Chemical Engineering Journal 409 (2021) 128226

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Chemical Engineering Journal

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Multiple perovskite layered lanthanum nickelate Ruddlesden-Popper

systems as highly active bifunctional oxygen catalysts
Sung Ryul Choi a, 1, John-In Lee a, 1, Hyunyoung Park a, Sung Won Lee a, Dong Yeong Kim a,
Won Young An a, Jung Hyun Kim b, Jongsoon Kim a, d, Hyun-Seok Cho c, Jun-Young Park a, *
a
HMC, Department of Nanotechnology and Advanced Materials Engineering, Sejong University, Seoul 05006, South Korea
b
Department of Advanced Materials Science and Engineering, Hanbat National University, Daejeon 34158, South Korea
c
New and Renewable Energy, Korea Institute of Energy Research, Daejeon 34129, South Korea
d
Department of Energy Science, Sungkyunkwan University, Suwon 16419, Republic of Korea

A R T I C L E I N F O A B S T R A C T

Keywords: A systematic study of the Ruddlesden-Popper structured Lan+1NinO3n+1 (n = 1, 2, 3, and 4) and its catalytic
Doped lanthanum nickelate performance in oxygen evolution (OER) and oxygen reduction reactions (ORR) is carried out with a view to
Ruddlesden-Popper structure design a highly-efficient and cost-effective electrocatalyst. In particular, we introduce for the first time a novel
Bifunctional electrocatalyst
La5Ni4O13-δ with a 4-layered perovskite structure (n = 4) for use as a highly active and durable bifunctional
Oxygen evolution reaction
Oxygen reduction reaction
oxygen catalyst for OER/ORR. Concretely, La5Ni4O13-δ catalysts has demonstrated performance of 1.65 V at 10
Oxygen electrode activity mA⋅cm− 2 and 0.66 V at near half-wave potential (–3 mA⋅cm− 2) for OER and ORR, respectively, this indicates
excellent intrinsic OER/ORR kinetics. Furthermore, by controlling the fuel-to-oxidizer ratio (using extremely
fuel-rich conditions) in the glycine-nitrate combustion technique, the 4-layered perovskite La5Ni4O13-δ catalysts
are synthesized as a single Ruddlesden–Popper phase with various dopants to further boost its bifunctional
oxygen electrode activity. Among OER/ORR catalysts, La5Ni3CoO13-δ catalysts exhibit exceptional electro­
catalytic activity with low overpotential and Tafel slope (35/76 mV‧dec-1 for OER/ORR). Outstandingly, the
La5Ni3CoO13-δ is able to achieve an extremely low overpotential of 370 mV at 10 mA‧cm− 2 in 0.1 M KOH for
OER, surpassing Ir/C catalysts and any metal oxide catalyst ever reported. The high catalytic performance of
La5Ni3CoO13-δ can be attributed to its favorable electronic structure enriched with oxygen defects and electronic
charge carriers (increased Ni oxidation state) as well as to the promoted lattice-oxygen oxidation mechanism
pathway that comes from strong metal–oxygen covalency (high oxygen-ion diffusion rate).

1. Introduction activity (for example, Pt/C for ORR and Ir/C for OER); however, the
scarcity, high cost, and low bifunctionality of Pt/C and Ir/C have seri­
The use of conventional fossil fuels to generate energy is having ever- ously impeded the worldwide commercial application of these devices
increasing detrimental effects on the environment and climate, this [6]. Over the past few decades, nanostructured transition metal (e.g. Ni,
problem has stimulated many comprehensive investigations and pieces Co, and Fe)-based oxides have emerged as promising candidates for this
of research to develop clean, renewable next-generation energy storage kind of catalyst due to their abundance, bifunctionality, and reasonable
and conversion technologies [1,2]. Of utmost importance for the per­ activities for both OER and ORR [7-9]. In particular, perovskite-
formance of these next-generation electrochemical energy devices are structured oxides with a general formula of ABO3, in which A is a
the quality of the oxygen reduction reactions (ORR) and oxygen evo­ rare-earth or alkaline earth material and B is a transition metal, can host
lution reactions (OER) that take place within them, these reactions have a myriad of structures (single, double, and triple) and compositions
intrinsically sluggish kinetics due to multistep electron and ion transfers created by substitution of ions of different radii and valences in the A
[3-5]. To date, precious metal-based electrocatalysts have been identi­ and B-sites [10-14]. Nevertheless, perovskite oxide-based electro­
fied as the gold standard oxygen electrode catalysts, owing to their high catalysts have several major drawbacks: large overpotential for

* Corresponding author.
E-mail address: [email protected] (J.-Y. Park).
1
Sung Ryul Choi and John-In Lee contributed equally as first authors.

https://doi.org/10.1016/j.cej.2020.128226
Received 15 October 2020; Received in revised form 8 December 2020; Accepted 17 December 2020
Available online 5 January 2021
1385-8947/© 2020 Elsevier B.V. All rights reserved.
S.R. Choi et al. Chemical Engineering Journal 409 (2021) 128226

