Aligned Co3O4–CoOOH heterostructure nanosheet arrays grown on carbon paper with oxygen vacancies for enhanced and robust oxygen evolution

Developing efficient and stable non-noble metal oxygen evolution reaction (OER) electrocatalysts for sustainable overall water-splitting is extremely desirable but still a great challenge. Herein, we developed a facile strategy to fabricate Co₃O₄–CoOOH heterostructure nanosheet arrays with oxygen vacancies grown on carbon paper (Co₃O₄–CoOOH/CP). Benefiting from the unique 3D architecture, large surface area, synergistic effects between Co₃O₄, CoOOH and oxygen vacancies, the obtained self-supporting Co₃O₄–CoOOH/CP presents excellent electrocatalytic OER activity (low overpotentials of 245 and 390 mV at 10 and 100 mA cm⁻²) and robust long-term stability in alkaline condition. The present strategy provides the opportunities for the future rational design and discovery of high-performance non-noble metal based electrocatalysts for advanced water oxidation and beyond.     

Se-doped cobalt oxide nanoparticle as highly-efficient electrocatalyst for oxygen evolution reaction

Electrolysis of water has been one of the most promising approaches for renewable energy resources while the efficient oxygen evolution reaction (OER) remains challenging. Herein, a series of different ratio of Se doped Co₃O₄ nanoparticles XSe-Co₃O₄ are prepared by hydrothermal method and applied as OER electrocatalysts. Se^2? is doped into the Co₃O₄ crystal lattice by substituting of O^2? and a large number of oxygen vacancies are generated, which provides more available activity sites for OER. Se doping increases the surface ratio of Co²⁺/Co³⁺ and accelerates the electron transport that favors OER activity promotion. The optimized doping ratio of 6%Se–Co₃O₄ presents low overpotential of 281 mV at 10 mA cm^?2, as well as a low Tafel slope of 70 mV dec^?1 in 1 M KOH solution, which has great advantages compared to the recently reported Co₃O₄-based OER electrocatalysts. This work provides new ideas for the development of efficient Co₃O₄-based OER electrocatalysts.     

Oxygen vacancy-based ultrathin Co3O4 nanosheets as a high-efficiency electrocatalyst for oxygen evolution reaction

Enhancing the catalytic activity of Co₃O₄ electrocatalysts featuring abundant oxygen vacancies is required to enable their application in oxygen evolution reaction (OER). However, developing a harmless defect engineering strategy based on mild conditions to realize such an enhancement remains a challenge. Here, ultrathin Co₃O₄ nanosheets with abundant oxygen vacancies were prepared through a simple two-step method comprising a hydrothermal process and pre-oxidation to study the catalytic activity of the nanosheets toward OER. The ultrathin sheet structure and the Co₃O₄ nanosheets surface provide abundant active sites. The oxygen vacancy not only improves the catalyst activity, but also improves the electron transfer efficiency. These advantages make ultrathin Co₃O₄ nanosheets with abundant oxygen vacancies an excellent electrocatalyst for oxygen evolution. In an alkaline medium, ultrathin Co₃O₄ nanosheets exhibited excellent OER catalytic activity, with a small overpotential (367 mV for 10 mA/cm²) and faster reaction kinetics (65 mV/dec).Moreover, the electrocatalyst still maintained 68% of its original catalytic activity after 24 h operation. This work provides an extensive and reliable method for the preparation of low-cost and highly efficient OER electrocatalysts.     

Zeolitic-imidazolate frameworks-derived Co3S4/NiS@Ni foam heterostructure as highly efficient electrocatalyst for oxygen evolution reaction

Transition metals sulfide-based nanomaterials have recently received significant attention as a promising cathode electrode for the oxygen evolution reaction (OER) due to their easily tunable electronic, chemical, and physical properties. However, the poor electrical conductivity of metal-sulfide materials impedes their practical application in energy devices. Herein, firstly nano-sized crystals of cobalt-based zeolitic-imidazolate framework (Co-ZIF) arrays were fabricated on nickel-form (NF) as the sacrificial template by a facile solution method to enhance the electrical conductivity of the electrocatalyst. Then, the Co₃S₄/NiS@NF heterostructured arrays were synthesized by a simple hydrothermal route. The Co-ZIFs derived Co₃S₄ nanosheets are grown successfully on NiS nanorods during the hydrothermal sulfurization process. The bimetallic sulfide-based Co₃S₄/NiS@NF-12 electrocatalyst demonstrated a very low overpotential of 119 mV at 10 mA cm^?2 for OER, which is much lower than that of mono-metal sulfide NiS@NF (201 mV) and ruthenium-oxide (RuO₂) on NF (440 mV) electrocatalysts. Furthermore, the Co₃S₄/NiS@NF-12 electrocatalyst showed high stability during cyclic voltammetry and chronoamperometry measurements. This research work offers an effective strategy for fabricating high-performance non-precious OER electrocatalysts.     

