Research Article

ChemCatChem doi.org/10.1002/cctc.202401759

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Oxygen-Vacancy Rich Co3O4/CeO2 Interface for Enhanced

Oxygen Reduction and Evolution Reactions
Suranjana Patowary,[a, b] Amber Watson,[b] Rashmi Chetry,[a] Putla Sudarsanam,[c]
Andrea E. Russell,*[b] and Pankaj Bharali*[a]

Oxygen reduction and evolution reactions (ORR and OER, respec- vacancies and semicrystalline nature are inferenced to play a
tively) are the two most extensively studied reactions in electro- dominant role in altering the collective catalytic efficiency of
chemistry. Herein, we report the synthesis of Co3 O4 /CeO2 /GNP Co3 O4 /CeO2 /GNP. High concentration of oxygen vacancy defects
(GNP = graphene nanoplatelet) electrocatalyst for ORR and (68%) in Co3 O4 /CeO2 /GNP is presumed to play a dominant role
OER that exhibits an early onset potential (0.85 V) and half- here. The catalyst is bifunctional for ORR and OER with a bifunc-
wave potential (E1/2 ) of 0.69 V for ORR. The reported catalyst tionality index of 0.98 V and operates at an overpotential of
is highly durable with 87.6% retention of its initial current ƞ10 = 440 mV for OER. Ex situ X-ray absorption studies indi-
after a 6 h chronoamperometry test compared to 72.5% by cate an increased average oxidation state of Co by 15% in
Pt/C. It exhibits a negligible shift of E1/2 after 10,000 potential Co3 O4 /CeO2 /GNP compared to Co3 O4 /GNP, aiding in preserving
cycles for ORR. Heterogeneous oxide/oxide interfaces, oxygen its inherent catalytic nature of spinel Co3 O4 .

1. Introduction Significant efforts have been made in the design and devel-
opment of non-Pt metal group (non-PGM) based catalysts
About 80% of the world’s total energy demand is met by fossil (mostly first row transition metals) to meet the three major tar-
fuel-based materials. The exhaust from these natural gases and gets: cost, performance and durability.[4] Transition metal oxides
petroleum generates harmful greenhouse gases. To reach the with spinel (AB2 O4 ) and perovskite (ABO3 ) structures are seen to
sustainable development goals (SDGs), switching to sustainable be promising category of catalysts for ORR and OER in alkaline
modes of energy conversion is the primary step. Oxygen elec- fuel cells. Among them, cobalt (Co)-based electrocatalysts have
trochemistry is an integral part of sustainable energy devices. particularly gained attention due to the multivalent nature of
Oxygen reduction and evolution reactions (ORR and OER respec- cobalt, as well as its high abundance and low-cost, 10–15 USD/lb,
tively) are the two most important reactions that drive fuel compared with noble metals.[5] Great amount of research has
cells and water electrolysers.[1] Currently these reactions rely been dedicated toward improving the catalytic performances
on the use of precious metal-based catalysts such as 20 wt% of spinel cobalt oxides (Co3 O4 ).[6] The shuttle between Co2+ Td
Pt/C (for ORR) and RuO2 or IrO2 (for OER).[2] The market price and Co3+ Oh enables the Co3 O4 -based catalysts to be inherently
of these is high, around $800–$1000 per ounce, which hinders bifunctional toward ORR and OER. Engineering the molecu-
the widespread commercialization of green energy devices.[3] lar and electronic structure of a generic Co3 O4 by employing
Although Pt/C, RuO2 , and IrO2 are highly active for the target MO|MO (MO: metal oxide) interface is a versatile technology
reactions, they suffer degradation and dissolution on prolonged to boost its robustness.[7] The generation of a heterogeneous
use. Hence the stability issue is another bottleneck on the route interface provides greater number of transient active sites in
to commercialization.[1] Co3 O4 that allow facile electron transport for ORR and/or OER.
For instance, highly active Co-based electrocatalysts can be syn-
thesized with high intrinsic activity and stability by integration
[a] S. Patowary, R. Chetry, P. Bharali
with N-doped graphene oxides. But most of the time, these
Department of Chemical Sciences, Tezpur University, Napaam, Tezpur, require prolonged and harsh thermal treatment.[8,9] Hence, we
Assam 784 028, India need synthesis methodologies which are easier and more envi-
E-mail: [email protected] ronmentally friendly. One such methodology is the integration
[b] S. Patowary, A. Watson, A. E. Russell of the ceria (CeO2 ). CeO2 , a well-known oxygen buffer, proves
School of Chemistry and Chemical Engineering, University of Southampton, to be a highly efficient additive in modifying the inherent cat-
Southampton SO17 1BJ, UK
alytic activities of Co-based electrocatalysts. There are numerous
E-mail: [email protected]
reports on this but not much is understood about the mechanis-
[c] P. Sudarsanam
Department of Chemistry, Indian Institute of Technology Hyderabad, Kandi,
tic details.[10–16] A better understanding of the redox properties of
Telangana 502284, India Co3 O4 upon intergration with CeO2 is key to developing highly
Supporting information for this article is available on the WWW under efficient cheaper electrocatalysts as substitutes for Pt/C, RuO2
https://doi.org/10.1002/cctc.202401759 and IrO2 . Since the 3d MOx have high electrical resistance, using

