Materials Science in Semiconductor Processing 174 (2024) 108213

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Materials Science in Semiconductor Processing

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

Unlocking efficient methanol electro-oxidation in alkaline medium with

non-stoichiometric 3D sphere-like Cu3Mo2O9@CoMoO4 heterostructure
Y. Veera Manohara Reddy a, 1, Nipa Roy b, 1, J. Pundareekam Goud c, G. Madhavi d,
Munirah D. Albaqami e, Bathinapatla Sravani f, ***, Gutturu Rajasekhara Reddy g, *, Sang
Woo Joo g, **
a
Department of Chemistry, Sri Venkateswara College (University of Delhi), New Delhi, 110021, India
b
Department of Physics, Yeungnam University, Gyeongsan, 38541, Republic of Korea
c
Department of Physics, Koneru Lakshmaiah Education Foundation, Bowrampet, Hyderabad, 500043, Telangana, India
d
Electrochemical Research Lab, Department of Chemistry, Sri Venkateswara University, Tirupati, 517502, India
e
Department of Chemistry, College of Science, King Saud University, P.O. Box 2455, Riyadh, 11451, Saudi Arabia
f
Nanoelectrochemistry Lab, Department of Chemistry, Υogi Vemana University, Kadapa, 516005, India
g
School of Mechanical Engineering, Yeungnam University, Gyeongsan, 38541, Republic of Korea

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

Keywords: In order to unlock the full potential of direct methanol fuel cells (DMFCs), there is a pressing need for the
Heterostructure development of cost-effective catalysts that don’t rely on precious metals. Within this context, we have suc­
Non-stoichiometric cessfully synthesized a non-stoichiometric three-dimensional (3D) sphere-like Cu3Mo2O9@CoMoO4 hetero­
Sphere-like Cu3Mo2O9@CoMoO4
structure using a straightforward two-step hydrothermal process. A range of analytical techniques was utilized to
Electrocatalyst
explore the physical and chemical properties of this Cu3Mo2O9@CoMoO4 in comparison to their constituents’
Methanol electro-oxidation
parts, one-dimensional (1D) rod-like Cu3Mo2O9 and CoMoO4 microstructures. X-ray photoelectron spectroscopy
(XPS) was employed for the quantitative assessment of the non-stoichiometric composition of elements such as
Cu, Co, and Mo within the heterostructure. This outcome was additionally corroborated by data obtained
through analysis using field emission scanning electron microscopy (FESEM) with energy-dispersive X-ray
spectroscopy (EDS). The heterostructure showed highly porous characteristics and displayed a large surface area
of 42.54 m2 g− 1 compared to Cu3Mo2O9 and CoMoO4. This configuration yields a notably preeminent current
response for methanol electro-oxidation (MOR), reaching 202.8 mA cm− 2 at a scan rate of 50 mV s− 1 within the
voltage range of 0.0–0.7 V (vs. Hg/HgO). In comparison, both Cu3Mo2O9 and CoMoO4 exhibit lower methanol
electro-oxidation currents of 154.9 mA cm− 2 and 120 mA cm− 2, respectively. After examination by chro­
noamperometry for 10 h, the Cu3Mo2O9@CoMoO4 exhibited good stability performance. This research illustrates
that the synergistic effects between Cu3Mo2O9 and CoMoO4 within Cu3Mo2O9@CoMoO4 heterostructure can
significantly boost electrocatalytic capabilities. This enhancement opens extensive avenues for advancing cost-
effective electrocatalyst materials for the broader advancement of efficient MOR processes.

1. Introduction tools for storing and transforming energy [1]. Consequently, Direct
Methanol Fuel Cells (DMFCs) have garnered substantial global scientific
The gradual deterioration of our environment and the swift attention as a significant field of research [2]. Presently, commercially
exhaustion of finite energy resources are progressively affecting the available DMFCs predominantly rely on costly Pt-based materials as
everyday lives of individuals. This has sparked an escalating desire for catalysts for the anode, chosen for their outstanding catalytic capabil­
substitute energy sources, propelling the advancement of state-of-the-art ities. Nevertheless, the elevated expenses and vulnerability to

* Corresponding author.
** Corresponding author.
*** Corresponding author.
E-mail addresses: [email protected] (B. Sravani), [email protected] (G.R. Reddy), [email protected] (S.W. Joo).
1
These authors are contributed equally.

https://doi.org/10.1016/j.mssp.2024.108213
Received 14 November 2023; Received in revised form 1 February 2024; Accepted 4 February 2024
Available online 8 February 2024
1369-8001/© 2024 Elsevier Ltd. All rights reserved.
Y.V. Manohara Reddy et al. Materials Science in Semiconductor Processing 174 (2024) 108213

intermediates hinder the widespread integration of DMFCs into com­ include defect engineering [18], introducing heteroatoms through
mercial applications [3,4]. Hence, there is an immediate necessity to doping [19], constructing heterostructures [20], incorporating
investigate cost-efficient alternatives to catalysts based on precious conductive carbonaceous materials [21], and harnessing synergistic ef­
metals. This endeavor encompasses the exploration of alloys, metal fects arising from metal-support interactions [9]. Among these strate­
oxides, and hydroxides as potential catalysts, intending to attain both gies, the design of heterostructure configurations stands out as a novel
remarkable catalytic performance and affordability. approach to enhancing material performance for a wide range of ap­
Transition metal oxides hold great promise as substitutes for noble plications. These heterostructures have found utility in diverse fields
metals in DMFCs owing to their diverse oxidation states and inherent such as supercapacitors [22], lithium-ion batteries [23], gas sensing
stability [5]. Significant research efforts have been directed toward [24], and catalysis [25]. Moreover, heterostructure metal molybdates
exploring the potential of metal oxides for methanol electro-oxidation have emerged as a promising avenue for enhancing the efficiency of
[6,7]. Yet, their inherent semiconducting characteristics and elevated MOR catalysts. These materials possess distinctive attributes resulting
onset potential present obstacles to their practical application. However, from the synergistic interactions between distinct components of metal
the amalgamation of various transition metal oxides displays a syner­ oxides, leading to an elevated catalytic performance [2]. This design
gistic catalytic performance surpassing that of individual oxides [4]. approach leverages the amalgamation of dissimilar metal oxides, often
This combined approach offers favorable attributes such as enhanced characterized by differing electronic and catalytic properties, to
electrochemical activity, robust stability, and improved resistance to generate interfaces that facilitate the oxidation of methanol molecules
carbon monoxide [8]. Building upon these findings, the pursuit of [20]. Based on previous studies [22–25], it is widely acknowledged that
advanced catalysts for DMFCs remains a dynamic and evolving field, combining heterostructure can enhance electrochemical activity by
aiming to unlock the full potential of alternative energy solutions. accelerating reaction kinetics. Many researchers have demonstrated
In recent times, novel mixed metal oxides characterized by the improved catalytic capabilities for methanol oxidation using this
general formula MMoO4 (where M = Mn, Cu, Co, or Ni) at the nano- and approach [2,8,20]. Moreover, the presence of non-stoichiometry or va­
microstructural levels have garnered significant interest due to their cancies involving metal and oxygen atoms within metal oxides has a
distinctive physicochemical attributes [4,9]. These compounds and their substantial impact on enhancing their characteristics across various
derivatives have recently undergone exploration as electrocatalysts for applications [18,26,27]. These vacancies or deficiencies within the
various applications including the oxygen evolution reaction (OER), metal oxide crystalline structure can serve as active agents, sites for
oxygen reduction reaction (ORR), lithium-ion batteries, and super­ absorption, and sources of electron donation, leading to alterations in
capacitors (SCs) [10–13]. Despite this exploration, only limited studies electronic structure and charge transport [26]. Based on this backdrop,
have delved into the potential of metal molybdates as electrocatalysts it is preferable to design transition metal oxide heterostructures with
for the methanol oxidation reaction (MOR) in alkaline conditions non-stoichiometric materials to optimize the electrochemically active
[14–16]. Remarkably, they have exhibited remarkable electrochemical surface area and provide numerous active sites for enhanced catalytic
prowess when employed as catalytic electrodes, indicating a promising activity in MOR applications. As of our current knowledge, there are no
avenue for advancing the domain of catalysis. Building upon this published findings regarding the electrocatalytic characteristics of the
foundation, the pursuit of enhancing the capabilities of metal molyb­ non-stoichiometric sphere-like Cu3Mo2O9@CoMoO4 heterostructure for
dates as electrocatalysts continues to unfold, holding potential for MOR.
transformative contributions in the field. P. R. Jothi and co-researcher In our research, we have successfully synthesized a sphere-like het­
presented their findings on non-precious NiMoO4 nanorods incorpo­ erostructure known as Cu3Mo2O9@CoMoO4 using a straightforward
rated with carbon and graphene through a one-pot hydrothermal tech­ two-step hydrothermal method. We subjected this heterostructure to a
nique. Their study unveiled a peak current density of 49 mA cm− 2, comprehensive characterization process, exploring its physical and
observed at a scan rate of 50 mV s− 1 with a typical mass loading of ~3 chemical properties. To assess the potential of the electrocatalytic per­
mg cm− 2 for the working electrode [4]. Similarly, in a separate study, N. formance of the Cu3Mo2O9@CoMoO4 heterostructure in MOR was
Padmanabhan et al. developed a honeycomb-like β-NiMoO4-NF catalyst, investigated through electrochemical measurements. Notably, the
achieving a significant current density of 41.78 mA cm− 2 under the same Cu3Mo2O9@CoMoO4 heterostructure exhibited superior electrocatalytic
scan rate conditions with mass loading of ~2 mg cm− 2 [9]. Another activity compared to individual Cu3Mo2O9 or CoMoO4 components.
investigation conducted by N. Kumari et al. involved the synthesis of Impressively, a Chronoamperometry examination over 10 h demon­
mixed molybdates consisting of cobalt and nickel, employing a strated the enduring stability of Cu3Mo2O9@CoMoO4. This innovative
microwave-assisted co-precipitation method. Their efforts yielded an approach offers a promising avenue for addressing MOR utilizing a
impressive maximum current density of 164.5 mA cm− 2 [17]. Further­ catalyst-free of noble metals. The study underscores the remarkable
more, N. Padmanabhan and team contributed to the field by reporting synergistic effects between Cu3Mo2O9 and CoMoO4 within the
on the growth of nanocrystalline cobalt molybdate (CoMoO4) nano­ Cu3Mo2O9@CoMoO4 heterostructure, significantly amplifying its elec­
flakes directly onto carbon fiber cloth (CFC) via a straightforward hy­ trochemical prowess. This augmentation presents extensive possibilities
drothermal process, obviating the need for templates or surfactants. This for advancing cost-efficient electrocatalytic materials, thereby contrib­
CoMoO4/CFC composite displayed robust methanol electro-oxidation uting to the broader progression of efficient MOR processes.
performance, exhibiting a substantial current density of 25 mA cm− 2
at an exceptionally low onset potential of 0.38 V ’ [15]. Despite these 2. Experimental section
advancements, there are still many opportunities for enhancing the
MOR performance, particularly in terms of employing various strategies 2.1. Material synthesis
and the utilization of cost-effective catalysts. Nevertheless, the struc­
tural disparities and limited electrical conductivity exhibited by metal 2.1.1. Synthesis procedure of CoMoO4
molybdates impede their comprehensive exploitation in energy storage To synthesize CoMoO4, we began by dissolving 4 mmol of Co
and conversion devices. Hence, considerable research endeavors are (NO3)2⋅6H2O and 4 mmol of Na2MoO4⋅2H2O in 70 mL of deionized (DI)
imperative to unlock the catalyst material’s full potential for sustained water while subjecting the mixture to magnetic stirring. This process
applications over the long term. This can be realized through the resulted in a uniform solution, which was then transferred into a 100-mL
implementation of diverse strategies to modify metal molybdates. Teflon-lined stainless-steel autoclave. The autoclave was subsequently
In recent years, a variety of innovative approaches have emerged, heated to 180◦ C and maintained at this temperature for a duration of 12
focusing on modifying the electronic structures to enhance the inherent h. Following the completion of this reaction, the system was allowed to
catalytic capabilities of catalysts in the field of MOR. These methods naturally cool down to room temperature (RT). Once the reaction was