Vacancies and phosphorus atoms assembled in amorphous urchin-like Co3O4 for highly efficient overall water splitting

Designing highly efficient and low-cost electrocatalysts is essential for water splitting. Herein, urchin-like Co₃O₄ microspheres are firstly grown on nickel foam by a hydrothermal method, then Oxygen vacancies, phosphorus doping are effectively assembled in Co₃O₄ electrocatalysts. The introduction of oxygen vacancies and phosphorus doping will adjust the electronic structure of Co which increase the intrinsic catalytic activity and improve the adsorption energy of intermediates, simultaneously, progressively transform the crystal into randomly arranged atoms structure with short range order resulting in more active sites participate in the catalytic reaction. Moreover, the catalyst of vacancies Co₃O₄-Ov and phosphorus doping Co₃O₄–P demonstrate excellent performance in oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) in alkaline media, Co₃O₄-Ov sample served as anode while Co₃O₄–P as cathode to form an electrolytic cell needs only 1.58 V to reach 20 mA cm^?2 for overall water splitting.     

Highly efficient and stable bifunctional electrocatalyst for water splitting on Fe–Co3O4/carbon nanotubes

Replacement of precious platinum (Pt) or ruthenium oxide (RuO₂) catalysts with efficient, cheap and durable electrocatalysts from earth-abundant elements bifunctional alternatives would be significantly beneficial for key renewable energy technologies including overall water splitting and hydrogen fuel cells. Despite tremendous efforts, developing bifunctional catalysts with high activity at low cost still remain a great challenge. Here, we report a nanomaterial consisting of core-shell-shaped Fe–Co₃O₄ grown on carbon nanotubes (Fe–Co₃O₄/CNTs) and employed as a bifunctional catalyst for the simultaneous electrocatalysts on oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). The Fe–Co₃O₄/CNTs electrocatalyst outperforms the commercial RuO₂ catalyst in activity and stability for OER and approaches the performance of Pt/C for HER. Particularly, it shows superior electrocatalytic activity with lowering overpotentials of 120 mV at 10 mA cm^?2 for HER and of 300 mV at 10 mA cm^?2 for OER in 1 M KOH solution. The superior catalytic activity arises from unique core-shell structure of Fe–Co₃O₄ and the synergetic chemical coupling effects between Fe–Co₃O₄ and CNTs.     

Development of NiO/Co3O4 nanohybrids catalyst with oxygen vacancy for oxygen evolution reaction enhancement in alkaline solution

The oxygen evolution reaction (OER) is a significant reaction in water splitting and energy conversion. However, high price and sluggish kinetics catalysts prevent commercial applications. Generally, noble metals (e.g., iridium and ruthenium), which are expensive and unstable, have been used as catalysts for OER because of their high electrocatalytic activity. In this study, we report a high-performance OER catalyst with oxygen vacancies comprising NiO/Co₃O₄ nanohybrids. For OER, the NiO/Co₃O₄ heterostructure show good electrocatalytic performance with a low overpotential of 330 mV. This is higher than those of NiO, Co₃O₄, and benchmark IrO₂ candidates at current density of 10 mA cm^?2. Furthermore, the NiO/Co₃O₄ nanohybrids show long-term electrochemical stability for 10 h. The present research results show that NiO/Co₃O₄ heterostructure is an excellent electrocatalyst for OER.     