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Research Article
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a conductive carbon support is preferred, resulting in a MOx /C Brunauer–Emmett–Teller (BET) measurements, Fourier transform
type composite.[17] infrared spectroscopy (FTIR), inductively coupled plasma-optical
In this work, we report the design of a solvothermally emission spectroscopy (ICP-OES), X-ray photoelectron spectroscopy
(XPS), X-ray absorption near-edge structure (XANES), electron para-
synthesized Co3 O4 /CeO2 /GNP (GNP: graphene nanoplatelets),
magnetic resonance (EPR) and extended X-ray absorption fine
which provides a means to engineer the interface of the crys-
structure (EXAFS) spectroscopy, high resolution-transmission elec-
talline/amorphous (semicrystalline) spinel Co3 O4 toward ORR tron microscopy (HR-TEM). The details of the instruments employed,
and OER in alkaline media. The graphitic C promotes electrical and analysis procedures are provided in Supporting Information.
conductivity in the support,[2] whilst the flexible transformation
between Ce3+ and Ce4+ in CeO2 modifies the surface atomic
ratio of Co2+ and Co3+ ions in Co3 O4 . This, in turn, modifies the 2.4. Preparation of Working Electrodes
adsorption affinity toward oxygen species and modifies the ORR
and OER activity.[18] A systematic investigation has been carried A homogeneous suspension of the catalyst was prepared by ultra-
sonicating 5 mg sample with 500 μL each of water, isopropanol
out to study the underlying synergistic effects responsible for
and 0.5 wt% Nafion solution. A fine monolayer of 3 μL of catalyst
the higher catalytic performance of Co3 O4 /CeO2 /GNP compared ink was then dropcasted onto a finely polished PEEK surrounded
to their nonhybrid analogues, Co3 O4 /GNP and CeO2 /GNP. The 3 mm diameter (disk area is 0.0706 cm−2 ) glassy carbon rotating disk
catalysts were tested for bifunctionality, long-term durability and electrode (GC-RDE) purchased from Metrohm. This gives a catalyst
stability to examine their practical application. The goal of the loading of 0.142 mg cm−2 . The droplet was allowed to dry overnight
work was to develop an efficient and durable oxygen electrocat- at 35 °C in the oven under N2 conditions. Before dropcasting, the
alyst and to contribute to the understanding of key factors to disk was polished on a microcloth with a slurry of alumina powder
(initially with 1 μm for 12 min followed by 0.03 μm) until a mirror
design a bifunctional catalyst.
shining surface was obtained.

2. Experimental Section
2.5. Electrocatalytic Measurements
2.1. Reagents and Materials All electrochemical experiments were performed in an Autolab
PGSTAT 204 workstation (Metrohm, The Netherlands) and the soft-
Cobalt chloride hexahydrate CoCl2 6H2 O (≥98.0%), ammonium
ware used was NOVA. A standard three-electrode electrochemical
cerium nitrate (NH4 )2 [Ce(NO3 )6 ] (≥98.5%), urea (NH2 CONH2 , 99–
glass cell was used with a freshly prepared 3 M KCl filled Ag/AgCl
100.5%), and ethanol (ACS, ISO, Reag., ≥99.5%) were purchased from
reference electrode (Metrohm), a glass electrode with a clean Pt
Merck. Commercial 20wt % Pt/C, ruthenium (IV) oxide anhydrous
mesh at the tip as the counter electrode (CE) and the GC-RDE as
(RuO2 , 99.9%), graphene nanoplatelets (submicron particles, S.A.
the working electrode (WE). The supporting electrolyte used was
500 m2 /g), and Nafion R-1100 resin pellets were purchased from Alfa
0.1 M KOH. The electrochemical experiments using a stationary cyclic
Aesar. All reagents were analytically pure and used without further
voltammetry (CV) were carried out at a scan rate of 10 mVs−1 and
purification.
linear sweep voltammetry (LSV) at rotation rates 400, 900, 1600,
2500, 3600 rpm at 10 mVs−1 in the potential window of 0.2–1.2 V
versus RHE (Reversible Hydrogen Electrode) for ORR, and 1.2–1.8 V
2.2. Synthesis of Catalysts versus RHE for OER. An accelerated durability test (ADT) was done
for Co3 O4 /CeO2 /GNP to compare the shift in half-wave potential
CoCl2 6H2 O (45 mM) and (NH4 )2 [Ce (NO3 )6 ] (15 mM) were dissolved
(E1/2 ) before and after 10000 cycles of CVs. Chronoamperometry (CA)
together in 50 mL of deionized water. A 50 mL of 150 mM urea
was performed at 1600 rpm to compare the stability of the cata-
was added to the metal solution dropwise under continuous stir-
lyst with 20 wt% Pt/C. Ultrahigh purity nitrogen gas (UHP-N2 ) was
ring. The mixture was stirred for another 30 min, and then it was
purged into the electrolyte for 20 min to ensure elimination of any
transferred into a Teflon cup. The stainless-steel autoclave was kept
unwanted dissolved gases. UHP-O2 gas was then purged for 20 min
in the oven at 180 °C for 6 h. After cooling down to room tempera-
to ensure saturation of the the system with O2 for ORR. The O2 flow
ture, the precipitate was washed off with deionized water 3–4 times
was maintained at the surface of the electrolyte to form a blanket
and subsequently with ethanol for 2 times. The product was then
of O2 gas to avoid the dissolution of other gases from air. Before
dried at 60 °C. After complete drying, a 30:70 w/w mixture of the
performing ORR/OER, numerous fast scans were performed until the
product and graphene nanoplatelets (GNP) was prepared using a
voltammograms looked reproducible. All experiments were carried
simple mortar and pestle. This mixture was then sonicated for 1 h to
out at room temperature (25 ± 2 °C). Considering the ORR pro-
allow complete mixing of the components with ethanol as solvent
cesses as one-step reaction and follows first-order kinetics, we use
matrix and then allowed to dry at 60 °C. The obtained black colored
the Koutecky-Levich theory (K-L plot) to determine the number of
product is the as-synthesized catalyst. The final product is labeled as
electrons transferred (n).
Co3 O4 /CeO2 /GNP. The same synthesis procedure was used to syn-
thesize Co3 O4 /GNP and CeO2 /GNP by taking the cobalt precursor
(60 mM) and the cerium precursor (60 mM), respectively keeping all
experimental parameters intact. 3. Results and Discussion

