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Controlling lattice oxygen activity of oxygen

Cite this: DOI: 10.1039/d1re00209k
carrier materials by design: a review and
perspective
Wen Liu

Chemical looping is a class of emerging process intensification technologies that enable emission
Published on 06 July 2021. Downloaded on 8/12/2021 6:04:12 PM.

Received 31st May 2021,
Accepted 6th July 2021
DOI: 10.1039/d1re00209k
rsc.li/reaction-engineering
reduction of a wide range of chemical processes. The performance of oxygen carrier materials is critical to
the effectiveness of the chemical looping processes. Over the past two decades, understanding of how
oxygen carriers behave over chemical looping cycles continued to improve, leading to encouraging
advancements in recent years, including several newly developed chemical looping applications showing
promise to achieve lower CO2 footprints compared to conventional reactor technologies. Amongst the
key material design considerations, having appropriate lattice oxygen activity is critical for maximising the
product yield and selectivity of chemical looping processes. In this minireview, material design approaches
enabling the development of oxygen carriers with well-defined and well-regulated lattice oxygen activity
are overviewed and critically assessed. Besides the significant progress made, there remain key knowledge
gaps in the area of lattice oxygen engineering. Lastly, the potential roles which computational tools could
play in designing oxygen carriers with targeted lattice oxygen activities are discussed.

Introduction significantly reduced carbon footprints. This target can be

Given the worsening global climate due to rapidly increasing
anthropogenic CO2 emission,1,2 there is an imperative need
to transform the current energy and chemical sectors, two of
the major emitters of greenhouse gases,3,4 to operate with
School of Chemical and Biomedical Engineering, Nanyang Technological University, 62
Nanyang Drive, Singapore 637459, Singapore. E-mail: wenliu@ntu.edu.sg
Dr. Wen Liu is an assistant
professor at the School of
Chemical and Biomedical
Engineering, Nanyang
Technological University. His
research involves employing
experimental and computational
tools to understand and develop
novel oxygen carrier materials for
chemical looping applications,
with particular focus on fine-
tuning the lattice oxygen activities
and incorporating catalysis to
Wen Liu
chemical looping processes. He
also works extensively in understanding metal–support interactions
in heterogeneous catalysis for green chemistry, CO2 conversion and
emission control applications.
achieved by increasing the use of low-carbon energies,
developing a circular economy and improving the efficiency
of chemical processes, e.g. by adopting process
intensification technologies.5–7 One emerging class of process
intensification technologies is chemical looping. In essence,
chemical looping technologies split a conventional chemical
reaction into multiple steps, each (usually a redox reaction
between a gas and a solid) taking place in a separate reactor.
Examples of two-step chemical looping processes are
depicted in Scheme 1. The overall reaction is facilitated by
circulating a carrier material between the reactors.
Continuous operation can be achieved using a circulating
fluidized bed system or an array of fixed bed reactors with
alternating feed compositions. The carrier material works
analogously to a heterogeneous catalyst, except that a
“turnover” of the carrier material is completed as it
completes one round of circulation through all the reactors,
instead of an adsorption–reaction–desorption cycle as in a
conventional catalytic reactor.
The chemical looping approach offers a number of unique
advantages. First, different reactants are physically isolated.
Therefore, the cost of product separation is low.8,9 Secondly,
reactors in the same chemical looping system can operate
under vastly different conditions, allowing each reactant to
be activated at favourable temperature, pressure and
residence time in a dedicated reactor. One application
exploiting this advantage is chemical looping dry reforming

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Scheme 1 Conceptual illustration of chemical looping involving
oxygen transfer (chemical looping ammonia synthesis is not included).
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MO and M represent the oxidised and reduced forms of the oxygen
carrier.
of methane (CL-DRM).10 In conventional DRM, a delicate
balance between the kinetics of C–H activation and CO
activation on the catalyst surface is required to achieve a
satisfactory rate of methane conversion and to mitigate
carbon deposition.11 In CL-DRM, however, the residence time
of the carrier in the CO2 activation step can be much longer
than that in the CH4 activation step, such that all the carbon
deposited on the surface of the catalytic carrier can be
effectively removed via the reverse Boudouard reaction (C +
CO2 ⇌ CO), completely eliminating potential issues
associated with the accumulation of carbon in the system.12
Another example is chemical looping ammonia synthesis, in
which the activation of H2 and N2 is conducted in separate
reactors under vastly different conditions, enabling a notable
rate of ammonia production at 150 °C and 1 atm; these are
significantly more moderate conditions than those used by
the Haber process.13 Thirdly, by avoiding reactant mixing,
chemical equilibrium limitations commonly seen in single-
reactor systems may be circumvented. Metcalfe et al.