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Y.V. Manohara Reddy et al. Materials Science in Semiconductor Processing 174 (2024) 108213

Fig. 1. Comparison of (a) XRD profiles of CoMoO4 (pink), Cu3Mo2O9 (black), and Cu3Mo2O9@CoMoO4 heterostructure (blue) with standard JCPDS cards. (b) Raman
spectra of CoMoO4 (violet), Cu3Mo2O9 (orange), and Cu3Mo2O9@CoMoO4 heterostructure (magenta).

fully accomplished, the sediment that had settled at the bottom of the ultrasonication in a 1 M HCl solution, deionized water, and absolute
autoclave was meticulously collected. This collected precursor under­ ethanol for 10 min each, effectively eliminating the surface oxide layer.
went a rigorous washing procedure using DI water, followed by multiple Subsequently, the cleaned Ni foam was dried at 80◦ C for 3 h. Following
rinses with absolute ethanol to eliminate any undesirable impurities the cleaning steps, a mixture comprising the active material (Cu3Mo2O9,
(forming CoMo-based carbonate hydroxide precursor). Subsequently, CoMoO4, and Cu3Mo2O9@CoMoO4) PVDF (binder), and carbon black
the cleansed material was dried at 80◦ C for a period of 12 h. Finally, an (conductive material) in an 80:10:10 wt ratio was dispersed in a 0.5 mL
annealing process was carried out in an air environment at 400◦ C for 3 h, solution of NMP. The resulting slurry was drop-casted onto the prepared
resulting in the formation of rod-like CoMoO4 microstructures. Ni foam, covering a working area of 1 × 1 cm− 2, and subsequently dried
at 80◦ C for 10 h. To conclude, a pressure of 10 MPa was applied to form a
2.1.2. Synthesis procedure of Cu3Mo2O9 thin film of Cu3Mo2O9, CoMoO4, and Cu3Mo2O9@CoMoO4-coated Ni
The synthesis of Cu3Mo2O9 followed a procedure analogous to that of foams, forming the working electrodes. The loading of catalysts on
CoMoO4, with the sole variation being the substitution of Co electrodes was ~4 mg cm− 2.
(NO3)2⋅6H2O with Cu(NO3)2⋅6H2O as the precursor. All other conditions In contrast to the loadings of similar oxides on Ni or other substrates
and steps remained identical to the CoMoO4 synthesis process, ulti­ investigated in prior studies [4,9,15,17], a notably higher loading of the
mately resulting in the formation of rod-like Cu3Mo2O9 microstructures. oxide catalyst on Ni (i.e., 4 mg cm− 2) was employed and consistently
maintained.
2.1.3. Synthesis of Cu3Mo2O9@CoMoO4 heterostructure
To synthesize the hierarchical Cu3Mo2O9@CoMoO4 heterostructure,
a two-step hydrothermal approach was employed. Initially, the CoMo- 2.3. Material characterization
based carbonate hydroxide obtained previously was placed within a
100 mL autoclave. Alongside this, a reaction solution comprising 4 The supporting information section contains comprehensive details
mmol Cu(NO3)2⋅6H2O, 4 mmol Na2MoO4⋅2H2O, and 70 mL of DI water regarding the materials utilized in the synthesis, along with a thorough
was prepared. For the growth process investigation, the homogeneous physiochemical and electrocatalytic characterization of the hetero­
solution was introduced into a 100 mL autoclave, along with the CoMo- structure employed in this study.
based carbonate hydroxide, and heated to 160◦ C for 15 h. Following the
reaction, the mixture was allowed to naturally cool down to RT. Upon 3. Results and discussion
completion, the precipitate at the autoclave’s bottom was collected and
subjected to thorough washing using DI water, followed by multiple In Fig. 1(a), we presented the X-ray diffraction (XRD) patterns of the
rinses with absolute ethanol to eliminate any remaining nanoparticle Cu3Mo2O9@CoMoO4 heterostructure (blue), as well as Cu3Mo2O9
debris. The cleansed material was then dried at 80◦ C for 12 h. Ulti­ (black) and CoMoO4 (pink). The XRD patterns of Cu3Mo2O9 and
mately, the prepared powders were annealed at a rate of 2◦ C per minute CoMoO4 correspond to the standard XRD patterns of Cu3Mo2O9 in the
in an air environment, reaching 400◦ C, and held at this temperature for orthorhombic phase (JCPDS No: 01-070-2493) [28] and CoMoO4 in the
2 h. This process yielded the formation of the three-dimensional (3D) monoclinic phase (JCPDS No: 00-021-0868) [15], respectively. When
sphere-like Cu3Mo2O9@CoMoO4 heterostructure. Cu3Mo2O9 and CoMoO4 are combined, the XRD pattern of the hetero­
structure (blue) displays characteristic peaks from both Cu3Mo2O9 and
CoMoO4. The synthesized samples showed no signs of additional phases
2.2. Fabrication of electrodes or impurities, suggesting their purity and absence of any other phases.
All samples demonstrated a higher degree of crystallinity, with the
The commercially acquired Ni (2.5 × 1 cm− 2) foam served as the Cu3Mo2O9@CoMoO4 heterostructure exhibiting the highest crystal­
current collector for depositing the active electrode material (catalyst). linity, followed by Cu3Mo2O9 and CoMoO4 in decreasing order. For
The Ni foam underwent a cleaning process involving sequential CoMoO4, Cu3Mo2O9, and Cu3Mo2O9@CoMoO4, the dominant XRD

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Y.V. Manohara Reddy et al. Materials Science in Semiconductor Processing 174 (2024) 108213

Fig. 2. FESEM images and equivalent EDS spectrum with inset table of quantification results of CoMoO4 (a–c), Cu3Mo2O4 (d–f), and Cu3Mo2O9@CoMoO4 heter­
ostructure (g–i), FESEM image and corresponding elemental mapping of Cu3Mo2O9@CoMoO4 (j–m), TEM (n) and HRTEM (o) images of Cu3Mo2O9@CoMoO4
heterostructure.