3.1. Physicochemical Characterization

2.3. Materials Characterization
The as-synthesized materials were characterized by powder X-ray The schematic illustration of the catalyst’s synthesis is shown
diffraction (PXRD), Raman spectroscopy, thermogravimetry (TGA), in Figure 1a. Figure 1b shows the indexed PXRD spectra of the

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Figure 1. (a) Schematic illustration of the catalyst’s synthesis, (b) PXRD pattern of Co3 O4 /CeO2 /GNP, (c) Raman spectra, and (d) BET adsorption/desorption
isotherms with BJH pore distribution (inset) of various catalysts.

Co3 O4 /CeO2 /GNP catalyst. The miller indexes of all the observed (0.71), whereas that for Co3 O4 /GNP, CeO2 /GNP and GNP are ∼0.6.
XRD peaks correspond to JCPDS card nos. 65–3130 (for Co3 O4 ; This indicates that there are ∼17% more defects in the overall
crystallizes in the cubic Fd3̅m space group), 81–0792 (for CeO2 ; structure of Co3 O4 /CeO2 /GNP.
crystallizes in the cubic Fm3̅m space group) and 89–8487 for Powdered samples are rarely smooth at the atomic level.
GNP. The corresponding data for all synthesized catalysts and To determine the textural porosity of the catalysts, N2 gas
GNP is provided in Figure S1 (Supporting Information). The pres- adsorption isotherms were measured. Prior to measurement, the
ence of multiple phases in the crystalline structures of the catalysts were outgassed at 80 °C for 1 h and 120 °C for 3 h under
as-synthesized catalysts depicts their polycrystalline nature. A vacuum to remove moisture and any possible contaminants. The
clear observation from the broad peaks in the diffraction pat- adsorption/desorption curves are presented in Figure 1d. The
tern is that Co3 O4 /CeO2 /GNP is not purely crystalline but is isotherms exhibit Type IV curves with an H3 hysteresis loop.
amorphous to some extent compared to its individual counter- This indicates the presence of capillary condensation and slit-
parts Co3 O4 , CeO2 and GNP. This is better visualized in Figure like pores.[20] This feature is attributed to nonrigid aggregates of
S1. Although Co3 O4, CeO2 and GNP exhibit sharp diffraction partially exfoliated stacks of the graphene nanoplatelets in the
peaks, Co3 O4 /CeO2 /GNP exhibit comparatively broader peaks, catalysts. The pore size distribution curve from the adsorption
more prominently from CeO2 . isotherm employing the Barrett–Joyner–Halenda (BJH) model is
Raman spectra are shown in Figure 1c. The as-synthesized also shown in inset of Figure 1d. The average pore width of the
catalysts display sharp response for D-band at 1353 cm−1 , G- catalysts fall in the range of 41–43 Å (∼4 nm), indicating that the
band at 1582 cm−1 and 2D band at 2700 cm−1 . The intensities catalysts are mesoporous in nature. The average pore volumes
of the D-band depict the presence of sp3 defects in the car- are similar (∼0.2 cm3 /g) for the three catalysts. The total specific
bon lattice comprising the graphene nanoplatelets. whereas the surface areas as calculated from the Brunauer−Emmett−Teller
G-band reflects E2g phonons arising out of in-plane stretching (BET) equation are listed in Table S1 and follows the order:
modes.[19] The ID /IG intensity ratios were calculated as this value Co3 O4 /CeO2 /GNP < Co3 O4 /GNP < CeO2 /GNP. This is in reverse
is indicative of the extent of defects in the overall structure. It is order to their ECSAs (shown in Figure 6h). This is possibly
observed that the ID /IG value is the highest for Co3 O4 /CeO2 /GNP due to the overlapping of Co3 O4 and CeO2 particles which