catalyzing OER/ORR and low mass activity that results from the small The Ni-site transition metal (M = Fe, Co)-doped La5Ni4-xMxO13-δ (x
electrochemically active surface area. Hence, further advances in terms = 0.5, 1.0, 1.5, and 2.0) catalysts were also prepared using the GNC
of activity and stability are still crucial for their use to become prevalent process. Iron nitrate nonahydrate [Fe(NO3)2‧9H2O, 98% purity, Alfa
in next-generation energy storage and conversion technologies. Aesar], Cobalt nitrate hexahydrate [Co(NO3)2‧6H2O, 98% purity, Alfa
Recently, Suntivich et al. [15] proposed that catalytic activity for Aesar], lanthanum nitrate hexahydrate [La(NO3)3‧6H2O, 98% purity,
oxides is predominantly related to eg (σ*-orbital) occupation and the Alfa Aesar], nickel nitrate hexahydrate [Ni(NO3)2‧6H2O, 98% purity,
extent of B-site transition-metal–oxygen covalency. According to the Alfa Aesar] were dissolved with glycine in deionized water. The solution
volcano relationship that describes catalyst activity as dependent on eg was mixed with a magnetic bar and slowly dehydrated at 300 ◦ C until
electron numbers, perovskite-structured LaNiO3 was expected to pro­ the auto-combustion of the precursors. The ashes were ground and then
vide excellent OER/ORR electrocatalysts. More recently, there has been calcined at 1100 ◦ C for 5 h.
significant interest in La-Ni based layered perovskite compounds, these
are classified as Ruddlesden–Popper-type oxides with the formula 2.2. Characterization of layered lanthanum nickelate systems
Lan+1NinO3n+1 [16-19]. The Ruddlesden–Popper structured materials,
Lan+1NinO3n+1, are composed of perovskite (LaNiO3) layers inserted Crystalline structures of the catalysts were determined by X-ray
between two Rocksalt layers (LaO), stacking along the c-axis [20-23]. diffraction (XRD, Rigaku D/MAX 2500 Diffractometer) with filtered Cu
Shao et al. [24] conducted a systematic study on the OER/ORR perfor­ Kα radiation (λ = 1.5444 Å). The XRD data was collected by step
mances of Lan+1NinO3n+1 (LNO, n = 1, 2, and 3) and discovered that the scanning in the 2θ range of 20–80◦ with intervals of 0.02◦ . Each X-ray
catalytic activity of LNO is dependent on the n value at room tempera­ diffractogram was refined by profile matching using the Fullprof soft­
ture in alkaline medium. However, the case of n > 3 (3 < n < ∞) has not ware and Rietveld structural refinements were then conducted to
been reported yet, despite the fact that the n value significantly in­ determine the crystal structure parameters (atom coordinates and lattice
fluences the electrocatalytic properties of Ruddlesden-Popper LNO parameters). The chemical state and electronic structure of the catalysts
during OER/ORR. This may be because conventional solid-state tech­ were identified by X-ray photoelectron spectroscopy (XPS, VG Escalab
niques have only been successful in making polycrystalline samples with 220i, UK) using a monochromatic Al Kα X-ray source (hν = 1,486.6 eV).
n = 1–3 [25,26]. Moreover, the doping effect of LNO in La and Ni-sites Relative atomic concentrations were compared using the peak in­
on the electrocatalytic performances has not been studied systematically tensities of Ni 2p and O 1 s of the catalysts, normalized to their ionization
because of the technical difficulties in synthesizing single Rud­ cross-sections.
dlesden–Popper Lan+1NinO3n+1 phases with various dopants. The morphology of the catalysts was examined by field emission
Herein, we report on transition metal (M = Fe, Co)-doped Lan+1Nin- scanning electron microscopy (FESEM, S-4700 Hitachi, acceleration
xMxO3n+1 (LNM-x, n = 1, 2, 3, and 4, x = 0.5, 1.0, 1, 5, and 2.0) with n voltage of 15 kV) and high resolution transmission electron microscopy
layered perovskite structures that are highly active for OER/ORR in (HRTEM, JEM-F200, JEOL, acceleration voltage of 200 kV). Corre­
alkaline medium. The n layered perovskite LNM catalysts are synthe­ sponding energy-dispersive X-ray spectroscopy (EDX) elemental map­
sized using glycine-nitrate combustion (GNC) techniques [27-29]. By ping images of the component phases were taken with an Oxford
controlling the fuel-to-oxidizer ratio (to extremely fuel-rich conditions) instruments device the FESEM was equipped with. Electrocatalysts were
during the GNC technique, the 4-layered perovskite LNM catalysts can dispersed in ethanol by sonication to prepare specimens for FESEM and
be synthesized as a single Ruddlesden–Popper phase with various dop­ HRTEM. The Brunauer–Emmet–Teller (BET) surface area catalysts were
ants. Benefiting from n layered perovskite structures with transition analyzed using N2 adsorption/desorption medium (BELSORP-max, BEL)
metal dopants, La5Ni3CoO13-δ (LNC-1.0) catalysts exhibit outstanding at 77 K after drying the samples for 3 h at 250 ℃, their pore size dis­
bifunctional electrocatalytic activity for OER/ORR with low over­ tributions were calculated by the Barrett–Joyner–Halenda (BJH)
potential and Tafel slope (35/76 mV‧dec-1). Their oxygen electrode ac­ method from the adsorption branches of the isotherms.
tivity [ΔE = EOER (at 10 mA‧cm− 2)–EORR (− 3 mA‧cm− 2)] is as small as
0.942 V, which is comparable to any metal oxide catalyst ever reported 2.3. Electrochemical measurements of layered lanthanum nickelate
[30-32]. The high catalytic performance from LNC-1.0 is attributed to its systems
favorable electronic structure that is enriched with oxygen defects and
electronic charge carriers (increased Ni oxidation state) as well as the Electrochemical analysis of the bifunctional OER and ORR catalysts
promoted lattice-oxygen oxidation mechanism pathway that comes was performed on a rotating disk electrode (RDE) system (RRDE-3A,
from strong metal–oxygen covalency (high oxygen-ion diffusion rate) ALS) at room temperature. Catalyst inks were prepared by dispersing 10
[33-36]. mg of the catalyst powder and 5 mg of conductive carbon (Vulcan XC-
72R, Cabot) in 16 μL aqueous Nafion solution (Sigma-Aldrich), 250 μL
2. Experimental of isopropanol, and 750 μL of deionized water, this was followed by bath
sonication for 30 min. A 1 μL catalyst slurry was drop-cast onto a glassy
2.1. Synthesis of multiple perovskite layered lanthanum nickelate systems carbon disk electrode (diameter of 3 mm and 0.07069 cm2 electrode
area) and dried at room temperature to form a uniform thin film working
The Ruddlesden-Popper Lan+1NinO3n+1 (LNO, n = 1, 2, 3, and 4) electrode. Electrochemical testing was performed in a standard three-
family of catalysts were synthesized through a glycine nitrate combus­ electrode cell using a Pt wire counter electrode, an Hg/HgO (sat. 1 M
tion (GNC) process. To prepare LNO electrocatalysts, stoichiometric NaOH) reference electrode, and the as-prepared catalyst coated glassy
amounts of lanthanum nitrate hexahydrate [La(NO3)3‧6H2O, 98% pu­ carbon working electrode. All potentials reported in this study were
rity, Alfa Aesar], nickel nitrate hexahydrate [Ni(NO3)2‧6H2O, 98% pu­ converted to the reversible hydrogen electrode (RHE) scale, unless
rity, Alfa Aesar] were mixed with glycine (NH2CH2COOH) as the fuel in otherwise specified. All electrochemical experiments were conducted on
deionized water. In order to drive the combustion reaction with the a potentiostat/galvanostat electrochemical analyzer (SP-150, Biologic,
maximum energy, a high glycine to nitrate molar ratio of 8.5 was used, France).
this allowed us to synthesize high numbers of perovskite layers in the Cyclic voltammetry (CV) scans were performed between 0.05 and
Ruddlesden-Popper structure. The mixture was then heated to 300 ◦ C 1.2 V for 50 cycles (scan rate of 100 mV s− 1) to clean the surface of the
while stirring with a magnetic bar (120 rpm) to form a homogeneous catalyst before electrochemical tests. For OER activity measurements,
suspension. After auto-ignition of the mixture, the ashes were collected, the CV was obtained in O2-saturated 0.1 M KOH electrolyte solution at a
ground with a mortar and pestle, and then calcined at 1100 ◦ C for 5 h to scan rate of 5 mV‧s− 1 (1,600 rpm) between 1.2 and 1.7 V. Overpotentials
obtain the Ruddlesden-Popper structure LNO powders. were obtained by subtracting the thermodynamic potential for water

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S.R. Choi et al. Chemical Engineering Journal 409 (2021) 128226

oxidation from the measured potential at a current density of 5 and 10 images), using a bounded three-dimensional diffusion model [35-37].
mA‧cm− 2. ORR activity measurements were conducted in an O2-satu­
rated 0.1 M KOH solution by LSV from 1.2 to 0.2 V at a scan rate of 5 mV‧ 3. Results and discussion
s− 1 (rotating speeds of 400, 900, 1,600, and 2,500 rpm). To compensate
for the effect of solution resistance, all the potentials are iR-corrected 3.1. Structural and microstructural characterizations of catalysts
potentials (=E-iR where i is the current density and R is the uncom­
pensated ohmic electrolyte resistance recorded via SP-150 electro­ Crystalline structures of the synthesized Ruddlesden-Popper
chemical impedance spectroscopy (EIS, BioLogic). EIS measurements Lan+1NinO3n+1 (LNO, n = 1, 2, 3, and 4) family of catalysts were
were carried out in the frequency range of 100 kHz − 100 mHz. The AC investigated by x-ray diffraction (XRD). Fig. 1a shows the XRD patterns
amplitude was set at 10 mV. The resistance components of catalysts of the Lan+1NinO3n+1 materials, as well as their Rietveld refinement
were separated as the ohmic (Rohmic), charge-transport (Rct), and mass- results. The XRD patterns of the La2NiO4+δ (L2N1), La3Ni2O7-δ (L3N2),
transport resistances (Rmt) from the fitted equivalent circuit using EC- La4Ni3O10-δ (L4N3), and La5Ni4O13-δ (L5N4) powders show the forma­
Lab software. tion of the Ruddlesden-Popper K2NiF4 structure (inorganic crystal
The potential difference between the OER and ORR characteristics structure data, ICSD, no. 39004) free of any undesirable phases (For
was calculated to assess the comprehensive oxygen electrode activity of your information, L5N4 was not yet recorded in the ICSD) [38]. The
the catalysts. Electrochemical active surface area (ECSA) of the catalysts crystal structures (space group) of L2N1 was identified as tetragonal (I/
was estimated by dividing the double-layer capacitances (Cdl) by the 4mmm), while L3N2, L4N3, and L5N4 were indexed with the tetragonal
specific capacitance (Cs ≈40 μF‧cm− 2). ECSA tests were carried out (Fmmm) phase [16,24,39]. The Ruddlesden-Popper structured LNO
under the potential window of 0.1–0.2 V (vs. RHE) with different scan consists of alternating rock-salt layers (LaO) and perovskite layers
rates of 10, 20, 50, 100, 150, and 200 mV‧s− 1. Durability was evaluated (LaNiO3)n along the crystallographic c direction, as shown in Fig. 1b.
by LSV curves under a potential sweep of 1.25–1.65 V for 1,000 cycles The lattice constants of the Ruddlesden-Popper structured catalysts
(scan rate of 200 mV s− 1) for OER and a sweep of 0.6–1.1 V for 10,000 calculated using the Rietveld refinements were comparatively invariant
cycles (scan rate of 200 mV s− 1) for ORR. The oxygen intercalation and for a- and b-axes. The lattice parameters, a (and b) of L2N1, L3N2, L4N3,
diffusion coefficient measurements were performed in an N2-saturated and L5N4 were 3.8625 (3.8625), 5.3993 (5.4468), 5.4147 (5.4601), and
1 M KOH aqueous solution at a scan rate of 20 mV⋅s− 1 (GC working 5.4184 Å (5.4635 Å), respectively (Table 1). On the other hand, the c-
electrode, Pt wire counter electrode, and Hg/HgO reference electrode) axis lattice constants of the catalysts showed remarkable differences,
[36]. Chronoamperometry experiments were performed by applying a they progressively increased from 12.6916 Å to 20.4778, to 28.0081,
50 mV more anodic of the halfway potential between the peak currents and to 35.9460 Å for L2N1, L3N2, L4N3, and L5N4, respectively, this
for oxygen insertion and extraction at 2000 rpm rotation rate. The ox­ demonstrates the formation of higher order Ruddlesden-Popper phases
ygen ion diffusion coefficient (Do) was calculated by the equation λ = a with increasing n (=the number of perovskite layers) in this structure.
(Dot)-1/2, where λ dimensionless shape factor [assumed to be 2, esti­ Size and morphology of the LNO catalysts were investigated by
mated the values from a sphere (1.77) and cube (2.26)] and a is the FESEM and HRTEM. The LNO particles synthesized with the glycine-
radius of the particles (obtained from the measurement of radius by SEM nitrate combustion method show an agglomerated sheet-like grain

Fig. 1. (a) XRD diffraction patterns with their Rietveld refinement results for as-synthesized Ruddlesden-Popper structured catalysts. (b) Crystalline structure of
La2NiO4+δ, La3Ni2O7-δ, La4Ni3O10-δ, La5Ni4O13-δ, and La5Ni4-xMxO13-δ (M = Co, Fe). (c) XRD patterns of as-synthesized La5Ni4-xFexO13-δ (x = 0, 0,5, 1.0, 1.5, and 2.0).
(d) XRD patterns of as-synthesized La5Ni4-xFexO13-δ (x = 0, 0,5, 1.0, 1.5, and 2.0) catalysts.