demonstrated that the equilibrium limitation of the water–
gas-shift reaction (CO + H2O ⇌ CO2 + H2) can be alleviated
by operating a packed bed of La0.6Sr0.4FeO3−δ in a chemical
looping fashion,14 resulting in the complete conversion of
CO and H2O into CO2 and H2, respectively, at 820 °C. At the
same temperature, a single water–gas-shift reactor is being
constrained by chemical equilibrium with Kp ∼ 1. Solar
thermochemical water splitting also benefits from the
chemical looping scheme, which can reduce the operating
temperature of water splitting from >3000 °C (in the absence
of a carrier material) to <2000 °C.15,16 Fourthly, the activity
of lattice oxygen can be easily tuned across many orders of
magnitude. Such a level of precise control is challenging in
conventional chemical reactors, in which the activity of the
oxidant depends on the partial pressures of the oxidising
gases. This point is best illustrated by the oxidative
conversion of ethane, which can undergo various degrees of
oxidation:
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C2H6 + 3.5O2 = 2CO2 + 3H2O (1)
C2H6 + 2.5O2 = 2CO + 3H2O (2)
C2H6 + 1/2O2 = C2H4 + H2O (3)
In this chemical system, high oxygen activity favours the
production of carbon oxides (reactions (1) and (2)), whereas the
formation of ethylene (reaction (3)), a much more valuable
product, is favoured by low oxygen activity. Therefore,
suppressing the oxygen activity can effectively promote the
process economics. By using lattice oxygen as the sole oxidant,
the oxygen activity can be easily suppressed to achieve desirable
ethylene yields, as demonstrated by Li and co-workers
employing a chemical looping oxidative dehydrogenation (CL-
ODH) process.17–19 Likewise, the chemical looping approach
has been adopted for a variety of applications, including the
ODH of propane and ethyl benzene,20,21 selective oxidation of
methane to methanol,22,23 oxidative coupling of methane
(OCM),24–26 and the epoxidation of ethylene to ethylene
oxide.27–30 Lastly, reactions in chemical looping systems take
place much closer to equilibria than those in conventional
reactors, meaning that chemical looping systems generally
exhibit higher exergy efficiency.31,32 The aforementioned
advantages have made chemical looping technologies
increasingly popular amongst reaction engineers in recent
years. In addition to the applications mentioned above, there
are also catalytic processes that do not use the term “chemical
looping”, but embody the same essential idea, such as
Dupont's maleic anhydride process utilising a vanadium
phosphorous oxide (VPO) redox catalyst and the oxidative
functionalisation of glucose using the lattice oxygen of CuO by
Amaniampong et al.33–35
The majority of the chemical looping applications
developed so far involve the transfer of oxygen (e.g. as shown
in Scheme 1). Accordingly, the performance of oxygen carriers
is of paramount importance to chemical looping processes.
As discussed above, the supply of lattice oxygen by the oxygen
carriers determines the rate and the product selectivity of
chemical looping reactions. Selectivity control is especially
important to the partial oxidation of hydrocarbon feedstocks,
e.g. ODH, epoxidation, OCM, DRM and selective methane
oxidation to methanol:
C2H6 + MO = C2H4 + H2O + M (4)
C2H4 + MO = C2H4O + M (5)
2CH4 + MO = C2H6 + H2O + M (6)
CH4 + MO = CO + 2H2 + M (7)
CH4 + MO = CH3OH + M (8)
where MO and M are the reduced and oxidised forms of the
oxygen carriers, typically consisting of redox-active metal
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oxides, often supported on refractory materials to provide
additional resistance against sintering and attrition. For each
new chemical looping application, a great deal of research is
required to understand how the oxygen carrier formulations
determine the activity of the lattice oxygen. For example,
Donat and Müller linked the electrophilic lattice oxygen (O2−
in the lattice) to the partial oxidation of methane to syngas,
whereas the nucleophilic lattice oxygen was associated with
the complete oxidation of methane to CO2 and H2O.36 This
minireview aims to critically assess recent advances in
designing oxygen carriers with well-defined lattice oxygen
activity and to rationalise the relevant oxygen carrier design
strategies. Hopefully, the findings can be used to guide the
development of new oxygen carrier formulations that can
simultaneously achieve high conversion, high product
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selectivity and high cyclic stability. Interested readers are also