MgO as promoter for electrocatalytic activities of Co3O4–MgO composite via abundant oxygen vacancies and Co2+ ions towards oxygen evolution reaction

Oxygen evolution reaction (OER) is known as bottleneck problem during the water splitting process due to high energy barrier and non-availability of efficient nonprecious electrocatalysts. The cobalt oxide (Co₃O₄) in the spinel phase has limited OER activity and stability in the alkaline media. For this purpose, we have carried out the synthesis of Co₃O₄–MgO (CM) composite by wet chemical method and it offers abundant oxygen vacancies and Co²⁺ concentration for the efficient OER reaction. The effect of different amounts of MgO on the OER activity of Co₃O₄ was also studied. Despite inactivity of MgO towards OER, it creates high density of oxygen vacancies and favored the formation Co²⁺ ions at the surface, thus accelerated the OER kinetics. The physical studies were performed to investigate the morphology, crystalline structure, surface information and chemical composition using several analytical techniques. The optimized CM-0.1 composite produced an overpotential of 274 mV at 10 mAcm⁻² which is lower in value than the pristine Co₃O₄. The significant enhancement in the OER activity was verified by the large value of electrochemical active surface area values 12.8 μFcm⁻² and the low charge transfer resistance of 45.96 Ω for the optimized CM-0.1 composite. The use of abundance materials for the synthesis of CM composite revealed an enhanced OER performance, suggesting the dynamic role of MgO, therefore it could be used for improving the electrochemical properties of extended range of metal oxides for specific application especially energy conversion and storage devices.     

Synthesis of CuCo2S4 nanosheet arrays on Ni foam as binder-free electrode for asymmetric supercapacitor

Recently more and more concerns have been paid on ternary metal sulfides for use in supercapacitors because of their better electrochemical performances compared with binary counterparts. In this work, CuCo₂S₄ nanosheet arrays on Ni foam were prepared by a sequential ion-exchange strategy under hydrothermal conditions, where Co₃O₄ was converted into Co₄S₃ by an anion-exchange reaction between Co₃O₄ and S^2? ions, subsequently the Co₄S₃ was transformed into CuCo₂S₄ through a cation-exchange reaction with Cu²⁺ ions. The as-prepared CuCo₂S₄ was characterized by powder X-ray diffraction, high-resolution X-ray photoelectron spectroscopy, field emission scanning electron microscopy and transmission electron microscopy. The CuCo₂S₄ arrays were composed of interconnected thin nanosheets with thickness of about 10 nm. The CuCo₂S₄ nanosheet arrays on Ni foam were directly employed as a binder-free electrode showing a high specific capacitance of 3132.7 F g^?1 at a current density of 1 A g^?1. Besides, an asymmetric supercapacitor based on this synthesized CuCo₂S₄ electrode as positive electrode and active carbon as negative electrode can deliver a high energy density of 46.1 Wh kg^?1 at a power density of 991.6 W kg^?1, and exhibits good rate capability and cycling stability.     

A facile top-down approach for constructing perovskite oxide nanostructure with abundant oxygen defects as highly efficient water oxidation electrocatalyst

Developing highly efficient electrocatalysts for oxygen evolution reaction (OER) is of significant importance for the application of many energy conversion and storage technologies. Perovskite oxides have attracted great attention as potential OER electro-catalysts. Their performance, however, are strongly limited by large particle size, owing to the high synthesis temperature. Herein, we report a facile top-down strategy for fabricating perovskite oxide nanostructures with large surface area and strongly improved intrinsic OER activity. SrNb_0.1Co_0.7Fe_0.2O_3-δ (SNCF) particles with micro size are treated by (NH₄)₂Fe(SO₄)₂ saturated solution for different time length at room temperature. The obtained catalysts exhibit significantly increased surface area with nanosheet structure in the outer layer. Furthermore, cobalt on the surface are reduced from Co³⁺ to Co²⁺, suggesting oxygen vacancy formation on the surface. The defective SNCF nanostructure exhibits significantly improved OER activity and good stability. The facile methodology reported in this work can be generally applied to other oxide electrocatalysts for energy applications.     

