Double doping of V and F on Co3O4 nanoneedles as efficient electrocatalyst for oxygen evolution

Rationally designing high-activity catalyst for oxygen evolution reaction (OER) is of primary importance due to its sluggish kinetic process in water splitting. Herein, we report a metallic (V) and nonmetallic (F) double doping in Co₃O₄ with nanoneedles structure, which is synthesized through facile oil bath and annealing. Electrochemical measurements show that the Co₃O₄ dopped with fluorine and vanadium (F_0.2-V-Co₃O₄-350) only needs a low overpotential of 320 mV to afford a current density of 10 mA cm^?2, which is superior to commercial RuO₂. The excellent electrocatalytic performance can be attributed to double doping of vanadium and fluorine which have strong electron absorption effect to optimize the density of electrons in Co₃O₄. Besides, nanoneedles structure can enlarge exposure of active sites. And its great durability is evaluated through 2000 cycles CV test. Furthermore, the optimal ratio of fluorine to vanadium and different annealing temperatures of the target catalyst are explored reasonably.     

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.     

Iridium-titanium oxides for efficient oxygen evolution reaction in acidic media

Active and highly stable oxygen evolution reaction (OER) electrocatalyst for PEM-based water electrolysis are currently in high demand. Herein, we report a rutile iridium-titanium oxide solid solution (IrTiO_x) through a facile one-step annealing of a Ti-based metal-organic framework precursor. The composite exhibits excellent OER activity and stability in acidic media, with a low overpotential of 296 mV at 10 mA cm⁻² while the OER activity was retained during a 100-h galvanostatic stability test at a constant current of 10 mA cm⁻² in 0.5 M H₂SO₄, outperforming the state-of-the-art IrO₂-based electrocatalysts. We further demonstrate the structure evolution of iridium-titanium oxide during OER operations. In contrast to the initial uniform distribution of Ir and Ti over the entire architecture, after OER stability test, a hollow morphology is formed, in which the particle surface is covered with an IrO_x-rich layer and entire particle becomes hollow. We ascribe the structure evolution to the Ir/Ti leaching and redeposition during the OER operations. We propose that the structure evolution of iridium-titanium oxide during the electrochemical process is responsible for the high OER activity and stability of IrTiO_x.     

Flower-like Co3O4 microstrips embedded in Co foam as a binder-free electrocatalyst for oxygen evolution reaction

Designing appropriate oxygen evolution reaction (OER) electrocatalysts to meet the requirements of high efficiency, long-term durability, and low cost remains the challenge for scientific community. Cobalt oxide (Co₃O₄) has been proven as a promising candidate for OER with attractive activity and stability in alkaline media. In this study, flower-like Co₃O₄ microstrips have been successfully prepared and directly embedded in Co foam (denoted as Co₃O₄@Co foam) by a green and facile two-step strategy including hydrothermal treatment and subsequent annealing process under relatively low temperatures. It demonstrates that the OER performance of the Co₃O₄@Co foam electrode can rival to the commercial RuO₂ on glassy carbon electrode. The Co₃O₄@Co foam electrode displays high OER activity with a low overpotential of 273 mV at a current density of 10 mA cm⁻², and a low Tafel slope of 61.8 mV dec⁻¹. The flower-like Co₃O₄ microstrips greatly increase the active surface area to expose more active sites, and the directly growth of Co₃O₄ microstrips on Co foam with intimate contact improves the electron transport and ensures the stability of the Co₃O₄@Co foam electrode.     

ZIF-67-derived Mn doped Co9S8 supported on N-Enriched porous carbon polyhedron as an efficient electrocatalyst for oxygen evolution reaction

Rational design of efficient oxygen evolution reaction (OER) electrocatalysts plays a significant role in various applications like water splitting and metal-air batteries. Simultaneous modulation of geometric and electronic structure is a promising strategy for boosting the electrocatalytic active of OER catalysts. Herein, a novel type of Mn doped Co₉S₈ supported on N-enriched porous carbon polyhedron composite material (Mn–Co₉S₈/NC) is constructed via absorption-pyrolysis-sulfurization treatment of Zeolitic-imidazolate frameworks (ZIF-67). ZIF-67 derived N-enriched porous carbon polyhedron serves as the porous skeleton for anchoring numerous Co₉S₈ nanoparticles. The results confirm that the incorporation of Mn in Co₉S₈/NC can improve the degree of graphitization compared with Co₉S₈/NC, implying the enhancement of the conductivity. Meanwhile, the incorporation of Mn can lead to electronic modulation of Co species to bump up the intrinsic activity of active site in Mn–Co₉S₈/NC. Due to the synergistic effect of Mn, Co₉S₈ and porous carbon structure, the specific surface area and electronic structure are optimized, endowing the maximum utilization of active sites. The Mn–Co₉S₈/NC electrocatalyst exhibits superior OER activity with the overpotential of 286 mV at current density of 10 mA cm⁻² in 1.0 M KOH electrolyte. This work provides prospective insights into the synergistic coupling of geometric and electronic structure of Metal-Organic Frameworks (MOFs) material for efficient electrocatalysts.     