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Figure 2. (a) HR-TEM image of Co3 O4 /CeO2 /GNP showing loosely bound aggregates on graphene sheets. (b) Histogram for particle size distribution. (c)
SAED pattern with concentric rings indexed to corresponding Miller planes. (d) Low resolution TEM image used to determine particle size distribution. (e)
HR-TEM image showing different crystallites of Co3 O4 and CeO2 with lattice fringes indexed in (f ).

blocks the internal pores of CeO2 in the Co3 O4 /CeO2 /GNP mixed in Figure 1d. Empty spaces (voids and crystal defects) and grain
oxide. However, the reduced total specific surface area does not boundaries between crystallites are seen in Figure 2e,f. The
adversely affect the electrocatalytic activity of the mixed oxide. selected area electron diffraction pattern (SAED) is typical of
The bonding and chemical composition of the as-synthesized polycrystalline material with overlapping rings (see Figure 2c).
catalysts were studied using FT-IR spectroscopy (Figure S2, Sup- The average size of the particles is determined to be 6.5 nm
porting Information). The bands in the spectra are assigned to using the TEM image shown in Figure 2d.The nanoparticle size
the respective functional groups and modes of vibration, which distribution histogram was determined using ImageJ software[21]
is explained in detail in the Supporting Information. TGA was by selecting 26 randomly distributed particles.
performed to confirm the 30:70 wt% ratio of catalyst to GNP To know more about the surface chemical composition of
which is also explained in the Supporting Information (Figure the catalysts, X-ray photoelectron spectroscopy (XPS) was carried
S3, Supporting Information). To confirm the correct loading of out on the as-synthesized catalysts. All peaks were deconvo-
the metals, the ICP-OES analysis of the Co3 O4 /CeO2 /GNP cata- luted using Gaussian fitting. The wide range survey spectrum
lyst was conducted, and the ratios are tabulated in Table S2. of Co3 O4 /CeO2 /GNP is presented in Figure S5 (Supporting Infor-
From wt% in Table S2, we confirm that the molar ratio of Co/Ce mation) and it reveals the presence of Co, Ce, O and C. The
is maintained at 3:1. The Co/Ce ratio is further confirmed by core level O 1s spectra of the three as-synthesized catalysts were
Energy-Dispersive X-ray Spectroscopy (EDS) analysis (Figure S4, deconvoluted into three distinct peaks (see Figure 3a); at 532.8 eV
Supporting Information). (for surface adsorbed oxygen or hydroxyl groups comprising
TEM and HR-TEM micrographs were taken to examine the possibly of Co(OH)2 represented as Oads at 531.5 eV for low-
microstructure of the particles. Figure 2a reveals loosely bound coordinated surface oxygen-deficient species (Ov ), and at 530 eV
aggregates. This observation is consistent with an H3 hystere- for those bounded to metal atoms or lattice oxygen (Olat ).[8,22,23]
sis loop observed in N2 adsoprtion/desorption isotherm shown The fractional percentages of Oads , Ov, and Olat are calculated

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Figure 3. (a) An overlay of core O 1 s XP spectra of Co3 O4 /GNP, CeO2 /GNP and Co3 O4 /CeO2 /GNP. (b) Bar diagram of fractions of Oads , Ov, and Olat in
Co3 O4 /GNP, CeO2 /GNP, and Co3 O4 /CeO2 /GNP. (c) Bar diagram of fractions of Co2+/3+ and Ce3+/4+ . (d) Co 2p core XP spectra of the mixed catalyst
Co3 O4 /CeO2 /GNP. (e) Ce 3d core XP spectra of the mixed catalyst Co3 O4 /CeO2 /GNP.

from the area integration of the deconvoluted peaks using the peaks (784.7 eV and 781.5 eV), representing Co+2 and Co+3
formula: respectively. Similarly, the high energy band at 797.5 eV could
be deconvoluted into two fitting peaks, at 798.7 eV and 797.3 eV,
[Ov ]
%Ov = representing Co2+ and Co3+ respectively. The relative% of Co2+
[Oads ] + [Ov ] + [Olat ]
and Co3+ as calculated from the area under the fitted peaks are
The comparison of relative oxygen vacancies in the three cat- found to be 52% and 48% respectively. The details of the Co 2p
alysts is shown in the bar diagram of Figure 3b. It was found XP spectra are listed in Table S3. The area ratio of Co2+ is higher
that the mixed catalyst Co3 O4 /CeO2 /GNP has the highest frac- than Co3+ , indicating the nonstoichiometric distribution of the
tion of oxygen vacancies (68%) which is accompanied by 23% of Co2+ Td and Co3+ Oh from the generic spinel formula AB2 O4 .
Ce3+ ions and an almost 1:1 ratio of Co2+ /Co3+ (i.e., 52%:48%, see The Ce 3d core-level XPS spectra were deconvoluted into
Figure 3c) to balance the charge neutrality. eight subpeaks (Figure 3e). Out of these eight, u’ and v“” repre-
The core-level Co 2p XP spectra of Co3 O4 /CeO2 /GNP sent the 3d10 4f1 electronic configuration of Ce3+ 3d3/2 and 3d5/2
(Figure 3d) show two spin-orbit doublets with 15.8 eV apart; respectively, whereas the rest represent the 3d10 4f0 electronic
a high energy doublet band at 797.5 eV for Co 2p1/2 and a low configuration of Ce4+ ions.[11,27] The u’ and v“” peaks are signifi-
energy doublet band at 781.7 eV for Co 2p3/2 , accompanied by cant which implicates the presence of the substantial amount of
two satellite peaks. The spin-orbit splitting energy difference Ce3+ ions on the surface. The Ce3+ /Ce4+ ratio is a crucial param-
of 15.8 eV is a characteristic of cubic Co3 O4 .[24,25] The satellite eter that correlates greatly with its catalytic efficiency due to
peak at 804.5 eV for Co 2p1/2 and another one at 789.1 eV for oxygen nonstoichiometry. This ratio depends greatly on the syn-
Co 2p3/2 are characteristics of spinel Co3 O4 .[26] The low energy thesis technique. Obtaining the desired ratio is a challenging
doublet band at 781.7 eV could be deconvoluted into two fitting task and is not very well understood.[28] The presence of both