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S.R. Choi et al. Chemical Engineering Journal 409 (2021) 128226

Table 1
Lattice parameters and structural information for Lan+1NinO3n+1 (n = 1, 2, 3, and 4), La5Ni3FeO13-δ, and La5Ni3CoO13-δ from Rietveld refinement and chemical titration
method.
Catalysts Space group(phase structure) Lattice parameter / nm c/a Oxygen non-stoichiometry Reliability factors (Rp, χ2)
a b c

La2NiO4+δ I4/mmm(Tetragonal) 3.8625 3.8625 12.6916 3.286 0.08 5.39%, 2.41

La3Ni2O7-δ Fmmm(Tetragonal) 5.3993 5.4468 20.4778 3.793 0.05 9.44%, 7.92
La4Ni3O10-δ 5.4147 5.4601 28.0081 5.173 0.13 8.40%, 4.93
La5Ni4O13-δ 5.4184 5.4635 35.9460 6.634 0.21 16.0%, 23.2

morphology with diameters of 50–250 nm, this is a typical shape for the CV curves), ohmic resistance-corrected potential (E–ir) vs. log j for
layered structure materials and is caused by a buildup of layers along the OER were produced, these are shown in Fig. 4b. The Tafel slopes of
c-axis (Fig. 2 and S1) [40]. Elemental mapping images of LNO based on L5N4, L4N3, L3N2, and L2N1 for OER were 70, 77, 87, and 114 mV‧dec-
1
SEM/EDX show that the constituent elements (La, Ni, and O) are uni­ , respectively, indicating the excellent OER kinetics of L5N4 (Table 3).
formly distributed without any observable elemental segregation. Fig. 4c represents the mass activity (normalized to the mass loading)
Table 2 summarizes the elemental composition of the LNO samples and specific activity (normalized to the surface area from BET mea­
derived from the EDX analysis. The relative atomic percentages of surements) of the LNO electrocatalysts at η = 450 mV (1.68 V vs. RHE) to
lanthanum and nickel are 2:1.0, 3:1.8, 4:3.1, and 5:4.2 for L2N1, L3N2, evaluate the potential for scalability of water-splitting catalysts [41].
L4N3, and L5N4, respectively, this confirms that lanthanum and nickel The L5N4 electrocatalyst exhibits a mass activity of 139 A‧g− 1, which is
were well synthesized at the desired ratio in the Ruddlesden-Popper ~ 3.2 and 3.6 times that of the L3N2 and L2N1 electrocatalysts,
LNO structure. The Ruddlesden-Popper structure in the LNO was respectively, indicating that this catalyst makes applicable in scaling-up
further confirmed by the selected area electron diffraction (SAED) of water electrolysis. It is well known that the specific activity also re­
pattern from the HRTEM image (Fig. 2g and S2). The inset of Fig. 2g veals the intrinsic OER activity of catalysts. The intrinsic activity of the
shows the representative points in the SAED pattern, these can be catalysts for OER followed the order from worst to best of L2N1 (4.55
indexed as (0 2 0) and (0010) reflections along the [1 0 0] zone axis of the mA‧cm-2BET) < L3N2 (5.95 mA‧cm-2BET) < L4N3 (8.18 mA‧cm-2BET) <
LNO. A well-organized arrangement of stacking layers of LaO (LaNiO3)4 L5N4 (18.2 mA‧cm-2BET), indicating the excellent intrinsic activity of
along the c-axis was observed. The repeated LaO layers along the c-axis high n value Ruddlesden-Popper structure electrocatalysts. Long-term
were separated by 35.91 Å as seen in the enlarged image for L5N4, this is OER stability of the synthesized catalysts was evaluated by potential
in agreement with the results obtained from the Rietveld refinement cycling tests between 1.25 and 1.65 V (vs. RHE, scan rate of 5 mV‧s− 1) in
(Table 1). Fig. 3 shows nitrogen adsorption–desorption isotherms and an O2 saturated 0.1 M KOH solution at 1,600 rpm. Fig. 4d shows OER
pore size distribution curves of all the LNO electrocatalysts. All LNO activity of L5N4 before and after the durability test. The potential dif­
samples showed similar BET surface areas of 0.85, 0.74, 0.80, and 0.77 ference of L5N4 at 10 mA‧cm− 2 was decreased by 6 mV after 1,000
m2‧g− 1 for L2N1, L3N2, L4N3, and L5N4, respectively (Table 2). The cycles, demonstrating the high stability of L5N4 electrocatalyst during
catalysts pore size distributions were calculated from adsorption- OER.
desorption isotherms, these exhibit type IV shapes with mesoporous The ORR activities of the LNO electrocatalysts were also quantified
features (mean pore diameter of 9.1–12.9 nm). by using a RDE in an O2-saturated 0.1 M KOH solution. The linear sweep
voltammetry (LSVs) measurements were taken at a rotation speed of
1600 rpm and a scan rate of 5 mV‧s− 1, these are depicted in Fig. 5a. L5N4
3.2. Electrochemical activity and stability of catalysts shows better ORR activity with lower overpotential than the other cat­
alysts. Onset potentials obtained from the LSV curves of L5N4, L4N3,
To investigate OER catalytic activity of the LNO catalysts, CV mea­ L3N2, and L2N1 were 0.760, 0.732, 0.729, and 0.713 V, respectively. In
surements were performed in an O2-saturated 0.1 M KOH solution at a addition, the half-wave potentials of L5N4, L4N3, L3N2, and L2N1 were
rotating speed of 1600 rpm and a scan rate of 5 mV‧s− 1 on RDE. As seen 0.664, 0.650, 0.645, and 0.617 V, respectively. Catalytic activities of the
in Fig. 4a, OER activity of the LNO increased with the number of LNO catalysts were also investigated using the Tafel plots in ORR po­
perovskite layers (n) in the Ruddlesden-Popper structure and thus L5N4 larization curves (Fig. 5b). The Tafel slopes of L5N4, L4N3, L3N2, and
exhibits better OER activity with a lower overpotential of 430 mV than L2N1 for ORR were 90, 121, 136, and 167 mV‧dec-1, respectively,
the other catalysts. More specifically, the overpotential (η) at 5 mA‧cm− 2 indicating the excellent ORR kinetics of L5N4 (Table 3). Additionally,
increased in the order: L5N4 (1.62 V), L4N3 (1.65 V), L3N2 (1.67 V), and the unique L5N4 catalyst achieved an ORR mass activity of 10.1 A⋅g− 1
L2N1 (1.68 V). To find the kinetic parameters of the LNO electro­ and a specific activity of 1.32 mA⋅cm–2BET, these are the highest among
catalysts, Tafel plots derived from polarization curves (negative scan of all the test samples, at 0.7 V vs. RHE (Fig. 5c).
The inverse measured current density (j-1) was plotted vs. inverse
Table 2 square root of the rotation speed (ω) at 0.4–0.7 V by Koutecky-Levich
Characterization data for catalysts from N2 adsorption analysis and FESEM/EDX analysis. In the Koutecky-Levich plot (Fig. 5d), L5N4 exhibited linear
elemental mapping. increases in inverse measured current density with increasing values of
BET analysis Elemental composition/EDX the inverse square root of the rotation speed, this reveals the first-order
Catalysts BET Mean pore La Ni La: Co or
electrochemical reaction kinetics toward dissolved oxygen [42].
surface diameter (%) (%) Ni Fe Transferred electron numbers per oxygen molecule calculated by the
area (nm) (%) empirical Koutecky-Levich equation for L2N1, L3N2, L4N3, and L5N4
(m2⋅g− 1) were 2.1, 2.3, 2.8, and 3.6, respectively, this implies that the 4-electron
La2NiO4-δ 0.85 9.1 13.5 7.0 2:1.0
process of the LNO catalysts can be used as a gauge for high ORR cat­
La3Ni2O7-δ 0.74 12.8 13.6 8.2 3:1.8
La4Ni3O10-δ 0.80 12.3 14.0 10.9 4:3.1 alytic activity. For long-term ORR stability testing, the LNO electro­
La5Ni4O13-δ 0.77 12.9 9.5 8.0 5:4.2 catalysts were cycled between 0.6 and 1.1 V (vs. RHE) for 10,000 cycles
La5Ni3.5Fe0.5O13- 1.22 9.1 19.1 12.0 5:3.1 1.9 in a 0.1 M O2-saturated KOH solution at 1600 rpm. As shown in Fig. 5e,
δ (Fe) L5N4 exhibits a decline in ORR activity of 37 mV at –3 mA‧cm− 2.
La5Ni3CoO13-δ 0.85 16.4 13.1 7.2 5:2.8 2.6
(Co)

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S.R. Choi et al. Chemical Engineering Journal 409 (2021) 128226

Fig. 2. FESEM images and EDX elemental mapping results for (a) La2NiO4+δ, (b) La3Ni2O7-δ, (c) La4Ni3O10-δ, (d) La5Ni4O13-δ, (e) La5Ni3.5Fe0.5O13-δ, and (f)
La5Ni4Co1O13-δ. (g) HRTEM image of La5Ni4O13-δ catalyst with its SAED pattern. Right inset shows a fast Fourier transform result for the (1 0 0) direction, and in­
dicates the observed lattice parameter for the c-axis.

