cu0.04Fe1.96O3 Ea=66.0 kJ/mol

This is similar to what has been reported in the literature
Cu0.10Fe1.90O3 Ea=41.1 kJ/mol
[1,2,4,44,45]. As shown in Fig. 10(b)(c), the lattice oxygen release pro-
Cu0.20Fe1.80O3 Ea=37.0 kJ/mol cess for the Cu2xFe2(1-x)O3 OCs consisted of four stages. By combined
0.0
0.8 0.9 1.0 1.1 with result with the DFT calculations, two distinct reaction steps were
1/1000T (K-1)
identified. The first reaction step is the preferential reactions of Cu
Fig. 9. The activation energy of Cu2xFe2(1-x)O3 (x = 0, 1, 2, 5 and 10%) reacted with H2.
atom sites with lower reaction barriers, followed by the reactions of Fe
atom sites with relatively higher reaction barriers. Therefore, stage I

100 0.0 100 0.0

-0.5 -0.5
80 80
-1.0 -1.0
(a)
DTG/%/min

DTG/%/min
-1.5 (b) -1.5
TG/%

60 TG 60
TG/%

DTG TG
-2.0 DTG -2.0
40 -2.5 40 -2.5
-3.0 -3.0
20 20
䊠 䊢 -3.5 䊠䊡 䊢 䊣 -3.5
䊡
0 -4.0 0 -4.0
0 10 20 30 40 50 0 10 20 30 40 50
Reaction Time/min Reaction Time/min

100 0.0
-0.5
80
-1.0
DTG/%/min

(c) -1.5
TG/%

60
TG -2.0
DTG
40 -2.5
-3.0
20
-3.5
0
䊠䊡 䊢 䊣 -4.0
0 10 20 30 40 50
Reaction Time/min

Fig. 10. TG and DTG curves of OCs reacted with H2, at 700 °C: (a) Fe2O3; (b) Cu2xFe2(1-x)O3 (x = 2%); (c) Cu2xFe2(1-x)O3 (x = 10%).