peaks produced average crystallite sizes of about 27.21 nm, 22.62 nm, along with pristine Cu3Mo2O9 (orange) and CoMoO4 (violet). Fig. 1(b)
and 22 nm respectively according to Scherrer’s equation [26]. CoMoO4 shows the distinctive Raman bands in the CoMoO4 Raman spectra (vi­
> Cu3Mo2O9 > Cu3Mo2O9@CoMoO4 is the order in which the average olet) at 945, 886, 822, 375, and 337 cm− 1. The peak at 945 cm− 1 is
crystallite sizes of the pristine and heterostructure samples decrease. associated with the symmetric stretching vibration mode of oxygen
Interestingly, among the three samples, Cu3Mo2O9@CoMoO4 showed involved in doubly coordinated bonding within the Mo–O structure
the smallest average crystallite size. This might have happened because [13]. The bands observed at 886 and 822 cm− 1 can be attributed to the
of the interaction between Cu3Mo2O9 and CoMoO4, potentially gener­ asymmetric stretching vibration of oxygen within the O–Mo–O config­
ating nucleation and growth inhibition, and resulting in the formation of uration [29]. Furthermore, the bands located at 375 and 332 cm− 1 are
smaller crystallites in the Cu3Mo2O9@CoMoO4 material. Furthermore, associated with the symmetric stretching mode of the Co–O–Mo.
the absence of the − 311 peak in the XRD pattern of CoMoO4, following Notably, our findings are in excellent agreement with existing literature,
its loading onto Cu3Mo2O9@CoMoO4, can be ascribed to the interaction further confirming the formation of CoMoO4 [13,29]. In Fig. 1(b) shown
occurring between Cu3Mo2O9 and CoMoO4 during the loading process. in orange, the Raman spectra of Cu3Mo2O9 reveal characteristic Raman
This interaction may result in the formation of a heterostructure with a bands at 965, 941, 900, 867, 845, 819, 507, 372, and 337 cm− 1. The
distinct crystallographic structure or phase composition, causing shifts peak at 941 cm− 1 is indicative of the symmetric stretching modes of the
and merging of XRD peaks. Moreover, the loading process is likely to Mo–O bonds, while the peak at 965 cm− 1 likely corresponds to the vi­
induce strain, both uniform, and non-uniform, or introduce defects (as bration along the zigzag row of Mo– –O bonds in Cu3Mo2O9 [30].
discussed in the XPS part) in the crystal lattice of CoMoO4, thereby Additionally, the bands observed at 900, 867, 845, and 819 cm− 1 can be
influencing the XRD pattern. Fig. 1(b) displays a comparison of the attributed to the stretching modes of two connected Mo–O–Mo bonds,
Raman spectra of the Cu3Mo2O9@CoMoO4 heterostructure (Magenta), resulting from the linkage of oxygen (OMo2). The bands centered at 507,

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Y.V. Manohara Reddy et al. Materials Science in Semiconductor Processing 174 (2024) 108213

Fig. 3. XPS analysis of Cu3Mo2O9@CoMoO4 heterostructure. (a) Survey, (b) O 1s, (c) Cu 2p, (d) Mo 3d, and (e) Co 2p.

372, and 337 cm− 1 indicate the presence of Cu–O in Cu3Mo2O9 [31]. This microsphere is composed of many nanoparticles that have self-
Importantly, these findings are in excellent agreement with the existing assembled to form a spherical shape [26]. The surface of the micro­
literature, further confirming the formation of Cu3Mo2O9 [30,31]. Fig. 1 sphere was rough and highly porous in nature (Cf. BET section), as
(b) displays the Raman spectra of the Cu3Mo2O9@CoMoO4 hetero­ shown in the high-resolution FESEM image (Fig. 2 (h)). Hence, the
structure (colored in magenta) showcasing Raman bands at 966, 935, morphology was transformed into 1D microrods of pristine samples
895, 873, 847, 816, 505, 410, 369, and 311 cm− 1. The observed peaks in (CoMoO4 and Cu3Mo2O9) to 3D microsphere Cu3Mo2O9@CoMoO4 het­
the Raman spectra of the Cu3Mo2O9@CoMoO4 heterostructure are a erostructure sample.
combination of characteristic peaks from both Cu3Mo2O9 and CoMoO4 This transformation from 1D micro-rods of the pristine samples
due to the coexistence of these two materials in the heterostructure (CoMoO4 and Cu3Mo2O9) to the 3D microsphere of the heterostructure
structure. The merging of their respective vibrational modes upon het­ (Cu3Mo2O9@CoMoO4) is attributed to several factors [15,33].
erostructure formation leads to a composite Raman spectrum featuring
peaks from both Cu3Mo2O9 and CoMoO4 components [32]. This suc­ i. When CoMoO4 and Cu3Mo2O9 are combined to form the heter­
cessful heterostructure formation is evident from the appearance of ostructure material, there could be chemical interactions be­
these combined Raman bands of CoMoO4, and Cu3Mo2O9. tween the two components. These interactions can induce a
Fig. 2 displays the Field emission scanning electron microscopy change in the growth pattern and lead to the self-assembly of
(FESEM) images of CoMoO4, Cu3Mo2O9, and Cu3Mo2O9@CoMoO4 het­ nanoparticles into a 3D microsphere.
erostructure. Fig. 2 (a,b) and (d,e) show the FESEM images of CoMoO4 ii. The heterostructure of CoMoO4 and Cu3Mo2O9 could lead to
and Cu3Mo2O9, respectively. Both samples showed one-dimensional different crystal growth and nucleation mechanisms, favoring the
(1D) rod-like morphology in the microscale range. The High- formation of a 3D microsphere over 1D microrods.
resolution FESEM images (Fig. 2 (b) for CoMoO4 and Fig. 2(e) for iii. The formation of the hierarchical Cu3Mo2O9@CoMoO4 hetero­
Cu3Mo2O9 show the surface of the rods was smooth. The Cu3Mo2O9 structure involves bidirectional templating effects, where both
microrods exhibited larger than CoMoO4 microrods. With microrods of Cu3Mo2O9 and CoMoO4 components mutually influence each
the Cu3Mo2O9, exhibited particle-like morphology, and some of the other during the nucleation and growth processes, contributing to
particles were decorated on the microrods [24]. Fig. 2(g and h) depicts the observed 3D microsphere morphology.
the FESEM images of the heterostructure material, which exhibits a iv. The different surface properties of CoMoO4 and Cu3Mo2O9 can
completely different morphology when compared to CoMoO4 and influence the self-assembly behavior of nanoparticles, resulting in
Cu3Mo2O9 samples. The heterostructure showed three-dimensional (3D) the formation of the microsphere structure.
sphere-like morphology in the microscale range.

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Y.V. Manohara Reddy et al. Materials Science in Semiconductor Processing 174 (2024) 108213

Table 1
XPS outcomes for the Cu3Mo2O9@CoMoO4 heterostructure. The comparison of the relative atomic percentages (at%), and elemental ratios (i.e.; Cu/Mo, Co/Mo, and
Cu/Co) of heterostructure results obtained from XPS and FESEM-EDS.
Sample Peak binding energy (eV±0.5)/[FWHM (eV)]/(relative at (%))

O 1s Mo 3d Co 2p Cu 2p

O1 O2 O3 O4 Mo1 Mo2 Co1 Co2 Cu1 Cu2

Cu3Mo2O9@CoMoO4 529.5 530.0 530.7 531.7 231.3 234.48 780.7 [3.5] 795.8 933.2 [3.5] 952.9
[1.11] [1.11] [1.11] [1.11] [1.03] (1.97) (18.86)
(40.04) (10.74) (8.02) (5.31) (15.06)
Elemental at%
Element O Mo Cu Co Cu/Mo Co/Mo Cu/Co
Experimental Theoretical Experimental Theoretical Experimental Theoretical
SEM- 63.07 14.98 18.76 2.10 1.25 1 0.15 1 9 1
EDS
XPS 64.11 15.06 18.86 1.97 1.25 1 0.13 1 9 1

Therefore, the transformation from 1D micro rods to 3D micro­ Cu3Mo2O9@CoMoO4 heterostructure.