Fig. 3. (a) Nitrogen adsorption–desorption isotherms and (b) total pore volume and pore size of the Ruddlesden-Popper structured catalysts.

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S.R. Choi et al. Chemical Engineering Journal 409 (2021) 128226

Fig. 4. (a) OER polarization curves, (b) corresponding OER Tafel slopes, and (c) specific and mass activity at 1.68 V (vs. RHE) of as-synthesized catalysts. (d) OER
polarization curves of La5Ni4O13-δ (L5N4) catalysts before and after 1,000 cycles of potential sweep (1.25–1.65 V).

Table 3
Detailed data on electrocatalytic activities of Lan+1NinO3n+1 (n = 1, 2, 3, and 4), La5Ni3FeO13-δ, and La5Ni3CoO13-δ with noble metal catalysts (Pt/C and Ir/C).
Catalyst OER ORR
Tafel slope Current density@ Mass activity@ Specific activity@ Tafel slope Current density@ Mass activity@ Specific activity@
(mV⋅dec− 1) 1.68 V(mA⋅cm− 2) 1.68 V(A⋅g− 1) 1.68 (mA⋅cm- (mV⋅dec− 1) 0.7 V(mA⋅cm− 2) 0.7 V(A⋅g− 1) 0.7 V (mA⋅cm-
2 2
BET) BET)

La2NiO4+δ 114 4.53 38.4 4.55 167 − 0.151 − 1.28 − 0.153

La3Ni2O7-δ 87 5.17 43.8 5.95 136 − 0.407 − 3.41 − 0.473
La4Ni3O10-δ 77 7.75 65.4 8.18 93 − 0.726 − 6.17 − 0.772
La5Ni4O13-δ 70 16.4 139 18.2 90 − 1.19 − 10.1 − 1.32
La5Ni3CoO13- 35 55.5 470 55.7 76 − 1.30 − 11.0 − 1.30
δ
La5Ni3FeO13- 89 10.2 86.6 8.66 122 − 0.686 − 5.82 − 0.582
δ
Ir/C 43 28.2 203 0.289
Pt/C 50 − 4.98 − 35.8 − 0.0397

3.3. Electrochemical activity of La5Ni4-xMxO13-δ (M = Fe and Co) K2NiF4 crystal structure in the XRD pattern with a minor phase that is
catalysts likely indexed to NiO at high doping concentrations (x = 1.5, 2.0) of Fe,
this indicates that the Co and Fe doping did not change the crystal
The Ni-site transition metal (M = Fe, Co)-doped La5Ni4-xMxO13-δ (x structure of L5N4. However, as shown in Fig. 1c and 1d, with the in­
= 0.5, 1.0, 1.5, and 2.0) Ruddlesden-Popper system is of interest due to crease of Fe-doping content, the peak of the LNF-x (2 2 0) lattice plane
the possible improvements catalytic activity it can provide for the OER exhibits a slight shift to a lower angle compared to that of pure L5N4. On
and ORR. The crystal structure of La5Ni4-xFexO13-δ (LNF-x) and the other hand, the increase of the Co-doping content in the LNC-x
La5Ni4-xCoxO13-δ (LNC-x) were studied by XRD as shown in Fig. 1c and catalysts tends to cause a shift toward a higher angle. Peak shifts in
1d. The major phases of all samples are identified as Ruddlesden-Popper the XRD patterns of the catalysts are governed by the relative ionic

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Fig. 5. (a) ORR polarization curves, (b) corresponding ORR Tafel slopes, (c) specific and mass activity at 0.7 V (vs. RHE), d) electron transfer numbers from
Koutecky-Levich plots of as-synthesized catalysts (at 0.4 V/RHE). (e) ORR polarization curves of La5Ni4O13-δ (L5N4) catalysts before and after 10,000 cycles of
potential sweep (0.6–1.1 V).

radius ratio of the Ni and dopants for the given oxidation state (0.69 Å or LSV measurements were also taken to investigate the ORR activity of
Ni2+ and 0.56 Å for Ni3+). These additional defect sites cause more the catalysts in an O2-saturated 0.1 M KOH solution with a 1600 rpm
exposed active sites after the modification of the electronic character­ rotating disk and a scan rate of 5 mV‧s− 1 (Fig. 6e and S3c). Additionally,
istics, this enhances the electrocatalysis for OER and ORR [43]. The the Pt/C catalyst (20 wt% Pt loading, HISPEC 3000) as the gold standard
electronic structure and elemental states of La5Ni4-xMxO13-δ are further catalyst for this reaction was tested under the same conditions. The ORR
discussed in the next section. Size and elemental distributions of the Co activity of the L5N4 was significantly improved by the doping of Co and
and Fe-doped La5Ni4-xMxO13-δ (M = Co, Fe, and × = 0.5, 1.0, 1.5, and Fe in the Ni-site of the Ruddlesden-Popper structure. In particular, the
2.0) Ruddlesden-Popper catalysts were investigated by FESEM. The LNC-1.0 catalysts showed prominent ORR activity compared to other
La5Ni3Co1O13-δ (LNC-1.0) and La5Ni2.5Fe0.5O13-δ (LNF-0.5) catalysts catalysts. Furthermore, LNC-1.0 showed a lower Tafel slope (with –76
also exhibit severely agglomerated flake-shape morphologies that are mV‧dec-1) than L5N4 (–90 mV‧dec-1) and LNF-1.0 (–122 mV‧dec-1) in
100–300 nm in size after synthesis by the glycine-nitrate combustion corresponding Tafel plots (Fig. 6f and S3d), this reveals the favorable
process, the constituent elements (La, Ni, Co, or Fe) were homoge­ kinetics of LNC-1.0 toward ORR. As shown in Fig. 6g, LNC-1.0 exhibits a
neously distributed without any noticeable elemental segregation decline in ORR activity of 75 mV at –3 mA‧cm− 2, this is comparable to
(Fig. 2e and 2f). In addition, LNC-1.0 and LNF-0.5 catalysts exhibit the Pt/C catalyst (55 mV at –3 mA‧cm− 2). Moreover, the onset and half-
similar BET surface areas of 0.85 and 1.22 m2‧g− 1, respectively, to that wave potentials obtained from the LSV curves of LNC-1.0 were 0.774
of L5N4 (Table 2). and 0.668 V, respectively, these are much lower than those of Pt/C
The electrocatalytic OER performance of the as-prepared La5Ni4-x (0.980 and 0.856 V) (Table 3). Thus, further improvements in ORR ac­
FexO13-δ and La5Ni4-xCoxO13-δ were evaluated in an O2-saturated 0.1 M tivity are necessary for the successful application of this material in a
KOH solution with a scan rate of 5 mV‧s− 1. Due to its status as the gold bifunctional oxygen electrode, this can be achieved through the size
standard catalyst, the Ir/C catalyst (20 wt% Ir loading, Premetek) was reduction of Ruddlesden Popper particles or hybridization with elec­
also tested under the same conditions. As shown in Fig. 6a and S3, LNC- trochemically conductive graphene materials to increase the electrical
1.0 exhibited the lowest overpotential of 370 mV for OER among all the conductivity of the catalyst [44,45].
samples tested and is even superior to that of Ir/C (388 mV). The To evaluate the oxygen electrode activities of the Ruddlesden-Popper
overpotential at 10 mA‧cm− 2, used as an evaluation standard for solar structured catalysts, the potential difference (ΔE) between OER (at 10
fuel-synthesis systems, was 1.60 V for LNC-1.0 (cf. 1.65 V for Ir/C). The mA‧cm− 2) and ORR potentials (at –3 mA‧cm− 2) were calculated quan­
Tafel slopes of LNF-1.0, LNC-1.0, and Ir/C from the OER polarization titatively, as shown in Fig. 6h and S4 [46]. A small ΔE specifies high
curves were 89, and 35, and 43 mV‧dec-1 (cf. 70 mV‧dec-1 for L5N4), bifunctional oxygen electrode activity, LNC-1.0 exhibited a reasonable
respectively, indicating exceptional OER kinetics for LNC-1.0 (Fig. 6b). ΔE value of 0.932, this is comparable to state-of-the-art oxygen catalysts
Furthermore, the LNC-1.0 electrocatalyst showed much better long-term (Table S2) [47-51]. As mentioned earlier, improvements in the catalytic
OER stability compared to Ir/C, as shown by Fig. 6c. The potential dif­ activity of LNC-1.0 during ORR through various possible approaches
ference of LNC-1.0 at 10 mA‧cm− 2 increased by 14 mV (cf., 78 mV for Ir/ will contribute to accomplishing excellent bifunctional oxygen electrode
C) after 1,000 cycles, demonstrating the high stability of the L5N4 activity.
electrocatalyst in OER conditions. More importantly, after an extensive
comparison of activities of other oxide catalysts it was found that LNC-
3.4. Mechanistic study of highly active LNC-1.0 catalysts
1.0 is the best-performing oxygen electrocatalyst for OER in alkaline
media ever tested (Fig. 6d and Table S1).
The outstanding electrocatalytic performances of LNC-1.0 for oxygen