482
N. Yuan, H. Bai, M. An et al.
involved the reduction reaction of Cu atom sites and a higher release
rate of lattice oxygen compared to those of the remaining stages of
Cu2xFe2(1-x)O3 OCs. The II, III, and IV stages of the Cu2xFe2(1-x)O3 OCs rep-
resented the reduction reaction of the Fe2O3 OC with a low reaction rate.
As shown in Section 3.1, these results were consistent with the reaction
mechanism of Cu2xFe2(1-x)O3 OCs calculated by DFT.
TGA experiments and DFT calculations were used to investigate the
reaction mechanism between Cu2xFe2(1-x)O3 OCs and H2 during chemi-
cal looping combustion. As shown in Fig. 11, taking Cu-Fe2O3 as exam-
ple, the reaction of H2 on the surface of Cu-Fe2O3 included two distinct
steps: (1) the oxidation of H2 molecules at Cu atom sites and the pro-
duction of H2O required a minimum energy barrier of 1.68 eV; (2) the
oxidation of H2 molecules at Fe atom sites required a minimum energy
barrier of 1.81 eV. However, the reaction of the single-component sur-
face of Fe2O3 was primarily the oxidation of H2 molecules at Fe atom
sites which required a minimum energy barrier of 2.30 eV. The analysis
of the mechanism of the microscopic reaction showed that the en-
hanced reactivity of Cu2xFe2(1-x)O3 OCs was mainly due to the existence
of atomic-scale Cu doped defects. This significantly decreased the reac-
tion energy barrier of the reaction between Fe2O3 and H2 and modu-
lated the reaction pathways. As shown in Section 3, the doped Cu
atoms entered the Fe2O3 lattice and changed its structure, including
the slight shrinkage of the crystal cell from 5.036 to 5.035 Å, the intro-
duction of a new bond type and Cu surface active sites, and the increase
of bond length .
In contrast to the Fe2O3 OC, the structure of the Cu2xFe2(1-x)O3 OCs
included not only Cu, Fe, and O atoms, but also a change to the chemical
environment around Fe atoms. Originally, the reaction primarily oc-
curred at Fe atom sites in the single-component Fe2O3 OC. The reaction
for the Cu2xFe2(1-x)O3 OCs occurred first at Cu atom sites, followed by
the Fe atom sites. In particular, the reaction energy barriers were
lower than those of the single-component Fe2O3 OC due to Cu doping.
Thus, the reactivity of the Cu2xFe2(1-x)O3 OCs were enhanced, consistent
with the results observed in the TGA experiments.
As discussed previously, the lattice oxygen release process of Cu2xFe2
(1-x)O3 OCs (x = 1, 2, 5 and 10%) included two distinct reaction steps, as
follows:
The first step: I:Cu2xFe2(1-x)O3 → Cu, Fe2O3;
The second step:II:Fe2O3 → Fe3O4; III:Fe3O4 → FeO; IV:FeO → Fe.
Fig. 11. Schematic diagram of Cu-Fe2O3 oxygen carrier reaction with H2.
483
Powder Technology 388 (2021) 474–484
During the first step, the Cu2xFe2(1-x)O3 OCs were mainly converted
to metallic Cu and Fe2O3 at a rapid reaction rate. The second step consti-
tuted the stepwise reduction of Fe2O3 accompanied by the coexistence
of metallic Cu reduced during the first step. The reactivities of the
Cu2xFe2(1-x)O3 OCs exceeded those of the Fe2O3 OCs. This result could
be attributed to the existence of atomic-scale Cu doped defects. The
bonding of the surface Cu atoms to O atoms (Cu\\O bonds) exhibited
higher activity. The energy barrier values of Cu atom sites were lower
than those of Fe sites. This result could be attributed to the high reactiv-
ity of Cu2xFe2(1-x)O3 OCs observed in the TGA experiments. In addition,
although the reaction rate of the Cu2xFe2(1-x)O3 OCs clearly exceeded
that of pure Fe-based OCs, the rate within the second step during the
chemical looping process remained lower, as observed in the experi-
ments and DFT calculations.
4. Conclusions
The present study conducted a comprehensive investigation of the
reaction mechanism and modulation of reactivity between Cu2xFe2(1-x)
O3 OCs and H2 during chemical looping combustion based on TGA ex-
periments and DFT calculations. The main conclusions are listed below.
(1) The Cu2xFe2(1-x)O3 OCs with atomic scale Cu doped defects were
prepared. The reactivity in chemical looping combustion was
evaluated by the TGA experiments. The results showed that the
activation energy of Cu2xFe2(1-x)O3 OCs was in the range of