spheres in the Cu3Mo2O9@CoMoO4 heterostructure is a result of com­ In Fig. 3, the X-ray photoelectron spectroscopy (XPS) results of the
plex interactions between the two materials during the heterostructure Cu3Mo2O9@CoMoO4 heterostructure were presented. The survey spec­
process. These interactions can drive changes in crystal growth, nucle­ trum of Cu3Mo2O9@CoMoO4 displays noticeable peaks corresponding
ation, and self-assembly behavior, leading to the observed morpholog­ to Cu, Co, Mo, and O (Fig. 3(a)), providing strong evidence for the
ical transformation. The Energy Dispersive X-ray Spectroscopy (EDS) successful formation of the Cu3Mo2O9@CoMoO4 heterostructure.
spectra of CoMoO4 and Cu3Mo2O9, respectively, are shown in Fig. 2(c) The O 1s spectra (Fig. 3(b)), for the heterostructure and profile was
and (f). The spectra show that both materials contain necessary chem­ deconvoluted into four distinct peaks, categorized as O1–O4. The het­
ical elements. Precisely, CoMoO4 holds Mo, Co, and O elements, whereas erostructure displayed distinct peaks at approximately 529.5 eV (O1),
Cu3Mo2O9 comprises Mo, Cu, and O elements. The inset tables in Fig. 2 530.0 eV (O2), 530.7 eV (O3), and 531.7 eV (O4). These peaks were
(c) and (f) show the quantification results of the elemental atomic per­ attributed to different constituents within the heterostructure. Specif­
centages (at %) for CoMoO4 and Cu3Mo2O9, respectively. The Co/Mo ically, the O1 peak (~529.5 eV) and O2 peak (~530.0 eV) were asso­
ratio in CoMoO4 is approximately 1, which matches the theoretical ciated with metal-oxygen bonds (M − O, where M = Cu/Co/Mo) and
(stoichiometric) value of 1 for Co/Mo in CoMoO4. Similarly, the Cu/Mo lattice oxygen, respectively. The O3 peak (~530.7 eV) was linked to
ratio in Cu3Mo2O9 is also approximately 1, matching the theoretical defect sites characterized by lower oxygen coordination, while the O4
(stoichiometric) value of 1 for Cu/Mo in Cu3Mo2O9. This indicates that peak (~531.7 eV) was connected to water molecules adsorbed on the
both samples are nearly stoichiometric, with the elemental ratios in line surface of the heterostructure [13,36]. The Cu 2p spectra for the het­
with the expected values for the chemical composition of CoMoO4 and erostructure at the core level are shown in Fig. 3(c). The spin-orbit split
Cu3Mo2O9. The data presented in the inset of Fig. 2(i) illustrates the doublet with Cu 2p3/2 and 2p1/2 components is characterized by two
quantification results of elemental atomic percentages (at%) for distinct peaks. The peaks were seen with binding energies of 933.2 eV
Cu3Mo2O9@CoMoO4. In this analysis, the Cu/Mo ratio shows a signifi­ (Cu1) and 952.9 eV (Cu2), respectively demonstrating the oxidation
cant increase beyond the stoichiometry value (=1.25), while the Co/Mo state is Cu +2. For the heterostructure, the energy difference between
ratio is notably lower than the stoichiometry value (0.15). The theo­ the spin-orbit coupling of the two bands was approximately 20 eV,
retical stoichiometry value for both cases is expected to be 1. These which is consistent with the results from earlier studies [37]. In Fig. 3
findings indicate that the Cu3Mo2O9@CoMoO4 materials, in their cur­ (d), the core-level Mo 3d spectra of the heterostructure and two distinct
rent state, exhibit a considerable excess of Cu and a deficiency of Co [15, peaks represent the spin-orbit splitting of the Mo 3d5/2 and 3d3/2 states.
34]. Fig. 2(j-m) presents the FESEM image and corresponding elemental These peaks are identified at 231.3 eV (Mo1) and 234.5 eV (Mo2)
mapping of Cu3Mo2O9@CoMoO4. The inset image in Fig. 2(j) displays binding energies, indicative of Mo (VI) in its normal state within the
the FESEM image. The mapping images for Cu3Mo2O9@CoMoO4 reveal heterostructure. Notably, there is a consistent 3-eV difference in binding
a uniform distribution of the primary elements: Co (red, Fig. 2(j)), Cu energy between the Mo 3d5/2 and 3d3/2 states in both samples, aligning
(green, Fig. 2(k)), Mo (yellow, Fig. 2(l)), and O (cyan, Fig. 2(m)). It is with findings reported in the literature [13]. In Fig. 3(e), we present the
evident from the mapping images that the Co content is lower than that Co 2p spectra of the heterostructure, revealing two discernible peaks
of Cu, Mo, and O. The microstructure and self-assembly of the hetero­ corresponding to the Co 2p3/2 and Co 2p1/2 spin-orbit interactions.
structure material were examined using transmission electron micro­ These observed peaks at 780.7 eV (Co1) and 795.8 eV (Co2) in the
scopy (TEM) analysis. In Fig. 2(n), the TEM image displays the heterostructure are in alignment with previous research and affirm the
Cu3Mo2O9@CoMoO4 heterostructure, revealing the presence of nano­ presence of Co in a +2-oxidation state within the heterostructure [26].
particles, which serve as the fundamental building blocks for its Table 1 displays the evaluation of XPS results for the heterostructure
sphere-like morphology [35]. Fig. 2(O) shows a high-resolution TEM material in terms of peak binding energies, FWHM, relative atomic
image of the heterostructure, and from this image, we derived the percentages (at%), and elemental ratios (i.e.; Cu/Mo, Co/Mo, and Cu/
d-spacing values of the heterostructure. From the high-resolution TEM Co). The Cu/Mo ratio surpasses the stoichiometric value (=1.25), indi­
(HRTEM) image, three regions, namely R1, R2, and R3, were chosen for cating a significant increase, whereas the theoretical value for the
analysis. We determined the d-spacing values and corresponding lattice Cu3Mo2O9@CoMoO4 heterostructure is 1. Similarly, the Co/Mo ratio
planes for these regions. Specifically, the d-spacing values were calcu­ falls notably below the stoichiometric value (0.15), with the theoretical
lated as 0.334 nm (CoMoO4) for the R1 region and 0.351 nm value being 1 in the Cu3Mo2O9@CoMoO4 heterostructure. Additionally,
(Cu3Mo2O9) for the R3 region, with corresponding lattice planes iden­ the Cu/Co ratio exhibits a substantial increase beyond the stoichiometric
tified as (002) and (131), respectively. Additionally, we computed the value (9), while the theoretical value remains 1 for the Cu3Mo2O9@­
d-spacing values for two directions in the R2 region. The results showed CoMoO4 heterostructure. These XPS findings are consistent with the
d-spacing values of 0.326 (CoMoO4) nm and 0.287 nm (Cu3Mo2O9), FESEM-EDS results, suggesting that the as-prepared heterostructure
corresponding to the (− 112) and (122) crystallographic directions, material is Cu-excess and Co-deficient. The surplus of Cu found in the
respectively. These TEM images indicate the formation of Cu3Mo2O9@CoMoO4 heterostructure can be explained by the differing

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Y.V. Manohara Reddy et al. Materials Science in Semiconductor Processing 174 (2024) 108213

Fig. 4. N2 absorption-desorption isotherms of (a) Cu3Mo2O9, (b) CoMoO4, and (c) Cu3Mo2O9@CoMoO4 and their inset represents BJH pore-size distribution curves.
(d) Comparison table of textural properties of three samples.

ionic radii of Co in various oxidation states and spin states. Specifically, radii of 68.5 p.m. for the low-spin state and 75 p.m. for the high-spin
the ionic radii of Co+2 in its low-spin and high-spin states measure 79 p. state. In contrast, Cu+2 possesses an approximate ionic radius of 87 p.
m. and 88.5 p.m., respectively. On the other hand, Co+3 exhibits ionic m. The larger ionic radii of Co in certain charge states, especially Co+2

Fig. 5. CV curves at different scan rates of (a) CoMoO4, (b) Cu3Mo2O9, and Cu3Mo2O9@CoMoO4 heterostructure within the potential window of 0.0–0.7 V (Hg/
HgO). (d) The linear relationship plot of peak current density versus scan rate of three electrocatalysts.

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Y.V. Manohara Reddy et al. Materials Science in Semiconductor Processing 174 (2024) 108213

Fig. 6. (a) Comparison of CV curves of bare Ni foam, CoMoO4, Cu3Mo2O9, and Cu3Mo2O9@CoMoO4 in 1 M KOH without MeOH at 50 mV s− 1, (b) comparison of CV
curves of CoMoO4, Cu3Mo2O9, and Cu3Mo2O9@CoMoO4 in 1 M KOH with 1 M MeOH at 50 mV s− 1, (c) CV curves of Cu3Mo2O9@CoMoO4 at different scan rates in 1
M KOH with 1 M MeOH, (d) various MeOH concentrations of Cu3Mo2O9@CoMoO4 at 50 mV s− 1, (e) CV curves of the Cu3Mo2O9@CoMoO4 electrode in the (1 M
KOH + 1 M MeOH) electrolyte at 10 mV s− 1 for different cycles, and (f) the Nyquist plots of CoMoO4, Cu3Mo2O9, and Cu3Mo2O9@CoMoO4 in 1 M KOH with 1
M MeOH.

and Cu+2, are less energetically favorable, leading to some Co deficits substantial contact area between the active materials and electrolytes
within the crystal lattice of the heterostructure [34]. It is worth noting [26]. Additionally, the larger pores within the Cu3Mo2O9@CoMoO4
that the presence of various Co charge states, coupled with Cu excess and facilitate the ingress of electrolytes with minimal resistance, enhancing
Co deficiencies, establishes a redox-rich environment within the their permeation into the active material. This advantageous feature
Cu3Mo2O9@CoMoO4 heterostructure. This unique environment signifi­ leads us to anticipate superior electrocatalytic performance results from
cantly enhances its electrochemical properties for MOR. the sphere-like morphology of the synthesized Cu3Mo2O9@CoMoO4
The N2 adsorption-desorption isotherm of the three samples is pre­ [35].
sented in Fig. 4. As depicted in Fig. 4 (a-c), it is evident that the Furthermore, the pore size distribution, determined through the
Cu3Mo2O9, CoMoO4, and Cu3Mo2O9@CoMoO4 exhibit characteristics Barrett–Joyner–Halenda (BJH) method and corresponding curves were
consistent with a type IV isotherm, closely resembling the typical presented in their inset in Fig. 4 (a-c), reveals that most pores in all the
behavior seen in mesoporous materials [38]. A summary of the results samples fall within the size range of 2–50 nm. This unequivocally con­
for all the synthesized samples is provided in Table of Fig. 4(d). Notably, firms that the synthesized materials exhibit mesoporous characteristics
the Cu3Mo2O9@CoMoO4 heterostructure stands out with the largest [39]. Lastly, the average pore diameters for Cu3Mo2O9, CoMoO4, and
surface area and pore volume, measuring 42.54 m2 g− 1 and 0.08 cm3 Cu3Mo2O9@CoMoO4 are calculated to be 24.27, 8.85, and 33.71 nm,
g− 1, respectively. This substantial surface area in the Cu3Mo2O9@Co­ respectively.
MoO4 translates to an abundance of sites and channels, fostering a

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Y.V. Manohara Reddy et al. Materials Science in Semiconductor Processing 174 (2024) 108213