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S.R. Choi et al. Chemical Engineering Journal 409 (2021) 128226

Fig. 6. (a) OER polarization curves and (b) corresponding OER Tafel plots of L5N4, LNC-1.0, LNF-1.0, and Ir/C catalysts. (c) OER polarization curves of LNC-1.0 and
Ir/C catalysts before and after 1,000 cycles of potential sweep (1.25–1.65 V). (d) Comparison of overpotential (η10) mA‧cm− 2 for LNC-1.0 and previously reported
results for other metal oxide catalysts. (e) ORR polarization curves, and (f) corresponding ORR Tafel slopes L5N4, LNC-1.0, LNF-1.0, and Ir/C catalysts. (g) ORR
polarization curves of LNC-1.0 and Pt/C catalysts before and after 10,000 cycles of potential sweep (0.6–1.1 V). (h) Comparison of oxygen electrode activity (ΔE) for
LNC-1.0 and previous reported results for other oxygen catalysts.

electrode reactions could be intrinsically dependent on its electronic valence [54,55]. Decisively, a recent lattice-oxygen oxidation mecha­
configuration. To clarify the fundamental origin of the excellent OER nism (LOM) for OER could lead to much enhanced OER activity, this
performances of LNC-1.0, XPS was performed to investigate the surface mechanism bypasses the inherent thermodynamic limitation in the
chemical states of the catalysts (Figs. 7 and S5). Fig. 7a shows the Ni 2p conventional adsorbate evolution mechanism (AEM) via a sequence of
core level XPS spectra of the Lan+1NinO3n+1 family of catalysts, here, the concerted proton–electron transfers on the transition metal (M)-ion
main chemical states of Ni are + 2 and + 3. The peaks at ~ 854.5 and ~ centers [56,57]. This LOM for OER is promoted by the high covalency of
851.5 eV are considered to be from Ni2+ (2p1/2) and Ni2+ (2p3/2), the M− O bond, this allows the allocation of the electroactive sites from
respectively, while the peaks at ~ 864.1 and ~ 849.9 eV can be assigned Mz+ to O2– with the formation of a ligand hole [58]. Furthermore,
to Ni3+ (2p1/2) and Ni3+ (2p3/2) [52]. Interestingly, the ratio of Ni3+/ transition metal (Co, Fe) doping can promote the OER activity for L5N4
Ni2+ increased with increasing n (the number of perovskite layers) of the oxides via the LOM pathway with a synergistic effect coming from the
Ruddlesden-Popper structure. The relative content of the various dopant and parent cation in the Ruddlesden Popper structure. That is,
oxidation states of Ni ions was estimated from the integrated area ratios great M− O covalency caused by high Co2+,3+ (or Fe2+,3+)/Ni2+,3+
of the sub-peaks, these are listed in Table 4. The ratio of Ni3+/Ni2+ as content in La5Ni4-xMxO13-δ results in activating surface lattice oxygen to
calculated were 0.52:1, 0.56:1, 0.69:1, 0.82:1 for L2N1, L3N2, L4N3, participate in the OER, this is likely the origin of the high intrinsic ac­
and L5N4, respectively. Hence, the calculated average valence of the Ni tivity of the Ruddlesden-Popper structured materials [59-61].
ions was determined to be 2.0, 2.50, 2.67, and 2.75 for L2N1, L3N2, The O 1 s core level XPS spectra of LNO are given in Fig. 7b, these
L4N3, and L5N4, respectively. This is because the multivalent Ni ions were deconvoluted into four main components: the molecular water
can be compensated by converting lower valence Ni+2 to higher valence absorbed on the surface (H2O, ~533 eV), surface absorbed oxygen (O2/
Ni+3 by increasing the number of oxygen vacancies in the perovskite OH− , ~531 eV), highly oxidative oxygen species (O2− 2 /O , ~530 eV)
−

layer in order to fulfill the electrical neutrality condition [53]. and lattice oxygen species (O2− , ~528.3 eV) [62]. The relative content
Additionally, according to previous theoretical and experimental of highly oxidative oxygen species on the L5N4 surface (41.1%) was
studies, the metal–oxygen covalency increases with the increased metal apparently higher than for other Ruddlesden-Popper materials. In

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S.R. Choi et al. Chemical Engineering Journal 409 (2021) 128226

Fig. 7. XPS spectra for (a) Ni 2p and (b) O 1 s of the L2N1, L3N2, L4N3, L5N4, LNF-0.5, and LNC-1.0 catalysts.

distortion of the lattice in perovskite systems, this generates the extra

Table 4
oxygen vacancies via structural deformation [63]. As calculated from the
X-ray photoelectron spectroscopy survey (showing calculated percentage ratio
Ni-site oxidation state using the iodometric titration method [64], the
of oxidative oxygen and lattice oxygen, as well as peak area ratios of various
oxidation states for Ni ions) for O 1 s and N 2p in the Lan+1NinO3n+1 (n = 1, 2, 3,
nonstoichiometric δ values of L2N1, L3N2, L4N3, L5N4, LNF-1.0, and
and 4), La5Ni3.5Fe0.5O13-δ, and La5Ni3CoO13-δ materials. LNC-1.0 were determined to be 0.08, –0.05, –0.13, –0.21, –0.45, and
–0.39, respectively, they are in good agreements with previously re­
Catalysts Oxidative Lattice Ni3+ : AverageNi-
oxygen(O2– Ni2+(with
ported results [65]. It is known that L2N1 has interstitial oxygen content
2 / oxygen site valence
O-) (%) (O2–) (%) Co/Fe) which resides in the LaO layers. Hence, the negative value of δ specifies
the generation of extra oxygen vacancies with increasing n (=the
La2NiO4+δ 36.51 24.80 0.52: 1.0 +2.34 (XPS)
La3Ni2O7-δ 39.31 26.52 0.56 : 1.0 +2.36 (XPS) number of perovskite layers) in the Ruddlesden-Popper structure, this is
La4Ni3O10-δ 40.38 27.17 0.69 : 1.0 +2.41 (XPS) in agreement with the results of the XPS O 1 s spectra analysis.
La5Ni4O13-δ 41.05 28.76 0.82 : 1.0 +2.45 (XPS) The high O2−2 /O
−
content can lead to an improved oxygen-ion
La5Ni3.5Fe0.5O13- 46.43 25.71 0.92 : 1.0 +2.53
diffusion rate and electrical conductivity due to the existence of abun­
(titration)
dant surface oxygen vacancies. We measured the oxygen-ion diffusion
δ
La5Ni3.0Co1.0O13- 54.29 20.24 1.13 : 1.0 +2.56
δ (titration) coefficient (Do) of L2N1, L5N4, and LNC-1.0 and evaluated their influ­
ence on the OER activity to further support LOM as being the origin of
the high intrinsic activity of LNC-1.0. Do was determined using com­
addition, Co– and Fe doping into L5N4 resulted in further increasing the bined chronoamperometry and CV measurements for the insertion and
relative content of highly oxidative oxygen species (46.4% and 54.3% extraction of oxygen-ions with an RDE (Fig. S6a) [35-37]. Current (i) vs.
for LNF-0.5 and LNC-1.0, respectively) on the catalyst surface (Table 4). t− 1/2 was plotted in Fig. S6b to obtain the intercept with the t− 1/2 axis (at
This result is also evidence of a synergistic effect from the dopant and i = 0). The Do value of LNC-1.0 was calculated to be 2.134 × 10− 11 cm2‧
parent cation in the Ruddlesden Popper structure via the LOM pathway. s− 1, this is ~ 5.0 and 3.6 times faster than that of L2N1 and L5N4,
Higher highly oxidative oxygen species content is correlated with the respectively, as presented in Fig. 8a. Consequently, fast Do will activate
surface oxygen vacancies in the catalysts. The increasing number of the surface lattice-oxygen by replenishing the surface oxygen consumed
perovskite layers (n) in the Ruddlesden-Popper Lan+1NinO3n+1 structure during the catalytic OER process. The pH dependence of OER activity on
can lead to the formation of high oxygen vacancy concentrations, this is the RHE scale also indicates LOM participation in alkaline medium re­
because the repeated stacking of lanthanide causes a structural actions, this is evidence for the presence of non-concerted

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S.R. Choi et al. Chemical Engineering Journal 409 (2021) 128226

Fig. 8. (a) Correlation of specific activity with oxygen-ion diffusion coefficient to scrutinize the intrinsic OER activity of catalysts. (b) OER kinetic currents of
catalysts in O2-saturated KOH (0.1, 0.5, and 1 M) electrolytes under various pH. (c) Charge-transfer (Rct) and mass transfer resistances (Rmt) of catalysts for OER at
1.7 V and ORR at 0.7 V from complex-plane Nyquist EIS plots. (d) Double layer charging current of catalysts calculated from CVs with different scan rate (10–200 mV‧
s− 1) in non-faradaic potential range.