referred to recent review papers for more comprehensive
accounts of recent developments in other aspects of chemical
looping research.37–40
Solid solution mixtures
Chemical looping systems typically operate between 600 and
950 °C. Solid compounds that are sufficiently redox-active
over this temperature range include the oxides of Mn, Fe, Co,
Ni and Cu. The thermodynamics of these monometallic
oxides are well-understood.41 However, such a small pool of
candidate oxygen carriers limits the potential to develop
Fig. 1 (a) Crystal lattices of the corundum (A2O3), spinel (AB2O4) and halite (AO) structures. (b) Temperature–composition phase diagram of the
Mn–Fe–O system in 5% O2. (c) Pressure–composition phase diagram of the Al2O3–Fe–O system at 850 °C. (d) Pressure–composition phase diagram
of the MgO–Fe–O system at 850 °C. (b) is reproduced with permission from ref. 54, copyright 2013 American Chemical Society. Both (c) and (d)
were calculated using MTDATA with the NPL Oxide Database.56,57
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versatile chemical looping applications, which require access
to a wider range of lattice oxygen activities at specific
temperatures and pressures. Therefore, the lattice oxygen
activity of the 3d transition metal oxides must be fine-tuned
by doping other metal cations, a strategy that is commonly
used by the heterogenous catalysis and semiconductor
communities. Here, the lattice oxygen activity of the doped
oxides is directly linked to the chemical states of the active
metal centres (i.e. Mn, Fe, Co, Ni and/or Cu).
Doping 3d transition metal oxides with cations of
comparable ionic radii could form various types of solid
solution mixtures. For example, two trivalent metal oxides
could form a corundum or a bixbyite solid solution. A
trivalent metal oxide and a divalent oxide could form a spinel
solid solution. Lastly, the interaction between two divalent
metal oxides could result in a halite solid solution. Fig. 1a
depicts the lattice structures of the solid solution phases
commonly seen in mixed oxide oxygen carriers. The
formation of solid solutions alters the coordination
environments of the active metal centres (especially in the
case of spinel solid solutions), the redox activity of the metal
centres, and the activity of the lattice oxygen.
For metal centres that are relatively stable in both +2 and
+3 oxidation states, e.g. Mn, Fe, and Co, doping cations of
comparable ionic radii would result in mixtures of bixbyite,
corundum, spinel and/or halite solid solution phases. The
complexity of the solid solution mixtures is illustrated by the
Al2O3–Fe–O, Mn–Fe–O and MgO–Fe–O phase diagrams, as
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shown in Fig. 1(b)–(d), respectively. Because the solid
solutions are compositionally flexible, one can further fine-
tune their cationic compositions to adjust the lattice oxygen
activity. In general, mixing a highly redox-active metal cation
with a non-reducible cation will result in moderated redox
activity.42,43 More specifically, doping cations that are stable
in high oxidation states reduces the lattice oxygen activity,
whereas doping cations that are stable in low oxidation states
promotes the lattice oxygen activity. Therefore, for chemical
looping applications requiring highly active lattice oxygen,
e.g. chemical looping combustion (CLC), the formation of
solid solutions consisting of stable trivalent cations is
undesirable. This is corroborated by the large number of
studies reporting that the formation of aluminate spinels
(e.g. CuAl2O4,44–46 NiAl2O4,47–49 CoAl2O4 (ref. 50 and 51) and
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FeAl2O4 (ref. 52 and 53)) hinders the activity of Cu, Ni, Co
and Fe-based oxygen carriers. On the other hand, structures
that are difficult to reduce, e.g. aluminate spinels, may be
suitable for chemical looping hydrogen (CLH) production.
For instance, reducing an Fe2O3/Al2O3 oxygen carrier will
result in an FeO/FeAl2O4 solid solution mixture (Fig. 1b),
which is capable of splitting water:
3xFeO + FeAl2O4 + xH2O ⇌ Fe1+3xAl2O4+4x + xH2 (9)
with a substantially higher equilibrium constant compared to
unmodified FeO at 800–1000 °C. Nevertheless, the reduction
to FeO/FeAl2O4 is kinetically sluggish compared to that to
FeO.52 Indeed, the trade-off between the rate of reduction
and the water-splitting performance of the reduced oxygen
carrier is an important design consideration for CLH.