3.1. Electrocatalytic performance of MOR these species with higher oxidation states contributed to the methanol
oxidation process simultaneously undergoing reduction to lower
The electrocatalytic MOR performance of the Cu3Mo2O9, CoMoO4, oxidation states as the potential was progressively swept in the forward
and Cu3Mo2O9@CoMoO4 electrocatalysts was assessed utilizing 1 M of direction [40,42]. The suppression of the oxidation peaks during the
KOH without and with methanol (MeOH) at RT. The cyclic voltammetry forward sweep can be attributed to the inhibitory influence stemming
(CV) profiles presented in Fig. 5(a-c) illustrate the electrochemical re­ from the methanol oxidation [41]. Notably, CuOOH, CoOOH, and
sponses of CoMoO4, Cu3Mo2O9, and the Cu3Mo2O9@CoMoO4 electro­ MoOOH were identified as the key active species facilitating methanol
catalysts. These responses were recorded at various scan rates ranging oxidation. Cu3Mo2O9@CoMoO4 demonstrates significantly elevated
from 5 to 100 mV s− 1, within the potential window of 0.0–0.7 V (versus anodic current density or response (202.8 mA cm− 2 at 50 mV s− 1; Fig. 6
Hg/HgO), under conditions of 1 M KOH electrolyte without MeOH. All (b)) in stark contrast to Cu3Mo2O9 (154.9 mA cm− 2) and CoMoO4 (120
three electrocatalysts display a strong pair of well-defined redox peaks mA cm− 2). This enhanced electrocatalytic performance of the hetero­
in their CV curves, indicative of reversible faradaic redox reactions structure is ascribed to the synergistic interplay among the distinct
accompanying the M-O/M-O-OH (where M = Cu, Mo, or Co) related to valence states of Cu, Co, and Mo [42]. Fig. 6(c) exhibits the CV curves of
OH− anions [35]. Notably, the CV curve shapes for all three electro­ the Cu3Mo2O9@CoMoO4 heterostructure over a range of scan rates
catalysts remain consistent despite varying scan rates from 5 to 100 mV spanning from 5 to 100 mV s− 1 within the potential window of 0.0–0.7 V
s− 1, underscoring the enhanced mass transport facilitated by the elec­ (Hg/HgO). Notably, with the increasing scan rate from 5 to 100 mV s− 1,
trocatalysts [26]. It is worth noting that the cathodic and anodic peaks the heterostructure electrocatalyst demonstrates a remarkable rise in
shift to lower and higher potentials, respectively, as scan rates increase. anodic current density. This augmentation in anodic current density at
This phenomenon can be ascribed to internal resistance and polarization higher scan rates can be attributed to the heightened electrochemical
effects that take place during the faradaic process [13,35]. In Fig. 5(d), kinetics and enhanced charge transfer mechanisms inherent to the
the linear plot illustrates the relationship between redox peak current Cu3Mo2O9@CoMoO4 heterostructure catalyst. The accelerated electro­
density and scan rate. These plots suggest that the diffusion-controlled chemical reactions at the electrode-electrolyte interface with increased
process was the prevailing in the MOR process [36]. scan rates facilitate a greater rate of redox processes and electron
In Fig. 6(a), the comparison CV profiles of the bare Ni foam, transfer [40]. This phenomenon is a typical indicator of enhanced cat­
Cu3Mo2O9, CoMoO4, and Cu3Mo2O9@CoMoO4 electrocatalysts tested in alytic activity and efficient utilization of the active sites within the
a 1 M KOH without methanol concentration within the potential win­ Cu3Mo2O9@CoMoO4 heterostructure material. Fig. 6(d) presents a bar
dow of 0.0–0.7 V (Hg/HgO) at 50 mV s− 1 scan rate. The electrochemical graph displaying the Cu3Mo2O9@CoMoO4 heterostructure electro cat­
behavior of the bare Ni foam is characterized by either minimal or alyst’s current density plotted against varying methanol concentrations
noticeably lower current response when contrasted with the other while maintaining a constant current density of 50 mV s− 1. The recorded
electrocatalysts. This indicates that the primary charge storage mecha­ current responses for methanol concentrations of 0.0 M, 0.5 M, 1.0 M,
nisms are attributed to the Cu3Mo2O9, CoMoO4, and Cu3Mo2O9@Co­ and 2.0 M in a 1 M KOH were 52.9, 153.4, 220.3, and 235.7 mA cm− 2,
MoO4 electrocatalysts. Notably, the enclosed area within the CV curve of respectively. Consequently, the heightened peak current response
Cu3Mo2O9@CoMoO4 heterostructure electrocatalyst surpasses that of detected upon introducing 1.0 M or 2.0 M methanol to a 1 M KOH can be
CoMoO4 and Cu3Mo2O9. This enhancement is possibly attributed to the attributed to improved accessibility of fuel molecules, improved charge
robust synergy between multiple metal cations, namely Cu, Mo, and Co transfer efficiency, and greater availability of reactants for the electro­
[37]. In comparison to the pristine CoMoO4 and Cu3Mo2O9, the chemical reactions occurring at the surface of the electrocatalyst [42].
Cu3Mo2O9@CoMoO4 exhibits significantly heightened response current Furthermore, the electrocatalytic stability of the Cu3Mo2O9@Co­
and a larger enclosed area, indicative of superior electrocatalytic per­ MoO4 heterostructure catalyst was investigated by CV test for 1000
formance. Fig. 6(b) illustrates a comparison among the CV profiles of cycles. In Fig. 6(e), the CV curves acquired during the initial cycle and
CoMoO4, Cu3Mo2O9, and Cu3Mo2O9@CoMoO4 electrocatalysts, ac­ the 1000th cycle are depicted, employing a scan rate of 10 mV s− 1.
quired at a scan rate of 50 mV s− 1 after the addition of 1 M methanol to Following 1000 cycles, a current density retention ratio of 66.2% is
the 1 M KOH. The introduction of methanol into the electrolyte triggers achieved. Nevertheless, the current density rebounded to 97.6% upon
notable alterations in the CV curves of as-synthesized three catalysts. immersing the electrode into a fresh blend of electrolyte and methanol
The catalysts exhibit a swift surge with the current response, indicative (1 M KOH + 1 M MeOH). Consequently, the decline in current density
of their catalytic engagement in the MOR. Conventionally, it is believed after the cycling test primarily stems from the consumption of methanol
that in heterogeneous reactions, electrocatalysts adsorb reactants (in during the cycling process. The decay in current density might be
this case, MeOH) onto their surfaces, leading to the formation of inter­ attributed to methanol utilization during cyclic tests and proximate in­
mediate products before transforming the reactants into final products termediate species formation during electrochemical reactions [40]. All
[40]. these findings highlighted the potential of the Cu3Mo2O9@CoMoO4
This underscores the importance of the anodic peaks’ features in the heterostructure to function as an incredibly stable and extremely reac­
forward reaction, as they influence the electrocatalytic performance of tive catalyst for the oxidation of methanol. Fig. S1(a) shows the Nyquist
the three catalysts in MOR. Meanwhile, the cathodic peaks indicate the plot of the CoMoO4, Cu3Mo2O9, and Cu3Mo2O9@CoMoO4 catalysts in
oxidation of intermediate species generated during the forward reaction the 1 M KOH measure in the frequency range of 1 MHz TO 100 mHz. The
[41]. The following equations can clarify the potential catalytic mech­ zoom-in view of EIS curves was presented in the inset of Fig. S1(a) at the
anism [40,41]: high-frequency part. The acquired EIS curves were matched with an
equivalent electronic circuit, depicted in Fig. S1(b). This circuit contains
CuOOH + CH3OH + 1.25 O2 → Cu(OH)2 + CO2 + 1.5 H2O (1) three main elements: charge-transfer resistance (Rct), series resistance
CoOOH + CH3OH + 1.25 O2 → Co(OH)2 + CO2 + 1.5 H2O (2) (Rs), and Warburg resistance (W). These elements play crucial roles in
elucidating the underlying electrochemical processes [26]. To delve
2 MoOOH + 2 CH3OH + 2.5 O2 → 2 Mo(OH)2 + 2 CO2 + 3 H2O (3) further into the specifics, series resistance (Rs) reflects the overall
resistance of the entire electrochemical system, encompassing contri­
At the initial stage, the metal atoms of Cu, Co, and Mo within the
butions from electrolytes, electrodes, and connections. Charge-transfer
heterostructure and pristine electrocatalysts structure underwent
resistance (Rct) offers insights into the rate of electron transfer at the
oxidation, leading to the elevation of their valence states within the KOH
electrode-electrolyte interface, essentially capturing the kinetics of the
electrolyte [42]. This process yielded the formation of CuOOH, CoOOH,
redox reaction [27]. Warburg resistance (W) is indicative of diffusion
and MoOOH species (as depicted in Equations (1)–(3)). Subsequently,
limitations, providing information about the mass transport processes

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Y.V. Manohara Reddy et al. Materials Science in Semiconductor Processing 174 (2024) 108213

Fig. 7. (a) LSV curves of Cu3Mo2O9 and CoMoO4, Cu3Mo2O9@CoMoO4 electrocatalysts in the presence of 1 M KOH + 1 M MeOH at the scan rate of 50 mV s− 1. (b)
CA profile of the Cu3Mo2O9@CoMoO4 heterostructure catalyst in the 1 M KOH + 1 M MeOH.