proton–electron transfer steps during the OER. OER currents from CV slopes of the measured charging current (ic) plots as a function of v
measurements were found to increase while increasing pH from 13.5 to (Fig. 8d) that come from the CVs of various scan rates (v = 10, 20, 50,
14.0 for the Ruddlesden-Popper structured LNO (n = 1–4) and LNC-1.0 100, 150, and 200 mV‧s− 1) (Fig. S8). The ECSA of LNC-1.0 was 4.30 cm2,
(seen in Fig. 8b), this in agreement with the results in previous literature which is higher than that of L2N1 (2.93 cm2), L3N2 (2.90 cm2), L4N3
concerning LOM participation in the OER [36,60,66,67]. (3.43 cm2), and L5N4 (3.78 cm2).
To understand the fundamental origin of the excellent OER perfor­
mances of LNC-1.0, electrochemical impedance spectroscopy (EIS) was 4. Conclusion
performed in a three-electrode cell to analyze the resistance components
[ohmic resistance (Rohmic) of solution electrolyte, charge-transfer resis­ We demonstrated transition metal (M = Fe, Co)-doped Lan+1Nin-
tance (Rct), and mass-transfer resistance (Rmt)] [67,68]. Fig. S7 shows xMxO3n+1 (n = 1, 2, 3, and 4) with an n layered perovskite structures are
complex-plane Nyquist plots of LNO and LNC-1.0 catalysts at 1.7 and highly active during OER and ORR in alkaline medium. In particular, 4
0.7 V (vs. RHE) for OER and ORR. The Rct and Rmt values of the catalysts layered perovskite LNM catalysts were successfully synthesized with
significantly decrease in the order from smallest to biggest decreases of various dopants via GNC techniques under extremely fuel-rich condi­
L2N1, L3N2, L4N3, and L5N4 for both OER and ORR. This indicates the tions. The formation of high order L5N4 Ruddlesden-Popper phases was
excellent intrinsic activity of high n Ruddlesden-Popper structure elec­ confirmed through quantitative analysis with FESEM (and HRTEM)/
trocatalysts (Fig. 8c). In addition, LNC-1.0 exhibits the lowest Rct of 2.15 EDX and SAED pattern observed along the [1 0 0] zone axis of HRTEM
and 1.65 Ω‧cm2 among all the test samples, at 1.7 and 0.7 V (vs. RHE) for image, this in agreement with the results obtained from the Rietveld
OER and ORR, respectively, this confirms the most effective conducting refinement of the XRD results. The catalytic activity of LNO increased
path for charged ionic/electronic species in oxygen electrode reactions. with the number of perovskite layers at room temperature in alkaline
The electrochemically active surface area (ECSA) of the catalyst was also medium. Benefiting from its 4 layered perovskite structure with transi­
calculated by dividing the double layer capacitance (Cdl) by specific tion metal dopants, the La5Ni3CoO13-δ catalysts exhibited outstanding
capacitance (Cs ≈ 0.04 mF‧cm− 2), this is a critical indicator of catalysts bifunctional electrocatalytic activity with low overpotential and Tafel
for catalytic activity [69,70]. Cdl was determined by calculating the slopes for both OER and ORR. LNC-1.0 showed superior OER activity

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S.R. Choi et al. Chemical Engineering Journal 409 (2021) 128226