Nitrogen doped graphene quantum dots (N-GQDs)/Co3O4 composite material as an efficient bi-functional electrocatalyst for oxygen evolution and oxygen reduction reactions

In this work, a facile development of a bi-functional electrocatalyst for oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) is reported. A composite material comprising of tiny particles of nitrogen doped graphene quantum dots (N-GQDs) embedded into cobalt oxide (Co₃O₄) flakes is prepared by sodium borohydride reduction method and followed by annealing at 600 °C under inert atmosphere. Structural, morphological and crystalline features are analyzed using FESEM, TEM, HRTEM, XRD and XPS studies. Moreover, optical and fluorescence properties of N-GQDs are studied using UV–visible and fluorescence spectroscopic techniques. These studies clearly reveal and confirm the formation of a composite material. Further electrochemical characteristics toward OER and ORR are investigated by using linear sweep voltammetry (LSV) and cyclic voltammetry (CV) techniques. Compared to the individual entities of pure Co₃O₄ and N-GQDs alone, the electrocatalytic activity of N-GQDs/Co₃O₄ composite material is significantly higher towards ORR. Similarly, the same composite material is also used as an electrocatalyst for OER in 0.1 M KOH aqueous electrolyte and it exhibits a lower overpotential of 330 mV to obtain a current density of 10 mA/cm² along with higher electrocatalytic activity and the reason is mainly attributed to the synergistic effect between N-GQDs and Co₃O₄. Thus, N-GQDs/Co₃O₄ composite material is demonstrated to be a high performance bi-functional electrocatalyst for ORR and OER.     

High electrochemical stability and low-agglomeration of defective Co3O4 nanoparticles supported on N-doped graphitic carbon nano-spheres for oxygen evolution reaction

The design of hybrid electrocatalysts with abundant active sites and long term stability is crucial for efficient oxygen evolution reaction (OER) application. Cobalt oxide is considered as one of the most promising electrocatalysts to replace noble metal due to its low cost, availability, and electrocatalytic activity towards the oxygen evolution reaction in alkaline media. However, nano-scale cobalt oxide suffers from severe surface self-agglomeration during the OER process, so that leading to poor activity and durability. Herein, ultra-small cobalt oxide nanoparticles are anchored on the surface of nitrogen doped porous 3D graphitic carbon nano-spheres (N-ACS@Co₃O₄) to increase the amount of exposed active site and avoid the self-agglomeration. The obtained electrocatalyst (N-ACS@Co₃O₄) is enriched with abundant oxygen vacancies and exhibits a superior OER activity (Overpotential of 237 mV at 10 mA.cm⁻²) and exceptional stability for at least 30 h in alkaline electrolyte (1 M KOH). The DFT calculations demonstrate that the strong adsorption of Co₃O₄ on N-doped graphene can prevent its agglomeration, and therefore improves the stability of Co₃O₄ nanoparticles during OER process in line with the experimental results.     

Synergistic coupling of CoFe-layered double hydroxide nanosheet arrays with reduced graphene oxide modified Ni foam for highly efficient oxygen evolution reaction and hydrogen evolution reaction

Novel CoFe-LDH (layered double hydroxide) nanosheet arrays in situ grown on rGO (reduced graphene oxide) uniformly modified Ni foam were synthesized by a citric acid-assisted aqueous phase coprecipitation strategy. Systematic characterizations indicates that the series of Co_xFe₁-LDH/rGO/NF (x = 4, 3, 2) all show Co_xFe₁-LDH nanosheets (150–180 × 15 nm) grown vertically on the surface of rGO/NF. Especially, the Co₃Fe₁-LDH/rGO/NF exhibits the best performance with overpotentials of 250 and 110 mV at 10 mA cm^?2 in 1 M KOH for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER), respectively. When it is used as cathode and anode simultaneously for overall water splitting, they require 1.65 and 1.84 V at 10 and 100 mA cm^?2, respectively. Excellent performance of Co₃Fe₁-LDH/rGO/NF is due to the nanosheet arrays structure with open channels, synergistic coupling between Co₃Fe₁-LDH and rGO enhancing electrical conductivity, and in-situ growth of Co₃Fe₁-LDH on rGO/NF enhancing stability.     

Porous Co3O4 decorated nitrogen-doped graphene electrocatalysts for efficient bioelectricity generation in MFCs

High-performance, low-cost, and robust oxygen reduction reaction (ORR) catalysts have played a very crucial role in the development of microbial fuel cells (MFCs). Herein, A novel in-situ Co₃O₄ nanoparticles (NPs) modified nitrogen-doped graphene with three-dimensional porous structure (3D GN-Co₃O₄) has been successfully synthesized and employed as an efficient ORR catalyst in MFCs. Benefiting from 3D porous architecture feature, highly intrinsic conductivity and synergistic effect between nitrogen-doped graphene and Co₃O₄ NPs, the 3D GN-Co₃O₄ as a cathode catalyst in alkaline condition realizes significantly enhanced electrochemical performance and outstanding cycling stability. Furthermore, the self-assembly of MFCs based on the 3D GN-Co₃O₄ cathode offers a high power density of 578 ± 10 mW m^?2, which is even comparable to the commercial Pt/C.     