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electron from the core shell 1 s orbital to a vacant 4p orbital.

This is most likely due to strong effective nuclear charge on
the absorbing atom (Co) in Co3 O4 /CeO2 /GNP. The position of
pre-edge (1 s → 3d) is the same for both, i.e., 7709 eV but the
intensity is greater for Co3 O4 /CeO2 /GNP (see Figure 5c), which
indicates that Co3 O4 /CeO2 /GNP has slightly more distorted octa-
hedral, making the spin forbidden 1 s → 3d transition a little
more pronounced. To qualitatively determine the average oxida-
tion state of Co in Co3 O4 /CeO2 /GNP and Co3 O4 /GNP, the XANES
of standards- Co foil, CoO and Co3 O4 were used.[35,36] The lin-
ear plot of oxidation states versus edge energies is shown in
Figure 5e. The straight line follows the empirical relation E0 =
(3.85 ± 0.16)x + (7708.9 ± 0.32) where E0 is the main edge energy
and “x” is the average oxidation state of Co. Using this calibra-
tion plot, the average oxidation state of Co in Co3 O4 /GNP and
Co3 O4 /CeO2 /GNP are 2.28 and 2.38, respectively.
The EXAFS spectra of Co3 O4 /CeO2 /GNP (Figure 5d and fit-
ting parameters in Table 1) and Co3 O4 /GNP (shown in Figure
S8 of Supporting Information) were fit to a three-shell model
Figure 4. EPR spectra of Co3 O4 /GNP and Co3 O4 /CeO2 /GNP. to investigate possible perturbation of the local coordination
environment of the Co (see Figure 5d). However, the structure
Ce3+ and Ce4+ proves the inherent redox nature of CeO2 and it distortion mentioned in Figure 5c is not reflected from bond
is an indication of charge imbalance and oxygen vacancies in the distance or co-ordination number in EXAFS. The most plausible
Co3 O4 /CeO2 /GNP catalyst. All details obtained from the Ce 3d XP reason for this could be that the oxygen vacancies found via XPS
spectra are listed in Table S4. may be restricted to the surface and not bulk. Another reason
The survey spectra of Co3 O4 /GNP and CeO2 /GNP along with could also be that the crystallite sizes are big enough (>5 nm)
individual core level XP spectra of the individual atoms present for EXAFS to detect these differences.
are also presented in Figures S6 and S7 (Supporting Information)
respectively. From Table S3, it is observed that binding ener-
gies of Co ions have a more positive shift in the mixed catalyst 3.2. Electrocatalytic Studies
Co3 O4 /CeO2 /GNP which confirms that bonds in Co3 O4 /CeO2 /GNP
are stronger than those in Co3 O4 /GNP. The three as-synthesized catalysts Co3 O4 /CeO2 /GNP, Co3 O4 /GNP
To provide strong evidence on oxygen vacancies, EPR is and CeO2 /GNP are ORR active with prominent reduction peak
acquired for Co3 O4 /GNP and Co3 O4 /CeO2 /GNP. The EPR spectra is occurring around 0.8 V versus RHE as shown in Figure 6a. The
presented in Figure 4. Most peaks in Co3 O4 /CeO2 /GNP are higher CVs and LSVs of Pt/C and GNP are shown in Figure S9 of Sup-
in intensity at g-value 2.34, depicting greater oxygen vacan- porting Information. The respective LSVs of the as-synthesized
cies and structural distortions. The more intense signals result catalysts at rotation rates 400–3600 rpm are shown in Figure
from the unpaired electrons present at the oxygen vacancy S10 of Supporting Information. Table S5 (Supporting Informa-
sites.[29–31] Broader EPR signals depict a higher degree of splitting tion) summarizes the onset potentials and current densities for
in Co3 O4 /CeO2 /GNP. The hyperfine splitting is more prominent ORR/OER.
in the case of Co3 O4 /CeO2 /GNP than in Co3 O4 /GNP. This also An overlay of the LSVs of the catalysts at 1600 rpm is shown
puts light on the fact that Co-sites in Co3 O4 /CeO2 /GNP and in Figure 6b with their respective current densities marked at
Co3 O4 /GNP are in different chemical environments. potentials 0.2 V, 0.4 V, and 0.6 V. Another plot of (i × iL )/(iL -
For in-depth information regarding oxidation states and crys- i) versus E is also presented in Figure 6c where i = current,
tal structure, XANES and EXAFS regions obtained from XAS were iL = limiting current, E = potential to provide a more correct
evaluated carefully. The XANES data are normalized using soft- comparison. This eliminates any error which might have come
ware ATHENA and the k2 -weighted EXAFS data were fitted using from residual ink drop cast or spillage beyond the effective
ARTEMIS.[32,33] geometric area of the GC-RDE.
Figure 5a reveals observable differences between the Co K- FromFigure 6b it is evident that all the studied catalysts
edge XANES features of the three standards ̶ Co, CoO, Co3 O4 and exhibit a skewed baseline below 0.4 V, except Pt/C. This is most
the as-synthesized catalysts Co3 O4 /CeO2 /GNP and Co3 O4 /GNP. plausibly assumed to be a characteristic feature of the GNP
The white line (1s → 4p) which appears around 7728 eV[34] of as observed from Figure S9c,d. The skewed baseline is some-
Co3 O4 /CeO2 /GNP has a positive shift compared to Co3 O4 /GNP what more pronounced in the case of CeO2 . So, this could also
(see Figure 5b). A white line is an indicative of a Laporte allowed be a characteristic feature of CeO2 . The skewed baseline which
transition (1s → 4p in this case). The shift in white line for starts appearing after an apparently short-lived plateau region
Co3 O4 /CeO2 /GNP toward higher energy (Figure 5b) indicates that at ∼0.5 V is indicative of extra components being reduced in
more energy is required by this catalyst in emitting a photo- addition to O2 . It is a common practice to compare the lim-