with extremely low overpotential (1.60 V at 10 mA‧cm− 2) and Tafel oxide/double perovskite bifunctional hybrid catalysts, J. Mater. Chem. A 5 (25)
(2017) 13019–13031.
slope (35 mV‧dec-1) that were superior to the other catalysts. Further­
[14] N.-I. Kim, Y.J. Sa, T.S. Yoo, S.R. Choi, R.A. Afzal, T. Choi, Y.-S. Seo, K.-S. Lee, J.
more, LNC-1.0 showed excellent long-term OER and ORR durability. Y. Hwang, W.S. Choi, S.H. Joo, J.-Y. Park, Oxygen-deficient triple perovskites as
Increasing the number of perovskite layers (n) in the Ruddlesden-Popper highly active and durable bifunctional electrocatalysts for oxygen electrode
Lan+1NinO3n+1 structure can lead to the formation of abundant surface reactions, Sci. Adv. 4 (6) (2018) eaap9360, https://doi.org/10.1126/sciadv.
aap9360.
oxygen vacancy concentrations and enriched electronic charge carriers [15] J. Suntivich, K.J. May, H.A. Gasteiger, J.B. Goodenough, Y. Shao-Horn,
due to the increased Ni oxidation state. Furthermore, the high O2− 2 /O
− A perovskite oxide optimized for oxygen evolution catalysis from molecular orbital
principles, Science 334 (6061) (2011) 1383–1385.
content can lead to an improved oxygen-ion diffusion rate and superior
[16] S. Takahashi, S. Nishimoto, M. Matsuda, M. Miyake, Electrode properties of the
electrical conductivity, this in turn results in the exceptional OER per­ Ruddlesden-Popper series, Lan+1NinO3n+1 (n=1, 2, and 3), as intermediate-
formances of LNC-1.0. temperature solid oxide fuel cells, J. Am. Ceram. Soc. 93 (2010) 2329-2333.
[17] S. Yoo, S. Choi, J. Shin, M. Liu, G. Kim, Electrical properties, thermodynamic
behavior, and defect analysis of Lan+1NinO3n+1+δ infiltrated into YSZ scaffolds as
cathodes for intermediate-temperature SOFCs, RSC Adv. 2 (11) (2012) 4648,
Declaration of Competing Interest https://doi.org/10.1039/c2ra20402a.
[18] S. Choi, S. Yoo, J.Y. Shin, G. Kim, High performance SOFC cathode prepared by
infiltration of Lan+1NinO3n+1 (n=1, 2, and 3) in porous YSZ, J. Electrochem. Soc.
The authors declare that they have no known competing financial
158 (2011) B995–B999.
interests or personal relationships that could have appeared to influence [19] S.N. Ruddlesden, P. Popper, New compounds of the K2NIF4 type, Acta Cryst. 10 (8)
the work reported in this paper. (1957) 538–539.
[20] E. Boehm, J.M. Bassat, P. Dordor, F. Mauvy, J.C. Grenier, P. Stevens, Oxygen
diffusion and transport properties in non-stoichiometric Ln2-xNiO4+δ oxides, Solid
Acknowledgments State Ionics 176 (2005) 2717–2725.
[21] M. Matsuda, M. Hashimoto, C. Matsunaga, T.S. Suzuki, Y. Sakka, T. Uchikoshi,
Electrophoretic fabrication of a-b plane oriented La2NiO4 cathode onto electrolyte
This research was supported by the Climate Change Technology in strong magnetic field for low-temperature operating solid oxide fuel cell,
Research Program (NRF-2015M1A2A2057042), Technology Develop­ Journal of the European Ceramic Society 36 (16) (2016) 4077–4082.
ment Program to Hydrogen Energy (NRF-2019M3E6A1064020) [22] D. Cetin, S. Poizeau, J. Pietras, S. Gopalan, Decomposition of La2NiO4 in
Sm0.2Ce0.8O2-La2NiO4 composites for solid oxide fuel cell applications, Solid State
through the National Research Foundation funded by the Ministry of Ionics 300 (2017) 91–96.
Science and ICT of Korea, and Technology Innovation Program [23] P. Li, B. Yu, J. Li, X. Yao, Y. Zhao, Y. Li, A single layer solid oxide fuel cell
(20011633) funded by the Ministry of Trade, Industry & Energy of composed of La2NiO4 and doped ceria-carbonate with H2 and methanol as fuels,
International Journal of Hydrogen Energy 41 (21) (2016) 9059–9065.
(MOTIE) Korea.
[24] J. Yu, J. Sunarso, Y. Zhu, X. Xu, R. Ran, W. Zhou, Z. Shao, Activity and stability of
Ruddlesden-Popper-Type Lan+1NinO3n+1 (n =1, 2, 3, and ∞) electrocatalysts for
Appendix A. Supplementary data oxygen reduction and evolution reactions in alkaline media, Chem. Eur. J. 22 (8)
(2016) 2719–2727.
[25] X. Ma, B. Wang, E. Xhafa, K. Sun, E. Nikolla, Synthesis of shape-controlled La2 NiO4
Supplementary data to this article can be found online at https://doi. +δ nanostructures and their anisotropic properties for oxygen diffusion, Chem.
org/10.1016/j.cej.2020.128226. Commun. 51 (1) (2015) 137–140.
[26] M.D. Carvalho, F.M.A. Costa, I.D.S. Pereira, A. Wattiaux, J.M. Bassat, J.C. Grenier,
M. Pouchard, New preparation method of Lan+1NinO3n+1-δ (n=2, 3), J. Mater.
References Chem. 7 (1997) 2107-2111.
[27] R.D. Purohit, B.P. Sharma, K.T. Pillai, A.K. Tyagi, Ultrafine ceria powders via
glycine-nitrate combustion, Materials Research Bulletin 36 (15) (2001)
[1] W.T. Hong, K.A. Stoerzinger, Y.-L. Lee, L. Giordano, A. Grimaud, A.M. Johnson,
2711–2721.
J. Hwang, E.J. Crumlin, W. Yang, Y. Shao-Horn, Charge-transfer-energy-dependent
[28] A. Varma, A.S. Mukasyan, A.S. Rogachev, K.V. Manukyan, Solution Combustion
oxygen evolution reaction mechanisms for perovskite oxides, Energy Environ. Sci.
Synthesis of Nanoscale Materials, Chem. Rev. 116 (23) (2016) 14493–14586.
10 (10) (2017) 2190–2200.
[29] A. Wain-Martin, A. Morán-Ruiz, K. Vidal, A. Larrañaga, M.A. Laguna-Bercero, M.
[2] J.W.D. Ng, M. Tang, T.F. Jaramillo, A carbon-free, precious-metal-free, high-
I. Arriortua, Scalable synthetic method for SOFC compounds, Solid State Ionics 313
performance O2 electrode for regenerative fuel cells and metal–air batteries,
(2017) 52–57.
Energy Environ. Sci. 7 (6) (2014) 2017, https://doi.org/10.1039/c3ee44059a.
[30] Z. Ming, Z. Lu, Y. Chunzhen, C. Yao, S. Zhongrong, C. Bo, All-nanosheet OER/ORR
[3] B.T. Zhao, L. Zhang, D.X. Zhen, S. Yoo, Y. Ding, D.C. Chen, Y. Chen, Q.B. Zhang,
bifunctional electrocatalyst for both aprotic and aqueous Li-O2 batteries, Nanoscale
B. Doyle, X.H. Xiong, M.L. Liu, A tailored double perovskite nanofiber catalyst
11 (2019) 2855–2862.
enables ultrafast oxygen evolution, Nat. Commun. 8 (2017) 14586.
[31] Y. Jiang, Y.P. Deng, J. Fu, D.U. Lee, R.L. Liang, Z.P. Cano, Y.S. Liu, Z.Y. Bai,
[4] J. Yang, T. Fujigaya, N. Nakashima, Decorating unoxidized-carbon nanotubes with
S. Hwang, L. Yang, D. Su, W.G. Chu, Z.W. Chen, Interpenetrating triphase cobalt-
homogeneous Ni-Co spinel nanocrystals show superior performance for oxygen
based nanocomposites as efficient bifunctional oxygen electrocatalysts for long-
evolution/reduction reactions, Sci. Rep. 7 (2017) 45384.
lasting rechargeable Zn-air batteries, Adv. Energy. Mater. 8 (2018) 1702900.
[5] S.-W. Kim, Y. Son, K. Choi, S.-I. Kim, Y. Son, J. Park, J.H. Lee, J.-H. Jang, Highly
[32] Y.X. Lin, L. Yang, Y.K. Zhang, H.L. Jiang, Z.J. Xiao, C.Q. Wu, G.B. Zhang, J. Jiang,
Active Bifunctional Electrocatalysts for Oxygen Evolution and Reduction in Zn–Air
L. Song, Defective carbon-CoP nanoparticles hybrids with interfacial charges
Batteries, ChemSusChem 11 (24) (2018) 4203–4208.
polarization for efficient bifunctional oxygen electrocatalysis, Adv. Energy. Mater.
[6] S. Gadipelli, T. Zhao, S.A. Shevlin, Z. Guo, Switching effective oxygen reduction
8 (2018) 1703623.
and evolution performance by controlled graphitization of a
[33] S. Yagi, I. Yamada, H. Tsukasaki, A. Seno, M. Murakami, H. Fujii, H. Chen,
cobalt–nitrogen–carbon framework system, Energy Environ. Sci. 9 (5) (2016)
N. Umezawa, H. Abe, N. Nishiyama, S. Mori, Covalency-reinforced oxygen
1661–1667.
evolution reaction catalyst, Nat. Commun. 6 (2015) 8249.
[7] J. Wandt, A.T.S. Freiberg, A. Ogrodnik, H.A. Gasteiger, Singlet oxygen evolution
[34] A. Grimaud, O. Diaz-Morales, B. Han, W.T. Hong, Y.-L. Lee, L. Giordano, K.
from layered transition metal oxide cathode materials and its implications for
A. Stoerzinger, M.T.M. Koper, Y. Shao-Horn, Activating lattice oxygen redox
lithium-ion batteries, Materials Today 21 (8) (2018) 825–833.
reactions in metal oxides to catalyse oxygen evolution, Nature Chem 9 (5) (2017)
[8] L. Du, L.L. Luo, Z.X. Feng, M. Engelhard, X.H. Xie, B.H. Han, J.M. Sun, J.H. Zhang,
457–465.
G.P. Yin, C.M. Wang, Y. Wang, Y.Y. Shao, Nitrogen-doped graphitized carbon shell
[35] J.T. Mefford, X. Rong, A.M. Abakumov, W.G. Hardin, S. Dai, A.M. Kolpak, K.
encapsulated NiFe nanoparticles: A highly durable oxygen evolution catalyst, Nano
P. Johnston, K.J. Stevenson, Water electrolysis on La1− xSrxCoO3− δ perovskite
Energy 39 (2017) 245–252.
electrocatalysts, Nat. Commun. 7 (2016) 11053.
[9] Y. Wang, J. Li, Z. Wei, Transition-metal-oxide-based catalysts for the oxygen
[36] Y. Pan, X. Xu, Y. Zhong, L. Ge, Y. Chen, J.-P.-M. Veder, D. Guan, R. O’Hayre, M. Li,
reduction reaction, J. Mater. Chem. A 6 (18) (2018) 8194–8209.
G. Wang, H. Wang, W. Zhou, Z. Shao, Direct evidence of boosted oxygen evolution
[10] Y. Xue, S. Sun, Q. Wang, Z. Dong, Z. Liu, Transition metal oxide-based oxygen
over perovskite by enhanced lattice oxygen participation, Nat. Commun. 11 (2020)
reduction reaction electrocatalysts for energy conversion systems with aqueous
2002.
electrolytes, J. Mater. Chem. A 6 (23) (2018) 10595–10626.
[37] F.R. Van Buren, G.H.J. Broers, A.J. Bouman, C. Boesveld, The electrochemical
[11] J.-I. Jung, M. Risch, S. Park, M.G. Kim, G. Nam, H.-Y. Jeong, Y. Shao-Horn, J. Cho,
determination of oxygen ion diffusion coefficients in La0.50Sr0.50CoO3− y, Journal of
Optimizing nanoparticle perovskite for bifunctional oxygen electrocatalysis,
Electroanalytical Chemistry and Interfacial Electrochemistry 88 (3) (1978)
Energy Environ. Sci. 9 (1) (2016) 176–183.
353–361.
[12] H. Asano, J. Hayakawa, M. Matsui, Preparation and properties of triple perovskite
[38] M. Jungbauer, S. Huhn, R. Egoavil, H. Tan, J. Verbeeck, G. Van Tendeloo,
La3− 3xCa1+3xMn3O10 ferromagnetic thin films, Appl. Phys. Lett. 71 (6) (1997)
V. Moshnyaga, Atomic layer epitaxy of Ruddlesden-Popper SrO(SrTiO3)n films by
844–846.
means of metalorganic aerosol deposition, Appl. Phys. Lett. 105 (2014), 251603.
[13] N.-I. Kim, R.A. Afzal, S.R. Choi, S.W. Lee, D. Ahn, S. Bhattacharjee, S.-C. Lee, J.
H. Kim, J.-Y. Park, Highly active and durable nitrogen doped-reduced graphene