within the electrode-electrolyte system [13]. For a more comprehensive forms interfaces that play a crucial role in facilitating the oxidation of
understanding of these components, we refer interested readers to our methanol molecules. The intricate interplay between Cu3Mo2O9 and
prior publication where we extensively expound upon their roles and CoMoO4 in the electrocatalytic system leads to improved performance,
significance in our research context [13,26]. Furthermore, when as evidenced by the favorable changes in current density and onset
examining the catalysts under investigation - CoMoO4, Cu3Mo2O9, and potential [6,9]. Using Chronoamperometry (i-t) curves, the stability of
Cu3Mo2O9@CoMoO4 -their respective Rs/Rct/W values present valuable the Cu3Mo2O9@CoMoO4 catalyst for the electro-oxidation of methanol
insights. The values for these catalysts are as follows: 0.83 Ω/0.76 was further investigated. This experiment was conducted in the presence
Ω/27.93 Ω s− 1/2, 0.99 Ω/1.54 Ω/319.3 Ω s− 1/2 and 0.91 Ω/0.56 of 1 M KOH +1 M MeOH for a duration of 10 h, as depicted in Fig. 7(b).
Ω/135.2 Ω s− 1/2. These value representations encapsulate the intricate In the initial moments, due to rapid polarization, there was a brief
interplay of the resistances and highlight the distinctive electrochemical decrease in current density lasting only a few seconds. This phenomenon
behaviors of the catalysts in our study. Among all, the heterostructure might be explained by the accumulation of intermediate products on the
catalysts showed lower Rct values compared to others. Fig. 6(f) illus­ electrode surface which are created during the adsorption and desorp­
trates the Nyquist plot portraying the electrochemical behavior of the tion of methanol, which would essentially poison the electrocatalyst
CoMoO4, Cu3Mo2O9, and Cu3Mo2O9@CoMoO4 catalysts in the presence [40,43]. However, the electrocatalysts exhibited remarkable stability
of a 1 M KOH + 1 M MeOH. To provide a closer examination of the EIS throughout the entire 10-h duration. This extended stability indicates
profiles at the high-frequency region, a magnified inset within Fig. 6(f) the catalyst’s exceptional performance as an electrocatalyst for meth­
presents a zoomed-in view of the curves. In the electrolyte composition anol oxidation.
of 1 M KOH +1 M MeOH, distinct electrochemical responses are The sphere-like Cu3Mo2O9@CoMoO4 heterostructure presents
observed for the CoMoO4, Cu3Mo2O9, and Cu3Mo2O9@CoMoO4 cata­ several advantages over other heterostructures or other related studies,
lysts. The corresponding Rs/Rct/W values for these catalysts are as fol­ making it a promising candidate for enhancing electrocatalytic perfor­
lows: 1.12 Ω/4.38 Ω/23.3 Ω s− 1/2 for CoMoO4, 1.09 Ω/1.2 Ω/298.5 Ω mance in MOR applications. Here are some key advantages supported by
s− 1/2 for Cu3Mo2O9, and 1.07 Ω/0.05 Ω/68.2 Ω s− 1/2 for Cu3Mo2O9@­ experimental evidence.
CoMoO4. Among the three catalysts investigated in the 1 M KOH +1 M
MeOH electrolyte, the lowest resistance values are observed for the i. The Cu3Mo2O9@CoMoO4 heterostructure exhibited a large sur­
Cu3Mo2O9@CoMoO4 heterostructure electrocatalyst. These lower face area of 42.54 m2 g− 1, surpassing individual Cu3Mo2O9 and
resistance values may indicate better electrochemical performance or CoMoO4 microstructures. This is crucial for MOR applications as
more efficient charge transfer characteristics for Cu3Mo2O9@CoMoO4 a larger surface area provides more active sites for electro­
under these experimental conditions. Moreover, the Cu3Mo2O9@Co­ chemical reactions, leading to improved catalytic performance.
MoO4 catalyst demonstrates Rs/Rct/W values of 1.19 Ω/0.25 Ω/80.6 Ω ii. The research emphasizes the synergistic interactions between
s− 1/2 following 1000 CV cycles. Cu3Mo2O9 and CoMoO4 within the heterostructure. The combi­
After undergoing a series of 1000 CV cycles, an evident alteration in nation of dissimilar metal oxides with distinct electronic and
Rs value is observed, accompanied by marginal adjustments in Rct value. catalytic properties creates interfaces that facilitate the oxidation
Concurrently, a slight reduction in the slope of the vertical line in the of methanol molecules. This synergistic effect is demonstrated by
lower frequency range is discerned. These observations collectively the notably preeminent current response for methanol electro-
imply heightened conductivity, commendable electrocatalytic perfor­ oxidation (MOR), reaching 202.8 mA cm− 2 at a scan rate of 50
mance, and remarkable stability of the Cu3Mo2O9@CoMoO4 hetero­ mV s− 1.
structure electrocatalyst [42]. iii. The Cu3Mo2O9@CoMoO4 heterostructure demonstrated good
Fig. 7(a) shows the linear sweep voltammetry (LSV) measurements stability performance during the Chronoamperometry examina­
of Cu3Mo2O9 and CoMoO4, Cu3Mo2O9@CoMoO4 electrocatalysts in the tion for 10 h. This indicates its potential for sustained applica­
presence of 1 M KOH + 1 M MeOH at the scan rate of 50 mV s− 1. tions over time, a critical factor for practical use in fuel cells.
Remarkably, the Cu3Mo2O9@CoMoO4 electrocatalysts demonstrated a iv. The synthesis of the Cu3Mo2O9@CoMoO4 heterostructure was
significantly higher current density and a lower onset potential when achieved through a straightforward two-step hydrothermal pro­
compared to the individual Cu3Mo2O9 and CoMoO4 counterparts. This cess, highlighting its cost-effective production compared to cat­
observed enhancement can be attributed to the synergistic interactions alysts relying on precious metals. This addresses the pressing
taking place between Cu3Mo2O9 and CoMoO4 within the hetero­ need for affordable alternatives in the development of catalysts
structure. The heterostructure, resulting from the combination of dis­ for direct methanol fuel cells (DMFCs).
similar metal oxides with unique electronic and catalytic properties,

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Y.V. Manohara Reddy et al. Materials Science in Semiconductor Processing 174 (2024) 108213

Table 2
Comparison of MOR performance of Cu3Mo2O9@CoMoO4 heterostructure with findings from other relevant studies.
Synthesis method Methanol (M) Current density (mA cm− 2) Ref.
Catalyst

CuCoMnO4/CuO Hydrothermal 1 145.7 [42]

(Ni–Cu) sulfide/MnO2 Hydrothermal 1 70 [44]
Co9S8@MoS2 One-pot synthesis 0.5 121.4 [45]
Cu–O|Cu3P CVD 1 232.5 [46]
NF/Co3O4/NiCo2O4 Hydrothermal 0.5 140 [47]
Ni/NiO Interface engineering 1 79.50 [48]
Cu/NiCu NWs/C One-pot strategy 1 34.90 [49]
Ni–MgO/C Electro-deposition 1 192 [50]
Cu(OH)2–CuO/Cu Anodization method 0.5 60.2 [51]
Co3O4/NiO Electro-deposition 0.5 50 [52]
1
Pt1/RuO2 Impregnation-adsorption method 1 mA mg− 6766 [53]
Pt/MnCo2O4-NG Self-assembly process 1 1508.3 [54]
Rh/SWCNH Solvothermal 1 784 [55]
CoMoO4 Hydrothermal 1 120 Current work
Cu3Mo2O9 154.9
Cu3Mo2O9@CoMoO4 202.8

v. In comparison to 1D rod-like Cu3Mo2O9 and CoMoO4 micro­ Declaration of competing interest

structures, the Cu3Mo2O9@CoMoO4 heterostructure exhibited
notably superior methanol electro-oxidation currents, further The authors affirm that they do not possess any recognized con­
supporting its enhanced electrocatalytic capabilities. flicting financial interests or personal relationships that might have
seemed to exert an influence on the research presented in this work.
Furthermore, Table 2 presents a comparative analysis of the
Cu3Mo2O9@CoMoO4 heterostructure’s efficiency in MOR processes Data availability
alongside findings from similar studies. Notably, the current density
values obtained are higher than those reported in other works. This Data will be made available on request.
observation leads to a clear inference that the sphere-like
Cu3Mo2O9@CoMoO4 heterostructure distinguishes itself through its Acknowledgments
expansive surface area, synergistic interactions between its components,
stability, and cost-effectiveness. These attributes position it as a prom­ The funding for this research was provided by the National Research
ising and practical choice for the advancement of economical electro­ Foundation of Korea under Grant NRF-2019R1A5A8080290. This work
catalytic materials, effectively addressing the challenges associated with was also partially funded by the Researchers Supporting Project Number
MOR processes in DMFCs. (RSP2024R267) King Saud University, Riyadh, Saudi Arabia.

4. Conclusions Appendix A. Supplementary data

A heterostructure of Cu3Mo2O9@CoMoO4 in a sphere-like configu­ Supplementary data to this article can be found online at https://doi.
ration was synthesized using a two-step hydrothermal treatment, fol­ org/10.1016/j.mssp.2024.108213.
lowed by annealing in an air atmosphere for a duration of 2 h. The
alterations in morphology and composition/non-stoichiometry during
Supporting Information
the process of forming the heterostructure were investigated. The
resulting Cu3Mo2O9@CoMoO4 exhibited a substantial surface area of
This section provides details regarding chemicals, material charac­
42.54 m2 g− 1, displaying heightened catalytic efficacy in the electro-
terization, and electrochemical measurements, including methanol
oxidation of methanol and remarkable stability over prolonged pe­
electro-oxidation. It also includes a comparison of Nyquist plots in a 1 M
riods under alkaline conditions. The exceptional electrochemical per­
KOH solution with and without methanol for three different electro­
formance is primarily ascribed to the considerable specific surface area,
catalysts. Additionally, an inset offers a closer look at the high-frequency
evident bimetallic synergy, and the formation of a three-dimensional
portion of the plots, along with information about the equivalent elec­
sphere-like structure within the heterostructure.
tronic circuit used for fitting the Nyquist plots.
CRediT authorship contribution statement
References
Y. Veera Manohara Reddy: Writing – original draft, Methodology,
[1] Y. Yu, B. Yang, Y. Wang, X. Shen, X. Hu, Low-temperature liquid phase synthesis of
Investigation, Data curation, Conceptualization. Nipa Roy: Writing – flower-like NiCo2O4 for high-efficiency methanol electro-oxidation, ACS Appl.
original draft, Software, Investigation. J. Pundareekam Goud: Soft­ Energy Mater. 3 (2020) 9076–9082, https://doi.org/10.1021/acsaem.0c01461.
ware, Formal analysis. G. Madhavi: Formal analysis. Munirah D. [2] G. Wang, X. Xie, X. Cui, J. Liu, L. Jiang, Photoinduced Pt/BiVO4/Bi2O3
heterostructures for methanol oxidation and new insights on the photo-/
Albaqami: Software, Investigation, Formal analysis. Bathinapatla electrocatalysis coupling mechanism, ACS Sustainable Chem. Eng. 9 (2021)
Sravani: Supervision, Software, Investigation, Data curation, Concep­ 4271–4281, https://doi.org/10.1021/acssuschemeng.1c00764.
tualization. Gutturu Rajasekhara Reddy: Writing – review & editing, [3] B. Dong, W. Li, X. Huang, Z. Ali, T. Zhang, Z. Yang, Fabrication of hierarchical
hollow Mn doped Ni(OH)2 nanostructures with enhanced catalytic activity towards
Validation, Supervision, Data curation, Conceptualization. Sang Woo electrochemical oxidation of methanol, Nano Energy 55 (2019) 37–41, https://doi.
Joo: Writing – review & editing, Supervision, Resources, Funding org/10.1016/j.nanoen.2018.10.050.
acquisition, Formal analysis. [4] P. Raja, S. Kannan, G. Velayutham, Enhanced methanol electro-oxidation over in-
situ carbon and graphene supported one dimensional NiMoO4 nanorods, J. Power
Sources 277 (2015) 350–359, https://doi.org/10.1016/j.jpowsour.2014.11.137.
[5] M.J.S. Mohamed, M.A. Gondal, A.M.I. Surrati, M.A. Almessiere, Facile synthesis of
surface oxygen vacancy and Ti3+ defects in SrTiO3 perovskite coupled g-C3N4