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Figure 5. (a) Overlay of XANES of three standards ̶ Co, CoO, Co3 O4 and the as-synthesized catalysts Co3 O4 /CeO2 /GNP and Co3 O4 /GNP. (b) White line region
and (c) pre-edge region of Co3 O4 /CeO2 /GNP and Co3 O4 /GNP. (d) k2 -weighted Fourier transform of Co K-edge EXAFS and their 1st shell fits obtained with
R = 1.2–3.4 Å. (e) Linear plot of edge energy versus oxidation states.

Table 1. Summary of 1st shell fitting of Co K-edge and the simulated 20 wt% Pt/C. Figure 6d shows how comparing limiting current
parameters like Co-ordination number (N), Bond-length (R), Debye-Waller densities at 0.2 V and 0.4 V (potential falling in the skewed
factor (σ 2 ), and inner potential shift (εo ). R-factor represents goodness of region) deceives in making the Co3 O4 /CeO2 /GNP catalyst appear
fit.
superior to that of 20 wt% Pt/C.
Catalysts Shell N R (Å) σ 2 (Å2 ) R-Factor Normalization of the limiting current density to the actual
Co3 O4 /CeO2 /GNP Co─O 12 1.953 ± 0.07 0.016 0.04 amount of metal-oxide is another way of expressing comparative
electrocatalysis. The mass- normalized activities (or mass spe-
Co─Co 12 3.360 ± 0.12 0.014
cific activities) are shown in Figure 6e which follows the order:
Co─Co 4 3.509 ± 0.12 0.006
Pt/C > Co3 O4 /CeO2 /GNP > Co3 O4 /GNP > CeO2 /GNP > GNP.
Co3 O4 /GNP Co─O 12 1.948 ± 0.07 0.018 0.08
The normalization method is explained in detail in the Sup-
Co─Co 12 3.350 ± 0.13 0.018
porting Information. The ECSA is the area of an electrode that
Co─Co 4 3.499 ± 0.13 0.009 is accessible to the electrolyte for charge transfer and stor-
age, and is considered to be an important feature of electrified
interfaces.[45] It is derived from CVs at different scan rates as
iting current densities at 0.2 V versus RHE.[37–44] However, we shown in Figure 6f and the derived CDL value is shown in
propose that comparing them at any potential below 0.5 V (say Figure 6g. The ECSAs and mass-specific ECSAs are in the order
0.2 V and 0.4 V in this case), will lead to erroneous interpreta- as shown in Figure 6h: Co3 O4 /CeO2 /GNP (239.3) > Co3 O4 /GNP
tion. Hence, the geometric current densities at 0.6 V (the most (219.9) > CeO2 /GNP (135.2). This decrease in ECSA could be corre-
appropriate region in this case) are considered as the limiting lated to the respective decrease in their current densities toward
current densities for comparison to ensure more precision in the ORR (see Table S5).
ORR study. In many cases, comparing the current densities at It is evident from Figure 6c that compared to commercial
potentials beyond the ORR plateau region might deceive one in Pt/C, the other catalysts exhibit slow kinetics. The kinetics of
interpreting a catalyst to be superior to the commercial standard these catalysts are further analyzed by employing Koutecky-