11
S.R. Choi et al. Chemical Engineering Journal 409 (2021) 128226

[39] R.K. Sharma, M. Burriel, E. Djurado, La4Ni3O10-δ as an efficient solid oxide fuel cell [56] M. Kim, H. Ju, J. Kim, Single crystalline Bi2Ru2O7 pyrochlore oxide nanoparticles
cathode: electrochemical properties versus microstructure, J. Mater. Chem. A 3 as efficient bifunctional oxygen electrocatalyst for hybrid Na-air batteries, Chem.
(2015) 23833–23843. Eng. J. 358 (2019) 11–19.
[40] N. Gauquelin, T.E. Weirich, M. Ceretti, W. Paulus, M. Schroeder, Long-term [57] A. Seong, J. Kim, O. Kwon, H.Y. Jeong, R.J. Gorte, J.M. Vohs, G. Kim, Self-
structural surface modifications of mixed conducting La2NiO4+δ at high reconstructed interlayer derived by in-situ Mn diffusion from La0.5Sr0.5MnO3 via
temperatures, Monatsh Chem 140 (9) (2009) 1095–1102. atomic layer deposition for an efficient bi-functional electrocatalyst, Nano Energy
[41] J. Kibsgaard, I.b. Chorkendorff, Considerations for the scaling-up of water splitting 71 (2020), 104564.
catalysts, Nat Energy 4 (6) (2019) 430–433. [58] Y. Zhu, W. Zhou, J. Yu, Y. Chen, M. Liu, Z. Shao, Enhancing electrocatalytic
[42] S. Liu, I.S. Amiinu, X. Liu, J. Zhang, M. Bao, T. Meng, S. Mu, Carbon nanotubes activity of perovskite oxides by tuning cation deficiency for oxygen reduction and
intercalated Co/N-doped porous carbon nanosheets as efficient electrocatalyst for evolution reactions, Chem. Mater. 28 (6) (2016) 1691–1697.
oxygen reduction reaction and zinc–air batteries, Chemical Engineering Journal [59] C. Li, X.P. Han, F.Y. Cheng, Y.X. Hu, C.C. Chen, J. Chen, Phase and composition
342 (2018) 163–170. controllable synthesis of cobalt manganese spinel nanoparticles towards efficient
[43] Y. Zhu, X.i. Liu, S. Jin, H. Chen, W. Lee, M. Liu, Y. Chen, Anionic defect engineering oxygen electrocatalysis, Nat. Commun. 6 (2015) 7345.
of transition metal oxides for oxygen reduction and evolution reactions, J. Mater. [60] W. Xu, N. Apodaca, H. Wang, L. Yan, G. Chen, M. Zhou, D. Ding, P. Choudhury,
Chem. A 7 (11) (2019) 5875–5897. H. Luo, A-site excessive (La0.8Sr0.2)1+xMnO3 perovskite oxides for bifunctional
[44] S.M. Zhou, X.B. Miao, X. Zhao, C. Ma, Y.H. Qiu, Z.P. Hu, J.Y. Zhao, L. Shi, J. Zeng, oxygen catalyst in alkaline media, ACS Catal. 9 (6) (2019) 5074–5083.
Engineering electrocatalytic activity in nanosized perovskite cobaltite through [61] H.M. Sun, Y.X. Ye, Z.F. Tian, S.L. Wu, J. Liu, C.H. Liang, Ni3+ doped cobalt–nickel
surface spin-state transition, Nat. Commun. 7 (2016) 11510. layered double hydroxides as high-performance electrode materials for
[45] S. Li, X. Meng, Q. Yi, J.A. Alonso, M.T. Fernández-Díaz, C. Sun, Z.L. Wang, supercapacitors, RSC Adv. 7 (77) (2017) 49010–49014.
Structural and electrochemical properties of LiMn0.6Fe0.4PO4 as a cathode material [62] L. Wang, K.A. Stoerzinger, L. Chang, J.L. Zhao, Y.Y. Li, C.S. Tang, X.M. Yin, M.
for flexible lithium-ion batteries and self-charging power pack, Nano Energy 52 E. Bowden, Z.Z. Yang, H.Z. Guo, L. You, R. Guo, J. Wang, K. Ibrahim, J.S. Chen,
(2018) 510–516. A. Rusydi, J.L. Wang, S.A. Chambers, Y.G. Du, Tuning bifunctional oxygen
[46] X.M. Xu, C. Su, W. Zhou, Y.L. Zhu, Y.B. Chen, Z.P. Shao, Co-doping strategy for electrocatalysts by changing the A-Site rare-earth element in perovskite nickelates,
developing perovskite oxides as highly efficient electrocatalysts for oxygen Adv. Funct. Mater. 28 (2018) 1803712.
evolution reaction, Adv. Sci. 3 (2016) 1500187. [63] R. Nakajima, J. Stohr, Y.U. Idzerda, Electron-yield saturation effects in L-edge x-ray
[47] S. Liu, H. Luo, Y. Li, Q. Liu, J.-L. Luo, Structure-engineered electrocatalyst enables magnetic circular dichroism spectra of Fe Co, and Ni, Phys. Rev. B 59 (1999)
highly active and stable oxygen evolution reaction over layered perovskite 6421–6429.
LaSr3Co1.5Fe1.5O10-δ, Nano Energy 40 (2017) 115–121. [64] D.Q. Guan, J. Zhou, Z.W. Hu, W. Zhou, X.M. Xu, Y.J. Zhong, B. Liu, Y.H. Chen, M.
[48] Y. Duan, S.N. Sun, Y.M. Sun, S.B. Xi, X. Chi, Q.H. Zhang, X. Ren, J.X. Wang, S.J. G. Xu, H.J. Lin, C.T. Chen, J.Q. Wang, Z.P. Shao, Searching general sufficient-and-
H. Ong, Y.H. Du, L. Gu, A. Grimaud, Z.C.J. Xu, Mastering surface reconstruction of necessary conditions for ultrafast hydrogen-evolving electrocatalysis, Adv. Funct.
metastable spinel oxides for better water oxidation, Adv. Mater. 31 (2019) Mater. 29 (2019) 1900704.
1807898. [65] J.S. Yoo, X.i. Rong, Y. Liu, A.M. Kolpak, Role of lattice oxygen participation in
[49] J.G. Lee, J. Hwang, H.J. Hwang, O.S. Jeon, J. Jang, O. Kwon, Y. Lee, B. Han, Y.- understanding trends in the oxygen evolution reaction on perovskites, ACS Catal. 8
G. Shul, A New Family of Perovskite Catalysts for Oxygen-Evolution Reaction in (5) (2018) 4628–4636.
Alkaline Media: BaNiO3 and BaNi0.83O2.5, J. Am. Chem. Soc. 138 (10) (2016) [66] Z.-F. Huang, J. Song, Y. Du, S. Xi, S. Dou, J.M.V. Nsanzimana, C. Wang, Z.J. Xu,
3541–3547. X. Wang, Chemical and structural origin of lattice oxygen oxidation in Co–Zn
[50] I. Yamada, M. Murakami, N. Hayashi, S. Mori, Inverse charge transfer in the oxyhydroxide oxygen evolution electrocatalysts, Nat Energy 4 (4) (2019) 329–338.
quadruple perovskite CaCu3Fe4O12, Inorg. Chem. 55 (4) (2016) 1715–1719. [67] Y.L. Zhu, H.A. Tahini, Z.W. Hu, Z.G. Chen, W. Zhou, A.C. Komarek, Q. Lin, H.J. Lin,
[51] J. Park, M. Risch, G. Nam, M. Park, T.J. Shin, S. Park, M.G. Kim, Y. Shao-Horn, C.T. Chen, Y.J. Zhong, M.T. Fernandez-Diaz, S.C. Smith, H.T. Wang, M.L. Liu, Z.
J. Cho, Single crystalline pyrochlore nanoparticles with metallic conduction as P. Shao, Boosting oxygen evolution reaction by creating both metal ion and lattice-
efficient bi-functional oxygen electrocatalysts for Zn–air batteries, Energy Environ. oxygen active sites in a complex oxide, Adv. Mater. 32 (2020) 1905025.
Sci. 10 (1) (2017) 129–136. [68] X. Wang, Z. Pan, X. Chu, K. Huang, Y. Cong, R. Cao, R. Sarangi, L. Li, G. Li, S. Feng,
[52] J. Park, M. Park, G. Nam, M.G. Kim, J. Cho, Unveiling the catalytic origin of Atomic-scale insights into surface lattice oxygen activation at the spinel/perovskite
nanocrystalline yttrium ruthenate pyrochlore as a bifunctional electrocatalyst for interface of Co3O4 /La0.3Sr0.7CoO3, Angew. Chem. Int. Ed. 58 (34) (2019)
Zn–air batteries, Nano Lett. 17 (6) (2017) 3974–3981. 11720–11725.
[53] Y. Li, Z.S. Wu, P. Lu, X. Wang, W. Liu, J. Ma, W. Ren, Z. Jiang, X. Bao, High-Valence [69] J.T. Mefford, X. Rong, A.M. Abakumov, W.G. Hardin, S. Dai, A.M. Kolpak, K.
Nickel Single-Atom Catalysts Coordinated to Oxygen Sites for Extraordinarily P. Johnston, K.J. Stevenson, Water electrolysis on La1-xSrxCoO3-δ perovskite
Activating Oxygen Evolution Reaction, Adv. Sci 7 (2020) 1903089–1903097. electrocatalysts, Nat. Commun. 7 (2016) 11053.
[54] N.-I. Kim, S.-H. Cho, S.H. Park, Y.J. Lee, R.A. Afzal, J. Yoo, Y.-S. Seo, Y.J. Lee, J.- [70] Y.L. Zhu, Q. Lin, Z.W. Hu, Y.B. Chen, Y.C. Yin, H.A. Tahini, H.J. Lin, C.T. Chen, X.
Y. Park, B-site doping effects of NdBa0.75Ca0.25Co2O5+δ double perovskite catalysts W. Zhang, Z.P. Shao, H.T. Wang, Self-assembled Ruddlesden-Popper/perovskite
for oxygen evolution and reduction reactions, J. Mater. Chem. A 6 (36) (2018) hybrid with lattice-oxygen activation as a superior oxygen evolution
17807–17818. electrocatalyst, Small 16 (2020) 2001204.
[55] C. Su, T. Yang, W. Zhou, W. Wang, X. Xu, Z. Shao, Pt/C–LiCoO 2 composites with
ultralow Pt loadings as synergistic bifunctional electrocatalysts for oxygen
reduction and evolution reactions, J. Mater. Chem. A 4 (12) (2016) 4516–4524.

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