As shown in the example above, high lattice oxygen
activity is not always beneficial. When Mn-based oxygen
carriers are used for chemical looping oxygen uncoupling
(CLOU), the decomposition of Mn2O3 to Mn3O4 and O2 is so
thermodynamically favourable that the regeneration of
Mn3O4 to Mn2O3 is challenging. To address this issue, Azimi
et al. mixed Mn2O3 with Fe2O3 to modulate the reducibility of
the oxygen carrier. The resulting hematite–bixbyite solid
solution mixtures (see Fig. 1c) are more regenerable during
CLOU cycles.54
Contrasting Al2O3, doping MgO could improve the
reducibility of trivalent oxides such as Fe3+ (see Fig. 1d). The
stability of Mg2+ contributes to the stability of the MgO–FeO
solid solution and ultimately the stability of the Fe2+ state.
Thermodynamically, this makes Fe3+ in the solid solution
mixture more reducible than those in Fe2O3 and Fe3O4.55
With the right MgO : Fe2O3 ratio, the MgO–Fe2O3 mixed
oxides could be excellent oxygen carriers for CLC.
Solid solutions can also be used as regenerative substrates
to prepare catalytically active oxygen carriers by exsolution;
this is particularly relevant to chemical looping applications
requiring the cleavage of C–C and C–H bonds, e.g. chemical
looping reforming (CLR). For instance, CoFe2O4 and NiFe2O4
spinels have been widely reported as good catalytic oxygen
carriers for CLR.12,58,59 In the reduction reactor of CLR, the
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spinel phases donate lattice oxygen to partially oxidise the
hydrocarbon feedstocks, accompanied by the precipitation of
metal nanoparticles, which serve as catalysts for the
activation of the hydrocarbons, e.g. CH4.60 Concomitantly,
the spinel solid solution regulates the lattice oxygen activity,
steering the selectivity towards syngas, whilst suppressing the
over-oxidation to CO2 and H2O. The surface carbon species
formed upon successive C–H cleavage could be readily
oxidised by the residual lattice oxygen, preventing the
accumulation of coke. As such, this multifunctional oxygen
carrier design is particularly beneficial to the production of
syngas via CLR.
Ternary oxide phases
Mixing 3d transition metal oxides with oxides of significantly
different cationic radii could result in the formation of stable
ternary oxide phases, having a nominal formula AxByOz. In
these ternary oxides, the A sites are often occupied by non-
redox active cations, while the transition metal cations
occupy the coordinatively well-defined B sites (as oppose to
the near-random site occupancies in solid solution mixtures).
Examples of such ternary oxide oxygen carriers include
NaFexAl1−xO2,55 SrFeO3 and its derivatives,61–64 Ca2Fe2O5 and
its derivatives,65–67 Fe-doped hexaaluminates,68–70
Ruddlesden–Popper phases (An+1BnO3n+1, n = 1, 2, …,
∞),30,71,72 etc. (the list is non-exhaustive), as depicted in
Fig. 2a. Using the ternary oxide phases as oxygen carriers
offers unique advantages, which are discussed in the
following.
Firstly, the structures of these ternary oxide phases are
considerably stable. Such stability allows transition metals to
be present at oxidation states that are inaccessible in their
native oxide phases, e.g. Fe4+ in SrFeO3 and Ni3+ in LaNiO3.73
These higher-than-usual oxidation states often correspond to
high lattice oxygen activity and the ability to release gaseous
oxygen; this is particularly relevant to chemical looping air
separation (CLAS) and chemical looping oxygen uncoupling
(CLOU).64,74 In other cases, transition metals can be
stabilised in their native oxidation states beyond the
thermodynamic limits of their native oxides. One typical
example is Fe3+ in Ca2Fe2O5, which is stable across a wide
range of pO2, as shown in the CaO–Fe–O phase diagram in
Fig. 2b. Consequently, the oxidation of a mixture of metallic
Fe and CaO to Ca2Fe2O5 is thermodynamically more
favourable than that from pristine Fe to FeO. Chan et al.