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Figure 6. (a) CVs of as-synthesized Co3 O4 /CeO2 /GNP, Co3 O4 /GNP and CeO2 /GNP under N2 and O2 -saturated 0.1 M KOH at scan rate 10 mVs−1 . (b) LSVs at
1600 rpm and current densities at 0.2 V, 0.4 V, and 0.6 V are marked. (c) Plot of (i × iL )/(iL -i) versus E. Potentials for each catalyst to reach the target ik are
marked. (d) Bar diagram representing current densities at potentials 0.2 V, 0.4 V, and 0.6 V. (e) Bar diagram representing mass specific activities at 0.6 V.
(f ) CVs of Co3 O4 /CeO2 /GNP taken at different scan rates from 5 to 60 mVs−1 and (g) corresponding slope CDL . (h) Bar diagram representing mass specific
ECSAs.

Levich (K-L) equation, assuming that K-L assumptions remain and an accelerated durability test (ADT). Following 10000 rounds
good in the mixed diffusion-kinetic region 0.5–0.75 V versus of the ADT, which involved cycling between 0.65 and 0.88 V at
RHE. The K-L plots are shown in Figure 7. Good linearity and 500 mV s−1 , the LSVs are compared in Figure 8a. The minimal
parallelism are observed for Co3 O4 /CeO2 /GNP, Co3 O4 /GNP and shift of 6 mV observed indicates that Co3 O4 /CeO2 /GNP could
CeO2 /GNP (Figure 7a–c). For GNP, parallelism is observed only up be a promising candidate when it comes to long-term stability
to 0.7 V (Figure 7d). The no. of electrons (n) transferred per mole and commercialization. The CA test (current versus time plot) is
of O2 reduced are carefully derived from the slopes of K-L plots presented in Figure S13b in the Supporting Information. This is
at potentials 0.5 V, 0.6 V, 0.7 V and 0.75 V, respectively. These are expressed in % of retention of current in Figure 8b. The current
shown in the bar diagram in Figure 7e. While for the other cat- retention of Co3 O4 /CeO2 /GNP is 87.6% compared to 72.5% for
alysts, 2.5 < n ≤ 3.5, for Co3 O4 /CeO2 /GNP 3.5 < n ≤ 4, which is Pt/C. The catalysts were also tested for their performance toward
close to that of the commercial standard 20 wt% Pt/C for a four- OER. Similar to their performance in ORR, Co3 O4 /CeO2 /GNP has
electron process (n = 4), indicating the superior performance of an earlier onset (1.64 V) than Co3 O4 /GNP and CeO2 /GNP which is
the mixed oxide catalyst. obvious from Figure 8c. The potential to reach 10 mA cm−2 (Ej10 )
The stability of the Co3 O4 /CeO2 /GNP was explored via a is a performance depicting parameter for OER activity. While the
chronoamperometric (CA) test, stepping the potential to 0.67 V, mixed oxide Co3 O4 /CeO2 /GNP has its Ej10 at 1.67 V, the other

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Figure 7. K-L plots for (a) Co3 O4 /CeO2 /GNP, (b) Co3 O4 /GNP, (c) CeO2 /GNP, (d) GNP, and (e) number of electrons (n) transferred in ORR in different potentials.

two catalysts do not reach 10 mA cm−2 up to 2.2 V versus RHE. nanofibers.[46] The bifunctionality index (E) for the catalyst is
The bifunctionality index is mostly expressed as the potential slightly lesser than or comparable to those of Co3 O4 − CeO2 /C
window between E(j10 ) for OER and E1/2 for ORR as shown in hybrid,[11] Co3 O4 /CeO2 @Co/N-CNF,[16] Co3 O4 -NC/N- rGO,[18] Oct-
Figure 8d and expressed as: E = Ej10 − E1/2 = 0.98 V. Co3 O4 /C,[40] Ag-CeO2 -Co3 O4 /C[14] and Co3 O4 @Pt/C nanofibers.[46]
As presented in Table 2, it is observed that the cur- From the above results and discussion, it is observed that,
rent catalyst Co3 O4 /CeO2 /GNP has an Eonset comparable the mixed oxide Co3 O4 /CeO2 /GNP exhibited a higher catalytic
to or slightly earlier than similar category of catalysts activity for both ORR and OER than Co3 O4 /GNP and CeO2 /GNP.
like Co3 O4 @Z67-N700@CeO2 ,[2] Co3 O4 − CeO2 /C hybrid,[11] This is attributed to the close contact of the two nonidentical
CoOx /CeO2 /RGO,[13] Ag-CeO2 -Co3 O4 /C,[14] Co3 O4 -NC/N- rGO[18] heterogeneous component oxides Co3 O4 /GNP and CeO2 /GNP
and Co3 O4 − CeO2 /KB.[47] Its half-wave potentials (E1/2 ) are that play complementary roles. The generation of a large
comparable to Co3 O4 − CeO2 /C hybrid,[11] Co3 O4 -NC/N- rGO[18] number of point defects, namely oxygen vacancies, enables
and Oct-Co3 O4 /C.[40] The overpotential (ƞ10 ) of the catalyst exposure of more active sites in Co3 O4 /CeO2 /GNP catalyst. The
is lesser than similar catalysts like Co3 O4 − CeO2 /C hybrid[11] generation of oxygen vacancies is believed to be a major factor
and Co3 O4 /CeO2 @Co/N-CNF,[16] whereas it is comparable to in inducing appropriate electronic changes that build up the
that of Co3 O4 -NC/N-rGO,[18] Oct-Co3 O4 /C[40] and Co3 O4 @Pt/C “synergistic effect” between the two oxides. The transition from