72.3–37.0 kJ/mol, exhibiting a superior reactivity compared to
that of Fe2O3 of 83.9 kJ/mol. DFT calculations confirmed that
the reaction energy barrier was in the range of 1.68–1.02 eV
and lower than that of Fe2O3 of 2.30 eV and in good agreement
with higher reactivity of Cu2xFe2(1-x)O3 OCs observed in the
TGA experiments.
(2) Systematic DFT calculations were conducted to reveal the micro-
scopic nature of reactivity enhancement for Cu2xFe2(1-x)O3 OCs.
The reaction mechanisms of Cu2xFe2(1-x)O3 OCs with different
doping concentrations and configurations were investigated.
The results indicated that the energy barriers of Cu2xFe2(1-x)O3
OCs with H2 gradually decreased from 1.68 eV to 1.02 eV with
an increase in the number of Cu atoms. The top sites of the Cu
atoms were identified to be the optimal reaction sites. It was
found that Cu doping and the modulation of the reaction path-
ways constituted the primary reasons for the enhancement of
the reactivity of Cu2xFe2(1-x)O3 OCs based on the analysis of tran-
sition state structures and the reaction mechanism.
(3) The mechanisms of the release of lattice oxygen of Cu2xFe2(1-x)O3
OCs were studied. A model containing two distinct reaction steps
was proposed. During the first step, Cu2xFe2(1-x)O3 OCs were
mainly converted to metallic Cu and Fe2O3 at a rapid reaction
rate. The second step constituted the stepwise reduction of
Fe2O3 under a slow reaction rate. Although the reactivities of
Cu2xFe2(1-x)O3 OCs were superior to those of Fe2O3, the rates dur-
ing the second step of the chemical looping process remained
lower. The results of the present study can act as a reference for
the screening, design, and optimization of Fe-based OCs.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgements
This work is mainly supported by National key research and devel-
opment program project (No. 2018YFB0605403-04), National Key
N. Yuan, H. Bai, M. An et al.
R&D Projects of China (No. 2018YFB0605401), Key R&D Projects of
Ningxia (No. 2018BCE01002), Natural Science Foundation of China
(No. 21868025), Financial supports from Innovation Program for Grad-
uate Students of Ningxia University (No. GIP2020054), Natural Science
Foundation Project of Ningxia (No. 2020AAC03020) and National Aca-
demic Subjects Construction Project of Ningxia (Chemical Engineering
and Technology, grant No. NXYLXK2017A04).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.powtec.2021.04.022.
References
[1] L. Fan, L. Zeng, S. Luo, Chemical-looping technology platform, AICHE J. 61 (2015)
2–22, https://doi.org/10.1002/aic.14695.
[2] P. Wang, N. Means, D. Shekhawat, D. Berry, M. Massoudi, Chemical-looping combus-
tion and gasification of coals and oxygen carrier development: a brief review, Ener-
gies 8 (2015) 10605–10635, https://doi.org/10.3390/en81010605.
[3] Th. Gauthier MYAF, CLC, a promising concept with challenging development issues,
Powder Technol. (2017)https://doi.org/10.1016/j.powtec.2017.01.003.
[4] S. Luo, L. Zeng, L.S. Fan, Chemical looping technology: oxygen carrier characteristics,
Annu. Rev. Chem. Biomol. Eng. 6 (2015) 53–75, https://doi.org/10.1146/annurev-
chembioeng-060713-040334.
[5] L. Zeng, Z. Cheng, J.A. Fan, L. Fan, J. Gong, Metal oxide redox chemistry for chemical
looping processes, Nat. Rev. Chem. 2 (2018) 349–364, https://doi.org/10.1038/
s41570-018-0046-2.
[6] M. An, J. Ma, Q. Guo, Transformation and migration of mercury during chemical-
looping gasification of coal, Ind. Eng. Chem. Res. 58 (2019) 20481–20490, https://
doi.org/10.1021/acs.iecr.9b04014.
[7] Z. Yu, Y. Yang, S. Yang, Q. Zhang, J. Zhao, Y. Fang, X. Hao, G. Guan, Iron-based oxygen
carriers in chemical looping conversions: a review, Carbon Resour. Convers. 2
(2019) 23–34, https://doi.org/10.1016/j.crcon.2018.11.004.
[8] Z. Cheng, L. Qin, J.A. Fan, L. Fan, New insight into the development of oxygen carrier
materials for chemical looping systems, Engineering 4 (2018) 343–351, https://doi.
org/10.1016/j.eng.2018.05.002.
[9] J. Hu, C. Li, Q. Zhang, Q. Guo, S. Zhao, W. Wang, D. Lee, Y. Yang, Using chemical
looping gasification with Fe2O3/Al2O3 oxygen carrier to produce syngas (H2+CO)