exploited this unique feature for CLH and demonstrated
improved steam conversion and hydrogen yields (measured
in terms of mol H2 per mol Fe per cycle) over unmodified
Fe2O3.65
Secondly, these ternary oxide phases are often capable of
accommodating a large amount of oxygen vacancies. One
typical example is ABO3−δ perovskite oxygen carriers, where 0
< δ < 0.5 denotes the amount of oxygen vacancies per unit
cell. These oxygen vacancies facilitate rapid oxygen transport
through the oxygen carrier.75 In certain cases, the oxygen
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Fig. 2 (a) Crystal lattices of the perovskite phase, brownmillerite phase, Ruddlesden–Popper phase (with the specific example of A3B2O7),
NaFe0.25Al0.75O2, and Ca-hexaaluminate (magnetoplumbite structure). (b) Pressure–composition phase diagram of the CaO–Fe–O system calculated
at 850 °C. The x-axis represents the total pressure of the system, exerted by O2 gas. The solid lines represent the phase boundaries. The phase
diagram was calculated using MTDATA with the NPL Oxide Database.56,57
transport through the oxygen-deficient structures is so fast
that the lattice oxygen activity would quickly equilibrate with
the gas phase. Metcalfe et al. exploited this fast-equilibrating
behaviour of perovskite-structured oxides (viz. La0.6Sr0.4-
FeO3−δ) and demonstrated a chemical looping water–gas-shift
scheme (CL-WGS) with the ability to overcome the chemical
equilibrium limitations commonly seen in conventional
water–gas-shift reactors.14
Thirdly, both the A sites (typically occupied by alkali
metals, alkaline earth metals and lanthanides) and the B
sites (often occupied by transition metals) of the ternary
oxide phases can be substitutionally doped with a variety of
cations to various extents without undergoing any major
phase change. Upon doping, the degree of lattice distortion,76
the charge balance77 and the metal–oxygen covalency will
change accordingly,78 thus altering the binding of lattice
oxygen and its activity.62 Examples of how lattice distortion
and transition metal–oxygen covalency change with the A-site
occupancy of perovskite phases are illustrated in
Fig. 3a and b.
Owing to the versatile applications of perovskite oxides in
heterogeneous catalysis,79,80 fuel cells, electrocatalysis,81–83
magnetism,84,85 etc., a significant number of research has been
done to establish ab initio material design principles for
perovskite oxides.86–88 In the context of chemical looping,
reducing the structural stability and increasing the degree of
lattice distortion (e.g. the degree of tilting of the BO6 octahedra)
could further promote the perovskites' ability to supply lattice
oxygen. Here, a first approximation of the structural stability
can be made by the Goldschmidt tolerance factor:89
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r A x þ r A′ ð1 − xÞ þ r 0
t ¼ pffiffiffi (10)
2½r B y þ r B′ ð1 − yÞ þ r 0 
where rA and r A′ are the ionic radii of the A site cations; rB and
r B′ are the ionic radii of the B site cations; x and 1 − x are the
occupancies of the A site cations; y and 1 − y are the
occupancies of the B site cations; rO is the ionic radii of O2−. t =
1 corresponds to an undistorted cubic perovskite lattice,
whereas t < 1 is likely to lead to tilted octahedral coordination
spheres and higher tendency of reduction to a brownmillerite
structure. The tolerance factor-based rationale was adopted by
Dou et al.,61 who doped Ca to SrFeO3 to destabilise the
perovskite structure and promote oxygen release for CLAS.
Lattice oxygen activity also depends on the electronic
properties of the B site cations. For example, although Co4+
has an ionic radius similar to Fe4+ (0.530 and 0.585 nm,
respectively), doping Co would significantly promote the
lattice oxygen activity of SrFexCo1−xO3−δ.61–63 Interestingly,
Wang et al. discovered the net electronic charge (Δe) of the
oxygen anions, a quantity derived from density functional
theory (DFT) calculations, to be a descriptor that correlates
well with the lattice oxygen activity, which is characterised by
the energy of the formation of an oxygen vacancy (a
thermodynamic property) and the lattice oxygen migration
barrier (a kinetic property), as shown in Fig. 3c and d. As far
as the SrFeO3 system is concerned, both the geometric effect
(by doping metals with different ionic radii) and the
electronic effect (by doping metals with different valencies)
can be captured by Δe.90
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Fig. 3 (a) The variation of the degree of FeO6 octahedral distortion with the amount of Ce doping in La1−xCexFeO3. Reproduced with permission
from ref. 76, copyright 2020 American Chemical Society. (b) The variation of Fe–O covalency, characterised by the charge transfer energy between
the unoccupied state centre of Fe3d and the occupied state centre of O2p as a function of the ionic radii of the rare earth metals in MFeO3
perovskites, where M = La, Pr, Sm or Gd. Reproduced from ref. 78, copyright 2021 Royal Society of Chemistry. (c) and (d) shows the correlation
between the formation energy of oxygen vacancy formation (ΔEv), the oxygen migration energy barrier and the net electronic charge of the
oxygen anion (Δe), in variously doped SrFeO3 perovskites. PCC stands for the Pearson correlation coefficient of the linear regression. Reproduced
with permission from ref. 90, copyright 2021 American Chemical Society.