Electrochemical synthesis of Li-doped NiFeCo oxides for efficient catalysis of the oxygen evolution reaction in an alkaline environment

Oxygen evolution reaction (OER) is an essential reaction for overall electrochemical water splitting. In this present study, we adopt a facile electrochemical deposition method to synthesize the Li-doped NiFeCo oxides for OER in an alkaline medium. The scanning electron microscopy, X-ray diffraction, Brunauer-Emmet-Teller method and X-ray photo-electron spectroscopy provides the information of morphology, structure, specific surface area and electronic state of the electrocatalysts respectively. Investigates the electrochemical properties by the thin-film technique on a rotating disk electrode and in a single-cell laboratory water electrolyzer connects with electrochemical impedance spectroscopy. Among the catalysts under investigation, Ni_0·9Fe_0·1Co_1·975Li_0·025O₄ exhibits the highest activity towards oxygen evolution reaction, and explains the activity by the oxygen binding energy; such knowledge can be helped to develop better catalyst. We achieve onset over potential 220 mV and receive 10 mA cm^?2 current density at over potential 301 mV with Tafel slope 62 mV dec^?1 in 1 M KOH solution. The results are similar to recently published catalysts in the literature. In water electrolyzer, the Ni_0·9Fe_0·1Co_1·975Li_0·025O₄ modified nickel foam anode exhibits a current density of 143 mA cm^?2 at a cell voltage of 1.85 V in 10 wt% KOH and a temperature of 50 °C.     

A facile method for reduced CoFe2O4 nanosheets with rich oxygen vacancies for efficient oxygen evolution reaction

The efficiency of electrochemical water splitting is greatly hindered by the thermodynamic uphill reaction of oxygen evolution reaction (OER). Thus, it is important to synthesize an active OER electrocatalysts with abundant active sites, favorable conductivity and good durability. Herein, a facile reduction method using NaBH₄ as readily available reductant has been developed to fabricate the reduced CoFe₂O₄ nanosheets (NS). The obtained reduced CoFe₂O₄ NS are rich in oxygen deficient sites, leading to more active sites as well as the enhanced conductivity than the pristine CoFe₂O₄ hollow nanosphere, which reaches the current density of 10 mA cm^?2 at the overpotential of 320 mV in 1 M KOH. Meanwhile, CoFe₂O₄ samples with three different morphology nanostructures including hollow nanospheres, bulk and nanoparticles have been provided to study the effect of different morphology on NaBH₄ reduction efficiency. As expected, after NaBH₄ reduction, CoFe₂O₄ hollow nanosphere with relatively higher surface area exhibits most obvious improvement for OER activity and also its corresponding reduced CoFe₂O₄ NS showed best OER performance than the reduced CoFe₂O₄ bulk as well as the reduced CoFe₂O₄ nanoparticles, implying the hollow nanospheres feature more accessible surface area than bulk and nanoparticles samples, thus greatly facilitate efficiency of NaBH₄ reduction treatment.     

An efficient palladium oxide nanoparticles@Co3O4 nanocomposite with low chemisorbed species for enhanced oxygen evolution reaction

Significant progress has been made in recent time to design and synthesize highly efficient and cost effective electrocatalysts for oxygen evolution reaction (OER). However, the electrocatalytic activity of most recently reported materials is limited by the large onset potential, poor electrical conductivity and low density of catalytic centers. In this study, we report facile deposition of palladium oxide nanoparticles onto cobalt oxide nanostructures (PdONPs@Co₃O₄) through the illumination of ultraviolet (UV) light. The fabricated PdONPs@Co₃O₄ nanocomposites offer high density of active sites, improved electrical conductivity and durability for OER activity. The synergetic effect between the Co and Pd ions at the interface of composite system might change the adsorption energy of reaction intermediates, thus enabled the reaction to proceed at lower energy consumption. Significantly, the prepared PdONPs@Co₃O₄ samples demonstrated a low overpotential of 250 mV at a current density of 20 mA/cm², with low charge transfer resistant of 48.5 Ωand high durability for more than 40 h during OER processes. The combined results suggest that incorporating of a low amount of PdONPs can tune the surface properties of Co₃O₄ and interfacial chemistry. This could led to accelerate the charge transport properties at the interface during a specific electrochemical application.     