from rice straw, Int. J. Hydrogen. Energ. 44 (2019) 3382–3386, https://doi.org/10.
1016/j.ijhydene.2018.06.147.
[10] W. Huang, Y. Kuo, P. Su, Y. Tseng, H. Lee, Y. Ku, Redox performance of Na-modified
Fe2O3/Al2O3 with syngas as reducing agent in chemical looping combustion process,
Chem. Eng. J. 334 (2018) 2079–2087, https://doi.org/10.1016/j.cej.2017.11.177.
[11] Q. Guo, M. Yang, Y. Liu, Q. Yang, Y. Zhang, Multicycle investigation of a sol-gel de-
rived Fe2O3/ATP oxygen carrier for coal chemical looping combustion, AICHE J. 62
(2016) 996–1006, https://doi.org/10.1002/aic.15100.
[12] S. Bhavsar, M. Najera, G. Veser, Chemical looping dry reforming as novel, intensified
process for CO2 activation, Chem. Eng. Technol. 35 (2012) 1281–1290, https://doi.
org/10.1002/ceat.201100649.
[13] D. Zeng, Y. Qiu, S. Zhang, L. Ma, M. Li, D. Cui, J. Zeng, R. Xiao, Synergistic effects of bi-
nary oxygen carriers during chemical looping hydrogen production, Int. J. Hydrogen.
Energ. 44 (2019) 21290–21302, https://doi.org/10.1016/j.ijhydene.2019.06.118.
[14] B. Wang, G. Xiao, X. Song, H. Zhao, C. Zheng, Chemical looping combustion of high-
sulfur coal with NiFe2O4 combined oxygen carrier, J. Therm. Anal. Calorim. 118
(2014) 1593–1602, https://doi.org/10.1007/s10973-014-4074-y.
[15] R. Siriwardane, H. Tian, J. Fisher, Production of pure hydrogen and synthesis gas with
Cu-Fe oxygen carriers using combined processes of chemical looping combustion
and methane decomposition/reforming, Int. J. Hydrogen. Energ. 40 (2015)
1698–1708, https://doi.org/10.1016/j.ijhydene.2014.11.090.
[16] G. Liu, Y. Liao, Y. Wu, X. Ma, Evaluation of Sr-substituted Ca2Fe2O5 as oxygen carrier
in microalgae chemical looping gasification, Fuel Process. Technol. 191 (2019)
93–103, https://doi.org/10.1016/j.fuproc.2019.03.019.
[17] D.D. Miller, R. Siriwardane, CaFe2O4 oxygen carrier characterization during the par-
tial oxidation of coal in the chemical looping gasification application, Appl. Energy
224 (2018) 708–716, https://doi.org/10.1016/j.apenergy.2018.05.035.
[18] F. Liu, J. Liu, Y. Yang, X. Wang, A mechanistic study of CO oxidation over spinel
MnFe2O4 surface during chemical-looping combustion, Fuel 230 (2018) 410–417,
https://doi.org/10.1016/j.fuel.2018.05.079.
[19] G. Wei, F. He, Z. Zhao, Z. Huang, A. Zheng, K. Zhao, H. Li, Performance of Fe-Ni bime-
tallic oxygen carriers for chemical looping gasification of biomass in a 10 kWth in-
terconnected circulating fluidized bed reactor, Int. J. Hydrogen Energ. 40 (2015)
16021–16032, https://doi.org/10.1016/j.ijhydene.2015.09.128.
[20] S. Jiang, L. Shen, J. Wu, J. Yan, T. Song, The investigations of hematite-CuO oxygen
carrier in chemical looping combustion, Chem. Eng. J. 317 (2017) 132–142.
484
Powder Technology 388 (2021) 474–484
[21] X. Niu, L. Shen, S. Jiang, H. Gu, J. Xiao, Combustion performance of sewage sludge in
chemical looping combustion with bimetallic Cu-Fe oxygen carrier, Chem. Eng. J.
294 (2016) 185–192, https://doi.org/10.1016/j.cej.2017.01.091.
[22] V. Frick, M. Rydén, H. Leion, Investigation of Cu-Fe and Mn-Ni oxides as oxygen car-
riers for chemical-looping combustion, Fuel Process. Technol. 150 (2016) 30–40,
https://doi.org/10.1016/j.fuproc.2016.04.032.
[23] L. Qin, M. Guo, Y. Liu, Z. Cheng, J.A. Fan, L. Fan, Enhanced methane conversion in
chemical looping partial oxidation systems using a copper doping modification,
Appl. Catal. B Environ. 235 (2018) 143–149, https://doi.org/10.1016/j.apcatb.2018.
04.072.
[24] L. Huang, M. Tang, M. Fan, H. Cheng, Density functional theory study on the reaction
between hematite and methane during chemical looping process, Appl. Energy 159
(2015) 132–144, https://doi.org/10.1016/j.apenergy.2015.08.118.
[25] F. Li, S. Luo, Z. Sun, X. Bao, L. Fan, Role of metal oxide support in redox reactions of
iron oxide for chemical looping applications: experiments and density functional
theory calculations, Energy Environ. Sci. 4 (2011) 3661–3667, https://doi.org/10.
1039/c1ee01325d.
[26] V. Shah, Z. Cheng, D.S. Baser, J.A. Fan, L. Fan, Highly selective production of syngas
from chemical looping reforming of methane with CO2 utilization on MgO-
supported calcium ferrite redox materials, Appl. Energy 282 (2021)