Site occupancy–activity relationships have also been
studied for other ternary oxide phases beyond perovskites.
Wang and co-workers conducted a series of studies on
transition metal substituted La- and Ba-hexaaluminates
(BaFexAl12−xO19, x ≤ 3) and found that the Fe3+ species in the
hexaaluminate structure could serve as active centres for
methane oxidation.68–70,91 They also reported that the FeO6
octahedral sites favour complete methane oxidation, whereas
the FeO5 trigonal bipyramidal and the FeO4 tetrahedral sites
were more selective towards methane reforming to syngas.
For Ca2Fe2O5 brownmillerite, despite its favourable
thermodynamics towards syngas production, its rate of
supply of lattice oxygen is slow. To overcome this drawback,
Liu et al. enhanced the redox activities of Ca2Fe2O5 by doping
the A-site and the B site with Sr and Co, respectively,
achieving substantially promoted kinetics of chemical
looping microalgae gasification.92,93
For ternary oxide oxygen carriers having Ruddlesden–
Popper structures (An+1BnO3n+1), the coordination
environments of the active metal centres could also be varied
by changing the value of n, with n = ∞ corresponding to a
conventional perovskite structure. For example, Gabra et al.
compared the performance of Ag catalysts supported on
SrFeO3 and Sr3Fe2O7 (n = 2) for chemical looping epoxidation
(CLE) of ethylene and found that the structures of the R–P
phases influenced the oxygen release and uptake, which
ultimately resulted in different ethylene oxide (EO) yields and
selectivities during CLE.30 Reportedly, a 1 : 1 mixture of
SrFeO3 and Sr3Fe2O7 gave optimal CLE performance in terms
of EO yield, EO selectivity and cyclic stability.
Similar to solid solution mixtures, ternary oxide phases
containing easily reducible metals (e.g. Cu and Ni) can serve as
substrates for the in situ exsolution of catalytic nanoparticles
during chemical looping reactions. These embedded catalytic
sites could promote reaction kinetics, especially in catalytically
demanding applications such as CLR and CLWGS.67,94,95
Compared to catalysts prepared by deposition methods, the
exsolved catalytic particles generally have stronger interaction
with the parent oxide phases, which could protect the catalytic
sites against deactivation due to sintering and carbon
deposition,96 thereby providing superior performance.
Core–shell structures
Synthetic approaches to design and prepare nanostructured
catalysts, in particular, core–shell structured catalysts, have
also been adopted for preparing core–shell structured oxygen
carriers. In typical core–shell designs, the 3d transition metal

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oxides are designated as the cores, partly due to their
tendency to sinter. Depending on the design, the shell could
offer a variety of functionalities, including (i) a high-melting
point shell to provide sintering resistance,97,98 (ii) a redox-
active oxide shell to regulate the supply of oxygen,99,100 (iii) a
catalytically active shell that complements the chemical
activity of the core,99,101 and (iv) a low-melting point shell
which forms a molten layer during high temperature
operation, promoting both oxygen transfer and
catalysis.17,72,102–104 In the context of regulating the lattice
oxygen activity, types (ii) and (iv) are the most relevant.
Among the various chemical looping applications
reported, the oxidative dehydrogenation (CL-ODH) of alkanes
to alkenes is amongst the most challenging in terms of
achieving high selectivity towards the desired product.
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attributed to the formation of a LiFeO2 layer encapsulating
the LaxSr2−xFeO4−δ core. The authors postulated that the Li-
rich layer prevents any direct contact between the lattice
oxygen and the hydrocarbons, suppressing the
transformation of O2− into electrophilic oxygen species,
which could over-oxidise ethane to CO2 and H2O, as
schematically illustrated in Fig. 4b. However, this postulate is
at odds with the study by Donat and Müller, who suggested
that electrophilic lattice oxygen favours partial oxidation.36 Li
and co-workers also developed core–shell oxygen carriers (viz.
MgMnO8@Na2WO4, FexMn2−xO3@Na2WO4 and La0.8Sr0.2-
FeO3@Li2CO3), in which the shells form molten layers during
chemical looping reactions.18,19,102 The molten layers both
regulate the activity of the lattice oxygen and facilitate fast
ionic transport through the shell. A remarkable example is

Indeed, the product distribution of CL-ODH is a strong
function of the lattice oxygen activity,20 and would benefit
from a core–shell design, in which the oxide shell regulates
the supply of lattice oxygen to the active sites.