11
Y.V. Manohara Reddy et al. Materials Science in Semiconductor Processing 174 (2024) 108213

decorated with Au ternary nanocomposites for enhancing electrocatalytic activity [28] N.F. Dummer, Z. Sodiq-Ajala, D.J. Morgan, T.E. Davies, Investigating the
from acidic and natural seawater conditions, Int. J. Hydrogen Energy 54 (2024) preparation of Cu3Mo2O9 as a photocatalyst, Catal. Commun. 163 (2022) 106414,
1436–1448, https://doi.org/10.1016/j.ijhydene.2023.12.009. https://doi.org/10.1016/j.catcom.2022.106414.
[6] R.S. Amin, S. Siracusano, V. Baglio, A. Stassi, A.S. Arico, Metal oxide promoters for [29] F. Liu, Y. Yang, S. Li, T. Chen, H. Long, H. Wang, M. Liu, Multi-dimensional CuO
methanol electro-oxidation, Int. J. Hydrogen Energy 39 (2014) 9782–9790, nanorods supported CoMoO4 nanosheets heterostructure as binder free and high
https://doi.org/10.1016/j.ijhydene.2014.04.100. stable electrode for supercapacitor, J. Mater. Sci. Mater. Electron. 29 (2018)
[7] X. Zhang, W. Hao, W. Ruan, B. Ma, G. Cheng, S. Shi, L. Wang, Z. Li, D. Wang, 10353–10361, https://doi.org/10.1007/s10854-018-9092-2.
F. Teng, A win-win strategy of wastewater recycling and treatment: synchronous [30] B. Saravanakumar, G. Ravi, R. Yuvakkumar, V. Ganesh, R.K. Guduru, Synthesis of
hydrogen production and norfloxacin degradation, Mater. Today Sustain. 22 polyoxometalates , copper molybdate (Cu3Mo2O9) nanopowders , for energy
(2023) 100346, https://doi.org/10.1016/j.mtsust.2023.100346. storage applications, Mater. Sci. Semicond. Process. 93 (2019) 164–172, https://
[8] E. Sadeghi, S. Chamani, E. Erdem, N.S. Peighambardoust, U. Aydemir, NiMo/ doi.org/10.1016/j.mssp.2019.01.002.
CoMoO4 heterostructure with confined oxygen vacancy for active and durable [31] S. Mehta, S. Kumaravel, S. Jha, M. Yen, S. Kundu, Impacts of structure-directing
alkaline hydrogen evolution reaction, ACS Appl. Energy Mater. 6 (2023) agents on the synthesis of Cu3Mo2O9 for flexible lignin-based supercapacitor
7658–7671, https://doi.org/10.1021/acsaem.3c01146. electrodes, J. Compos. Sci. 7 (2023) 155, https://doi.org/10.3390/jcs7040155.
[9] N. Padmanathan, H. Shao, K.M. Razeeb, Honeycomb micro/nano-architecture of [32] K.H. Shin, M. Seo, S. Pak, A. Jang, Observation of strong interlayer couplings in
stable β-NiMoO4 electrode/catalyst for sustainable energy storage and conversion WS2/MoS2 heterostructures via low-frequency Raman spectroscopy,
devices, Int. J. Hydrogen Energy 45 (2020) 30911–30923, https://doi.org/ Nanomaterials 12 (2022) 1393, https://doi.org/10.3390/nano12091393.
10.1016/j.ijhydene.2020.08.058. [33] L. Zhang, W. He, Y. Liu, M. Ling, P. Zheng, S. Guo, 3D hierarchical flower of copper
[10] K. Prasad, N. Mahato, K. Yoo, J. Kim, Morphology regulated hierarchical rods-, molybdate Cu3Mo2O9 : synthesis , nanostructure and lithium storage properties,
buds-, and sheets-like CoMoO4 for electrocatalytic oxygen evolution reaction, J. Alloys Compd. 723 (2017) 512–519, https://doi.org/10.1016/j.
Energies 16 (2023) 2441, https://doi.org/10.3390/en16052441. jallcom.2017.06.175.
[11] B. Guan, W. Sun, Y. Wang, Carbon-coated MnMoO4 nanorod for high-performance [34] N. Roy, H.R. Barai, A.N. Banerjee, J.S. Kim, S.W. Joo, Solvent-dependent structural
lithium-ion batteries, Electrochim. Acta 190 (2016) 354–359, https://doi.org/ and electrochemical properties of zinc cobaltite via a self-assembled mechanism for
10.1016/j.electacta.2016.01.008. battery-type supercapacitors, Chem. Eng. Sci. 277 (2023) 118834, https://doi.org/
[12] Y. Wang, H.N. Miras, Y. Li, Cross-linked CoMoO4/rGO nanosheets as oxygen 10.1016/j.ces.2023.118834.
reduction Catalyst, Catalysts 7 (2017) 375, https://doi.org/10.3390/ [35] X. He, Z.Z. Mo, H. Liu, C. Wang, Interface engineering of the NiO/CeO2@NF
catal7120375. heterostructure to boost the electro-oxidation of 5-hydroxymethylfurfural, Dalton
[13] G.R. Reddy, M. Dhananjaya, G.R. Dillip, G.L. Manjunath, S.W. Joo, Construction of Trans. 52 (2023) 9456–9464, https://doi.org/10.1039/D3DT01259J.
an ultra-high-energy density hybrid supercapacitor with self-assembled 3D [36] G.R. Reddy, G.R. Dillip, G.L. Manjunath, S.W. Joo, Boosting the electrochemical
hydrangea flower-like Mo-rich CoMoO4 microstructures, ChemNanoMat 9 (2023) performance of Mn-doped CuCo2O4/CuO heterostructures for all- solid-state
e202200490, https://doi.org/10.1002/cnma.202200490. asymmetric battery-type supercapacitors, J. Electrochem. Soc. 169 (2022) 060549,
[14] D. Muthu, T. Sadhasivam, T.H. Oh, Nickel molybdate nanorods synthesized on https://doi.org/10.1149/1945-7111/ac7753.
carbon cloth as an electrocatalyst for methanol oxidation and hydrogen evolution [37] G.R. Reddy, N.R. Reddy, G.R. Dillip, S.W. Joo, In Situ Construction of binder-free
reactions, Mater. Lett. 350 (2023) 134936, https://doi.org/10.1016/j. stable battery-type copper cobaltite and copper oxide composite electrodes for all-
matlet.2023.134936. solid- state asymmetric supercapacitors : cation concentration and morphology-
[15] N. Padmanathan, H. Shao, S. Selladurai, C. Glynn, C.O. Dwyer, K.M. Razeeb, dependent electrochemical performance, Energy Fuels 36 (2022) 5965–5978,
Pseudocapacitance of a α-CoMoO4 nanoflakes in non-aqueous electrolyte and its bi- https://doi.org/10.1021/acs.energyfuels.2c00767.
functional electrocatalytic activity for methanol oxidation, Int. J. Hydrogen Energy [38] G.R. Reddy, N.S. Kumar, B.D.P. Raju, G. Shanmugam, E.H. Al-Ghurabi, M. Asif,
40 (2015) 116297–116305, https://doi.org/10.1016/j.ijhydene.2015.09.127. Enhanced supercapacitive performance of higher-ordered 3d-hierarchical
[16] V.K.V.P. Srirapu, A. Kumar, N. Kumari, P. Srivastava, A comparative study of structures of hydrothermally obtained ZnCo2O4 for energy storage devices,
electrocatalytic performance of metal molybdates for the water oxidation, Int. J. Nanomaterials 10 (2020) 1206, https://doi.org/10.3390/nano10061206.
Hydrogen Energy 43 (2018) 16543–16555, https://doi.org/10.1016/j. [39] N. Roy, R. Mangiri, G. Phaneendra, A. Manohar, E. Chung, B.D. Prasad,
ijhydene.2018.07.060. G. Rajasekhara, S. Woo, Carbon nanofiber-supported elongated square bipyramid-
[17] N. Kumari, V.K.V.P. Srirapu, A. Kumar, R.N. Singh, Investigation of mixed like MnWO4 composite electrodes for high-performance battery-type
molybdates of cobalt and nickel for use as electrode materials in alkaline solution, supercapacitors : enhanced electrochemical performance via synergistic effect,
Int. J. Hydrogen Energy 45 (2020) 11040–11051, https://doi.org/10.1016/j. J. Electroanal. Chem. 947 (2023) 117764, https://doi.org/10.1016/j.
ijhydene.2020.02.006. jelechem.2023.117764.
[18] S. Wu, J. Liu, Y. Ye, Z. Tian, X. Zhu, C. Liang, Oxygen defects induce strongly [40] J. Acharya, B. Pant, G. Prasad, H. Kong, M. Park, Engineering triangular bimetallic
coupled Pt/metal oxides/rGO nanocomposites for methanol oxidation reaction, metal-organic-frameworks derived hierarchical zinc-nickel-cobalt oxide nanosheet
ACS Appl. Energy Mater. 2 (2019) 5577–5583, https://doi.org/10.1021/ arrays @ reduced graphene oxide-Ni foam as a binder-free electrode for ultra-high
acsaem.9b00756. rate performance supercapacitors and methanol electro-oxidation, J. Colloid
[19] M.S. Çögenli, A.B. Yurtcan, Heteroatom doped 3D graphene aerogel supported Interface Sci. 602 (2021) 573–589, https://doi.org/10.1016/j.jcis.2021.06.030.
catalysts for formic acid and methanol oxidation, Int. J. Hydrogen Energy 45 [41] A. Kumar, U. Narayan, V. Sharma, N. Hoon, J. Hee, Nanostructured CeO2/NiV-LDH
(2020) 650–666, https://doi.org/10.1016/j.ijhydene.2019.10.226. composite for energy storage in asymmetric supercapacitor and as methanol
[20] F. Sheikh, A. Arshad, F. Marriam, Z. Ahmad, A. Haider, M. Iqbal, M.A. Mansoor, oxidation electrocatalyst, Chem. Eng. J. 417 (2021) 128019, https://doi.org/
Fabrication of a nickel sulfide/nickel oxide heterostructure for efficient 10.1016/j.cej.2020.128019.
electrochemical oxidation of methanol, New J. Chem. 47 (2023) 17970–17983, [42] A. Manohar, J.P. Goud, M. Ouladsmane, K. Chaitanya, R. Mangiri, K. Hyeon,
https://doi.org/10.1039/D3NJ02855K. Unveiling the synergistic effect of mixed metal cations : self-assembled 3D cube-
[21] I.A. Khan, S. Ullah, F. Nasim, M. Choucair, M.A. Nadeem, A. Iqbal, A. Badshah, M. like CuCoMnO4/CuO composite for bifunctional battery-type supercapacitors and
A. Nadeem, Cr2O3-Carbon composite as a new support material for efficient methanol electro-oxidation, Mater. Sci. Semicond. Process. 168 (2023) 107833,
methanol electrooxidation, Mater. Res. Bull. 77 (2016) 221–227, https://doi.org/ https://doi.org/10.1016/j.mssp.2023.107833.
10.1016/j.materresbull.2016.01.037. [43] L. Zhang, D. Zhang, Z. Ren, M. Huo, G. Dang, F. Min, Q. Zhang, J. Xie, Mesoporous
[22] Y. Gong, Z. Yang, Y. Lin, J. Wang, H. Pana, Z. Xua, Hierarchical heterostructure NiCo2O4 micro/nanospheres with hierarchical structures for supercapacitor and
NiCo2O4@CoMoO4/NF as an efficient bifunctional electrocatalyst for overall water methanol electro-oxidation, Chemelectrochem 4 (2017) 441–449, https://doi.org/
splitting†, J. Mater. Chem. A 6 (2018) 16950–16958, https://doi.org/10.1039/ 10.1002/celc.201600638.
c8ta04325f. [44] Z. Mardani, M.B. Gholivand, Improvement of electrocatalytic activity of bimetal
[23] C. He, B. Han, S. Han, Q. Xu, Z. Liang, J.Y. Xu, M. Ye, X. Liu, J. Xu, Synthesis of sulfide of Ni-Cu by α-MnO2 for methanol oxidation, J. Electroanal. Chem. 923
hierarchical lamellar Co3O4–CoMoO4 heterostructures for lithium-ion batteries, (2022) 116822, https://doi.org/10.1016/j.jelechem.2022.116822.
J. Mater. Chem. A 7 (2019) 26884–26892, https://doi.org/10.1039/c9ta06920h. [45] L. He, S. Huang, Y. Liu, M. Wang, B. Cui, S. Wu, J. Liu, Z. Zhang, M. Du,
[24] Z. Li, P. Song, Z. Yang, Q. Wang, In situ formation of one-dimensional CoMoO4/ Multicomponent Co9S8@MoS2 nanohybrids as a novel trifunctional electrocatalyst
MoO3 heterojunction as an effective trimethylamine gas sensor, Ceram. Int. 44 for efficient methanol electrooxidation and overall water splitting, J. Colloid
(2018) 3364–3370, https://doi.org/10.1016/j.ceramint.2017.11.126. Interface Sci. 586 (2021) 538–550, https://doi.org/10.1016/j.jcis.2020.10.119.
[25] Y. Feng, Y. Shao, X. Chen, Y. Zhang, Q. Liu, M. He, H. Li, Sea-urchin-like hollow [46] A. Yarmolenko, B. Malik, E.S. Avraham, G.D. Nessim, One-step synthesis of a
CuMoO4 -CoMoO4 hybrid microspheres , a noble-metal-like robust catalyst for the binder-free, stable, and high-performance electrode; Cu-O|Cu3P heterostructure for
fast hydrogen production from ammonia borane, ACS Appl. Energy Mater. 4 the electrocatalytic methanol oxidation reaction (MOR), Nanomaterials 13 (2023)
(2021) 633–642, https://doi.org/10.1021/acsaem.0c02521. 1234, https://doi.org/10.3390/nano13071234.
[26] Z. Li, S. Ning, J. Xu, J. Zhu, Z. Yuan, Y. Wu, J. Chen, F. Xie, Y. Jin, N. Wang, [47] L. Qian, S. Luo, L. Wu, X. Hu, W. Chen, X. Wang, In situ growth of metal organic
H. Meng, S. Sun, In situ electrochemical activation of Co(OH)2@Ni(OH)2 frameworks derived hierarchical hollow porous Co3O4/NiCo2O4 nanocomposites
heterostructures for efficient ethanol electrooxidation reforming and innovative on nickel foam as self-supported flexible electrode for methanol electrocatalytic
zinc–ethanol–air batteries, Energy Environ. Sci. 15 (2022) 5300–5312, https://doi. oxidation, Appl. Surf. Sci. 503 (2020) 144306, https://doi.org/10.1016/j.
org/10.1039/D2EE01816K. apsusc.2019.144306.
[27] G.R. Reddy, B. Sravani, N. Jung, G.R. Dillip, S.W. Joo, Engineering rich-cation [48] K. Zhang, Y. Han, J. Qiu, X. Ding, Y. Deng, Y. Wu, G. Zhang, L. Yan, Interface
vacancies in CuCo2O4 hollow spheres with a large surface area derived from a engineering of Ni/NiO heterostructures with abundant catalytic active sites for
template-free approach for ultrahigh capacity and high-energy density enhanced methanol oxidation electrocatalysis, J. Colloid Interface Sci. 630 (2023)
supercapacitors, ACS Appl. Mater. Interfaces 15 (2023) 36500–36511, https://doi. 570–579, https://doi.org/10.1016/j.jcis.2022.10.057.
org/10.1021/acsami.3c08950.