116111–116123, https://doi.org/10.1016/j.apenergy.2020.116111.
[27] W. Zhang, F. Zhang, L. Ma, J. Yang, J. Yang, H. Xiang, Reaction mechanism study of
new scheme using elemental sulfur for conversion of barite to barium sulfide, Pow-
der Technol. 360 (2020) 1348–1354, https://doi.org/10.1016/j.powtec.2019.10.088.
[28] F. Liu, J. Liu, Y. Yang, Z. Wang, C. Zheng, Reaction mechanism of spinel CuFe2O4 with
CO during chemical-looping combustion: an experimental and theoretical study, P.
Combust. Inst. 37 (2019) 4399–4408, https://doi.org/10.1016/j.proci.2018.06.222.
[29] T. Li, Q. Wu, W. Wang, Y. Xiao, C. Liu, F. Yang, Solid-solid reaction of CuFe2O4 with C
in chemical looping system: a comprehensive study, Fuel 267 (2020) 117163,
https://doi.org/10.1016/j.fuel.2020.117163.
[30] G. Velde, F M B E JGST, Chemistry with ADF, J. Comput. Chem. 22 (2001) 931–967,
https://doi.org/10.1002/jcc.1056.
[31] V. Pershina, Relativistic effects on the properties of Lr: a periodic DFT study of the
adsorption of Lr on surfaces of Ta in comparison with Lu and Tl, Inorg. Chem. 59
(2020) 5490–5496, https://doi.org/10.1021/acs.inorgchem.0c00120.
[32] G. Te Velde, E.J. Baerends, Precise density-functional method for periodic structures,
Phys. Rev. B 44 (1991) 7888–7903, https://doi.org/10.1103/PhysRevB.44.7888.
[33] C. Lin, W. Qin, C. Dong, H2S adsorption and decomposition on the gradually reduced
α-Fe2O3(001) surface: a DFT study, Appl. Surf. Sci. 387 (2016) 720–731, https://doi.
org/10.1016/j.apsusc.2016.06.104.
[34] J.P. Perdew, K. Burke, Y. Wang, Generalized gradient approximation for the
exchange-correlation hole of a many-electron system, Phys. Rev. B Condens. Matter
54 (1996) 16533–16539, https://doi.org/10.1103/physrevb.54.16533.
[35] C. Lin, W. Qin, C. Dong, Reduction effect of α-Fe2O3 on carbon deposition and CO ox-
idation during chemical-looping combustion, Chem. Eng. J. 301 (2016) 257–265,
https://doi.org/10.1016/j.cej.2016.04.136.
[36] R.A. Evarestov, Quantum Chemistry of Solids: The LCAO First Principles Treatment of
Crystals, first ed. Springer Science & Business Media Press, Germany, 2007.
[37] H. Bai, W. Qiao, Y. Zhu, Y. Huang, Crystal orbital study on the combined carbon
nanowires constructed from linear carbon chains encapsulated in zigzag double-
walled carbon nanotubes, Curr. Appl. Phys. 15 (2015) 342–351, https://doi.org/10.
1016/j.cap.2015.01.008.
[38] H. Bai, Y. Zhu, W. Qiao, Y. Huang, Structures, stabilities and electronic properties of
graphdiyne nanoribbons, RSC Adv. 1 (2011) 768–775, https://doi.org/10.1039/
c1ra00481f.
[39] G. Henkelman, H. Jónsson, Improved tangent estimate in the nudged elastic band
method for finding minimum energy paths and saddle points, J. Chem. Phys. 113
(2000) 9978–9985, https://doi.org/10.1063/1.1323224.
[40] X. Xiao, W. Qin, J. Wang, J. Li, C. Dong, Effect of surface FeS hybrid structure on the
activity of the perfect and reduced α-Fe2O3(001) for chemical looping combustion,
Appl. Surf. Sci. 440 (2018) 29–34, https://doi.org/10.1016/j.apsusc.2017.12.252.
[41] L. Zhang, X. Wang, J.M. Millet, P.H. Matter, U.S. Ozkan, Investigation of highly active
Fe-Al-Cu catalysts for water-gas shift reaction, Appl. Catal. A Gen. 351 (2008) 1–8,
https://doi.org/10.1016/j.apcata.2008.08.019.
[42] H. Leion, T. Mattisson, A. Lyngfelt, Using chemical-looping with oxygen uncoupling
(CLOU) for combustion of six different solid fuels, Energy Procedia 1 (2009)
447–453, https://doi.org/10.1016/j.egypro.2009.01.060.
[43] C. Rhodes, G.J. Hutchings, Studies of the role of the copper promoter in the iron
oxide/chromia high temperature water gas shift catalyst, Phys. Chem. Chem. Phys.
5 (2003) 2719, https://doi.org/10.1039/b303236c.
[44] A. Pineau, N. KANARI, I. Gaballah, Kinetics of reduction of iron oxides by H2 part I:
low temperature reduction of hematite, Thermochim. Acta 447 (2006) 89–100,
https://doi.org/10.1016/j.tca.2007.01.014.
[45] T. Song, L. Shen, J. Xiao, Z. Gao, H. Gu, S. Zhang, Characterization of hematite oxygen
carrier in chemical-looping combustion at high reduction temperature, J. Fuel Chem.
Technol. 39 (2011) 567–574, https://doi.org/10.1016/S1872-5813(11)60036-4.