The presence of the shell layer will invariably affect mass
transfer. At the same time, the chemical activity of the lattice
oxygen can be effectively regulated by appropriately
formulating the composition of the shell layer. For example,
Li and co-workers reported that depositing Li on the surface
of LaxSr2−xFeO4−δ (a Ruddlesden–Popper phase) particles
could promote the ethylene selectivity from <10% (in the
case of bare LaxSr2−xFeO4−δ) to ∼90% for CL-ODH of ethane
at 700 °C (see Fig. 4a).72 Such a promotional effect was
the La0.8Sr0.2FeO3@Li2CO3 oxygen carrier prepared by Gao
et al.102 During the CL-ODH of ethane at 700 °C, the molten
Li2CO3 shell converted the lattice oxygen from La0.8Sr0.2FeO3
to O22− species, which was considered highly selective
towards ethylene.102 As a result, the La0.8Sr0.2FeO3@Li2CO3
oxygen carrier showed >90% ethylene selectivity with 59%
ethylene yield over 100 redox cycles.
Beyond the CL-ODH of ethane, Zhu et al. developed a
CaxMn1−xO@KFeO2 core–shell oxygen carrier (the core–shell
morphology is shown in Fig. 4e and f) for the CL-ODH of
ethylbenzene to styrene.21 In this design, the CaxMn1−xO
solid solution core acts as a lattice oxygen reservoir, whereas
the exterior surface of the KFeO2 shell provides active sites

Fig. 4 (a) Schematic illustration of a Li2O layer regulating the lattice oxygen transport from La0.6Sr1.4FeO4 to the surface of the oxygen carrier for
the CL-ODH of ethane. (b) Ethylene selectivity/ethane conversion/ethylene yield of (red ◇) pure LaSrFe, (pink ▲) 0.1LiFeO2–LaSrFe, (purple ×)
LiFeO2–LaSrFe, (black ★) 2.5LiFeO2–LaSrFe, (black +) LiFeO2/MgAl2O4, and (black ■) the blank experiment obtained over five cycles of the CL-ODH
of ethane at 700 °C with a space velocity of 3000 h−1. (c) and (d) shows the TEM micrograph of the 2.5LiFeO2–LaSrFe core–shell oxygen carrier.
(a)–(d) are reproduced with permission from ref. 72, copyright 2016 American Chemical Society. (e) EDS image and line scan (the inset of e) and (f)
high resolution TEM image showing the core–shell structure of the CaxMn1−xO@KFeO2 oxygen carrier. (g) shows the ethylbenzene conversion and
product selectivities of the CaxMn1−xO@KFeO2 oxygen carrier over 100 cycles of the CL-ODH of ethylbenzene to styrene at 600 °C. (e)–(g) are
produced from ref. 21, copyright 2021 Springer Nature.

This journal is © The Royal Society of Chemistry 2021 React. Chem. Eng.

Mini review
to oxidatively remove the hydrogen produced by
ethylbenzene dehydrogenation. In effect, the supply of
lattice oxygen is regulated by the core–shell structure, such
that the redox-active oxygen species on the oxygen carrier
surface are selective towards styrene, showing up to 97%
single-pass ethylbenzene conversion and >95% styrene
selectivity over 100 redox cycles (see Fig. 4g); this
corresponds to a 72% relative yield increase compared to
the commercial EB dehydrogenation process. As such, the
core–shell oxygen carrier design enables the regulation of
lattice oxygen activity, making CL-ODH a superior process
intensification technology with great potential to achieve
energy savings and emission reduction over conventional
reactor technologies.
Published on 06 July 2021. Downloaded on 8/12/2021 6:04:12 PM.