12
Y.V. Manohara Reddy et al. Materials Science in Semiconductor Processing 174 (2024) 108213

[49] D. Wu, W. Zhang, D. Cheng, Facile synthesis of Cu/NiCu electrocatalysts [53] Z. Zhang, J. Liu, J. Wang, Q. Wan, Y. Wang, K. Wang, Z. Wang, M. Gu, Z. Tang,
integrating alloy, core-shell, and one-dimensional structures for efficient methanol J. Lim, T. Zhao, F. Ciucci, Single-atom catalyst for high-performance methanol
oxidation reaction, ACS Appl. Mater. Interfaces 9 (2017) 19843–19851, https:// oxidation, Nat. Commun. 120 (2021) 15235, https://doi.org/10.1038/s41467-
doi.org/10.1021/acsami.7b03876. 021-25562-y.
[50] H.B. Hassan, Z.A. Hamid, R.M. El-Sherif, Electrooxidation of methanol and ethanol [54] Q. Zhang, M.-M. Yan, W.-F. Du, C.-Y. Yin, J. Zhang, L. Yang, Y.-Q. Kang, H.-Y. He,
on carbon electrodeposited Ni–MgO nanocomposite, Chin. J. Catal. 37 (2016) H.-J. Huang, Spatial construction of ultrasmall Pt-decorated 3D spinel oxide-
616–627, https://doi.org/10.1016/S1872-2067(15)61034-8. modified N-doped graphene nanoarchitectures as high-efficiency methanol
[51] S. Anantharaj, H. Sugime, S. Noda, Ultrafast growth of a Cu(OH)2–CuO nanoneedle oxidation electrocatalysts, Rare Met. 43 (2024) 186–197, https://doi.org/
array on Cu foil for methanol oxidation electrocatalysis, ACS Appl. Mater. 10.1007/s12598-023-02418-6.
Interfaces 12 (2020) 27327–27338, https://doi.org/10.1021/acsami.0c08979. [55] X.-J. Guo, Q. Zhang, Y.-N. Li, Y. Chen, L. Yang, H.-Y. He, X.-T. Xu, H.-J. Huang,
[52] J.B. Wu, Z.G. Li, X.H. Huang, Y. Lin, Porous Co3O4/NiO core/shell nanowire array Nanosized Rh grown on single-walled carbon nanohorns for efficient methanol
with enhanced catalytic activity for methanol electro-oxidation, J. Power Sources oxidation reaction, Rare Met. 41 (2022) 2108–2117, https://doi.org/10.1007/
224 (2013) 1–5, https://doi.org/10.1016/j.jpowsour.2012.09.085. s12598-021-01882-2.

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