Investigation of layered Ni0.8Co0.15Al0.05LiO2 in electrode for low-temperature solid oxide fuel cells

A symmetrical cell composed of Ce_0.9Gd_0.1O_2?δ electrolyte is constructed with 0.5 mm thickness and Ni_0.8Co_0.15Al_0.05LiO₂ (NCAL)-foam Ni composite electrodes. Electrochemical performance of the cell and electrochemical impedance spectra (EIS) are measured using the three-electrode method. The maximum power densities of the cell are 93.6 and 159.7 mW cm^?2 at 500 and 550 °C, respectively. The polarization resistances of the cathode are 0.393 and 0.729 Ω cm^?2 at 550 and 500 °C, indicating that NCAL has good ORR activity. HT-XRD results for NCAL do not show phase transitions or any additional new phases at elevated temperatures, indicating that NCAL has a stable phase structure. The surface characteristics of the NCAL powders are studied by XPS and FTIR. The results reveal that Li₂CO₃ and the cation-disordered “NiO-like” phase are formed on the surface of the layered NCAL structure due to prolonged exposure to air and contain a large number of oxygen vacancies. The cation-disordered “NiO-like” phase and Li₂CO₃ composite in the melt and partial melt states in the high temperature region are considered to possess very high ionic conductivity and lower activation energy for oxygen reduction reactions.     

Synergistically modulating the electronic structure of Cr-doped FeNi LDH nanoarrays by O-vacancy and coupling of MXene for enhanced oxygen evolution reaction

Water splitting is an environmentally friendly method of hydrogen generation. However, it is severely limited by the slow anodic oxygen evolution reaction (OER). Iron-nickel layered double hydroxides (FeNi LDH) are promising electrocatalysts for OER, but their intrinsically low electrical conductivity and activity limit the practical applications. Herein, chromium-doped FeNi LDH nanoarrays in situ vertically grown on the surface of the Ti₃C₂T_x MXene (Cr-FeNi LDH/MXene) are successfully synthesized. Remarkably, the robust interaction and electrical coupling between Cr–FeNi LDH and MXene, as well as conspicuous charge transfer and the oxygen vacancies optimizing the adsorption free energy of intermediates, equip the nanocomposites with brilliant catalytic activity and stability toward OER. Thus, the optimized Cr–FeNi LDH/MXene shows a considerable boost in the OER, which affords low overpotential (232 mV at 10 mA cm^?2) and excellent durability. This work offers a new path to designing highly efficient and earth-abundant catalysts for water splitting and beyond.     

Micro and nano-architectures of Co3O4 on Ni foam for electro-oxidation of methanol

Spinel Co₃O₄ material with different morphologies is directly grown on Ni foam by simple hydrothermal method and subsequent calcination processes. The direct growth of binder free active phase of Co₃O₄ on Ni foam is an effective approach to enhance the electrocatalytic activity of the material. The morphologies of Co₃O₄ strongly depend on the anion of the precursor salt used. Microflowers, microspheres and nanograss morphologies of Co₃O₄ are obtained using chloride, sulfate and acetate salts of cobalt, respectively. The BET surface areas of these cobalt oxide materials are found to increase in the order of microflower-Co₃O₄ (53 m² g^?1) < nanograss-Co₃O₄ (65 m² g^?1) < microsphere-Co₃O₄ (100 m² g^?1). The electrocatalytic activity of these Co₃O₄ materials has been tested for methanol oxidation by cyclic voltammetry and chronoamperometry. All three samples show low onset potentials (0.32–0.34 V) for methanol oxidation. The vanodic peak current of methanol oxidation is found to increase in the order of microflower-Co₃O₄ (28 A g^?1) < nanograss-Co₃O₄ (34.9 A g^?1) < microsphere-Co₃O₄ (36.2 A g^?1) at 0.6 V. This study highlights the significance of the morphology of cobalt oxide in the development of oxide based non-precious electrocatalysts for methanol oxidation.