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Figure 8. (a) LSVs of Co3 O4 /CeO2 /GNP before and after 10000 CV cycles. (b) CA for current retention of Co3 O4 /CeO2 /GNP at potential 0.67 V versus RHE. (c)
LSVs of commercial standard RuO2 and the as-synthesized catalysts Co3 O4 /CeO2 /GNP, Co3 O4 /GNP and CeO2 /GNP at 1600 rpm toward OER, and (e)
bifunctionality index of Co3 O4 /CeO2 /GNP.

Table 2. Comparison of the performance recently reported Co3 O4 -based electrocatalysts performance toward ORR/OER in 0.1 M KOH with our catalysts.

Catalyst ORR OER References

Eonset /V E1/2 /V E(j10 )/Va) E/Vb) ƞ10 /mV

Co3 O4 /CeO2 /GNP 0.85 0.69 1.67 0.98 440 This work
Co3 O4 @Z67-N700@CeO2 0.82 1.58 0.70 350 [2]
Co3 O4 − CeO2 /C hybrid 0.85 0.69 1.72 1.03 520 [11]
CoOx /CeO2 /RGO 0.83 1.59 0.76 360 [13]
Ag-CeO2 -Co3 O4 /C 0.85 1.74 0.94 340 [14]
Co3 O4 /CeO2 @Co/N-CNF 0.88 1.84 1.09 570 [16]
Co3 O4 -NC/N- rGO 0.82 0.68 1.68 1.0 440 [18]
Oct-Co3 O4 /C 0.89 0.68 1.68 1.00 450 [40]
Co3 O4 @Pt/C nanofibers 0.90 1.67 0.93 442 [46]
Co3 O4 − CeO2 /KB 0.82 [47]

a) −2
Overpotential at 10 mAcm (ƞ10 ): E(j10 ) ̶ 1.23
b)
The bifunctionality index is mostly expressed as the potential window between E(j10 ) for OER and E1/2 for ORR: E/V [E(j10 )−E1/2 )]

Ce3+ to Ce4+ enables release of an electron which participates nature of Co3 O4 /CeO2 /GNP is believed to boost charge transfer
in the transition of Co3+ to Co2+ , thereby facilitating OER. On between the active crystalline counterpart Co3 O4 and GNP,
the reverse transition from Ce4+ to Ce3+ , the electron released thereby strengthening metal-support interactions.[48] This, in
from conversion of Co2+ to Co3+ which facilitates ORR. This can turn, also enhances stability and durability as evidenced from
be best visualized from Scheme 1. The proximity of the interface CA and ADT tests. Another plausible reason behind generation
of Co3 O4 and CeO2 makes this quick electronic transfer feasible. of such a semi-crystalline nature could be from the influence
The accessibility of active sites in Co3 O4 /CeO2 /GNP can also be of the mild base urea added during synthesis. This predica-
believed to be boosted by the higher average oxidation state ment is based on the generation of highly crystalline similar
of Co ions as evidenced by XAS (Figure 5e). The semi-crystalline CeO2 -based components where the precipitating agent used

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Scheme 1. A visual understanding of the plausible electronic synergy between Co3 O4 /GNP and CeO2 /GNP.

was NaOH.[9,15,35] Also, the crystallite sizes of those were greatly of the University of Southampton, for helping with some of the
larger than that reported in the present work. The synthesis data interpretation.
route allows intricate alteration of electronic levels in the mixed
Co3 O4 /CeO2 /GNP in a manner that boosts the electrocatalytic
activity of Co3 O4 in the mixed oxide without bringing any
significant changes in the core crystal structures as evidenced Conflict of Interests
by EXAFS. This aspect is presumed to play a role in preserving
the inherent electrocatalytic nature of Co3 O4 which is evidenced The authors declare no conflict of interest.
from the same Eonset,ORR values (Table S5 in the Supporting
Information) for Co3 O4 /GNP and Co3 O4 /CeO2 /GNP.
Data Availability Statement
4. Conclusions The data that support the findings of this study are available
from the corresponding author upon reasonable request.
CeO2 paired with active Co3 O4 /GNP boosts generation of oxy-
gen vacancy which in turn enhances ORR/OER performance. The
Keywords: Co3 O4 -CeO2 • Cyclic voltammetry • Oxygen evolu-
facile Ce4+ /Ce3+ redox shuttle aids in faster shuttle between tion • Oxygen reduction • Supported catalysts
Co3+ /Co2+ which then consequently aids in faster and more effi-
cient ORR and OER. Co3 O4 /CeO2 /GNP exhibits superior charge-
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