Conclusions and perspectives
In this minireview, three types of strategies to control the
lattice oxygen activity of oxygen carriers for chemical
looping applications are discussed. In the first type (solid
solution mixtures), metal oxides with similar oxidation
states, cationic radii and structures are mixed to form solid
solutions. The resulting oxygen carriers consist of mixtures
of solid solution phases, the lattice oxygen activity of which
can be tuned by adjusting the cationic compositions. Thus,
the solid solution mixtures offer lattice oxygen activities that
are otherwise inaccessible by binary oxides. In the second
type (ternary oxide phases), redox active metals occupy the
B-sites of well-defined structures, e.g. ABO3, A2B2O5,
AB12O19, etc., where the A sites are occupied by larger
cations. For a given structure, the ratio of A : B are largely
fixed. By stabilising the B site cations at uncommon
oxidation states, e.g. Fe4+ and Ni3+, these ternary oxide
structures provide lattice oxygen activities that are distinctly
different from those in binary oxides and solid solution
mixtures. The lattice oxygen activity of these ternary oxide
structures can be fine-tuned by substitutionally doping the
A sites and B sites with cations of different ionic radii and
different electronic properties. For perovskite-structured
oxides, the consequence of A- and B-site doping is relatively
well-understood, allowing the tailoring of high-performance
oxygen carriers for specific chemical looping applications.
In the third type, viz. core–shell structured oxygen carriers,
the lattice oxygen reservoir materials are encapsulated by
functional shells, which are designed to prevent direct
contact between the gaseous reactants and the oxide core.
During the reaction, lattice oxygen species will migrate
through the shell whilst being converted to specific states
that favour the selective oxidation of hydrocarbons to value-
added products. This approach is frequently used for
designing oxygen carriers for the CL-ODH of alkanes to
produce alkenes.
The three control strategies discussed above, together with
the selected practical examples, could be useful to the future
development of high-performance oxygen carriers for existing
and new chemical looping applications, especially those
React. Chem. Eng.
View Article Online
Reaction Chemistry & Engineering
requiring specific product selectivity. Yet, the research to
fundamentally uncover the relationship between lattice
oxygen activity and product selectivity is still at an early stage,
as shown by the fact that most of the relevant studies
reviewed were from the recent 3–4 years. More research effort
is required to understand the role of lattice oxygen and its
evolution during chemical looping reactions. For example,
there is no agreement on how the nature of the oxygen
vacancies and the electrophilicity of the lattice oxygen are
correlated to the selectivity towards partial and complete
oxidation. Experimentally, carefully designed operando
measurements are required to elucidate how the lattice
oxygen in the bulk is transformed and transported onto the
surface. If the surface oxygen species on the oxygen carriers
are fundamentally different from those on conventional
heterogeneous catalysts (i.e. typically originated from the
dissociative adsorption of gaseous oxidants rather than
lattice oxygen), then the catalytic requirement for oxygen
carriers would also be different from those for conventional
catalysts; this potential complication merits further
investigation.
Although the majority of the research on oxygen carriers
has been experimental, there is an emerging trend to
complement experimental findings with theory (primarily by
DFT calculations).21,63,76,102,105,106 It is envisaged that
computational approaches will play increasingly important
roles in chemical looping research, ultimately enabling
computer-aided design of oxygen carriers. In recent years,
computationally generated material databases have been
developed to offer cheaper and more accessible alternatives
to experimental databases. These computational databases
can be used to perform high-throughput material screening
for a wide range of applications, including catalysis, energy
storage, electrochemistry, etc.107,108 In fact, in silico material
screening approaches have already shown promise in
discovering novel oxygen carriers.73,109 To correct the
disparity between the DFT-calculated thermodynamic
properties (at 0 K) and those at elevated temperatures, Bartel
et al. have employed a machine-learning approach (viz.
independence screening and sparsifying operator) and
identified a robust descriptor to predict the temperature
dependencies of the Gibbs free energy of formation of solid
materials up to 1800 K.110 The same group demonstrated the
utility of this descriptor by computationally screening
candidate nitrogen carriers and sulphur carriers for solar
thermochemical ammonia synthesis and chemical looping
sulphur oxidation, respectively.111,112 To date, most
computational screening methods focus on the material
properties of the bulk, which is comparably better-defined
compared to the surfaces. With the rapidly improving
understanding of how oxygen carriers behave and the
maturing computational material design tools, it is
foreseeable that the process of developing new oxygen
carriers will become substantially more efficient, eventually
enabling the commercial deployment of chemical looping
technologies.
This journal is © The Royal Society of Chemistry 2021

Reaction Chemistry & Engineering
Author contributions
Wen Liu: writing – original draft and review and editing.
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
The author acknowledges financial support from the Nanyang
Technological University Start-Up Grant, Ministry of
Education of Singapore (AcRF Tier 1, RG112/18) and the
National Research Foundation of Singapore under its Campus
for Research Excellence and Technological Enterprise
(CREATE) Programme.
Published on 06 July 2021. Downloaded on 8/12/2021 6:04:12 PM.
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