Ultrafine molybdenum silicide nanoparticles as efficient hydrogen evolution electrocatalyst in acidic medium

Molybdenum silicides are promising electrocatalysts for hydrogen evolution in acidic environment due to their dual characteristics of metal and ceramics as well as high electrical conductivity and acid resistance. At present, most of the transition metal silicides were synthesized at high temperature, resulting in large particle size and small specific surface area, which seriously limits their electrocatalytic applications. Herein, we report a low temperature strategy for the synthesis of ultrafine Mo₅Si₃ and MoSi₂ nanoparticles with diameter of ～5 nm by molten salt method. Results show that both of them demonstrated excellent electrocatalytic hydrogen evolution activity and stability in 0.5 M H₂SO₄ solution, in which the overpotentials of Mo₅Si₃ and MoSi₂ nanoparticles at 10 mA cm^?2 are 80 mV and 94 mV, respectively. This general strategy may light up the preparation of ultrafine transition metal silicides nanoparticles and facilitate their applications in electrocatalytic areas.     

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.     

Reduced CoFe2O4/graphene composite with rich oxygen vacancies as a high efficient electrocatalyst for oxygen evolution reaction

Oxygen evolution reaction (OER) is regarded as a limit-efficiency process in electrochemical water splitting generally, which needs to develop the effective and low-cost non-noble metal electrocatalysts. Oxygen vacancies have been verified to be beneficial to enhance the electrocatalytic performance of catalysts. Herein, we report the facile synthesis of reduced CoFe₂O₄/graphene (r-CFO/rGO) composite with rich oxygen vacancies by a citric acid assisted sol-gel method, heat treatment process and the sodium borohydride (NaBH₄) reduction. The introduction of graphene and freezing dry technique prevents the restacking of GO and the aggregation of CFO nanoparticles (NPs) and increases the electronic conductivity of the catalyst. Fast heating rate and low anneal temperature favors to obtain low crystallinity and lattice defects for CFO. NaBH₄ reduction treatment further creates the rich oxygen vacancies and electrocatalytic active sites. The obtained r-CFO/rGO with high specific surface area (108 m² g⁻¹), low crystallinity and rich oxygen vacancies demonstrates a superior electrocatalytic activity with the smaller Tafel slope (68 mV dec⁻¹), lower overpotential (300 mV) at the current density of 10 mA cm⁻², and higher durability compared with the commercial RuO₂ catalyst. This green, low-cost method can be extended to fabricate similar composites with rich defects for wide applications.     

Spinel NiCo2O4 3-D nanoflowers supported on graphene nanosheets as efficient electrocatalyst for oxygen evolution reaction

Efficient oxygen evolution reaction (OER) electrocatalysts with non-noble metals are very critical for the large-scale exploitation of electrocatalytic hydrogen production systems. To improve the catalytic activity of OER electrocatalysts, several design strategies, such as construction of nanostructures, porous structures and composite materials have been proposed. Herein, spinel NiCo₂O₄ 3-D nanoflowers supported on graphene nanosheets (GNs) are prepared by a simple solvothermal synthesis method as non-noble metal electrocatalysts for OER. The present NiCo₂O₄/GNs composite integrates multiple advantages of nanostructures, porous structures and composite materials, including high surface area, abundant catalytic sites and high stability. Benefiting from the favorable features, the NiCo₂O₄/GNs composite exhibits a better OER performance than NiCo₂O₄ and RuO₂ in alkaline medium, which has a low onset potential (1.50 V), a small Tafel slope (137 mV dec⁻¹). The present work opens a new window for the construction of the carbon-supported 3-D nanostructure of transition metal catalysts with optimizable electrocatalytic performances for electrocatalytic hydrogen production.     

Boron doped cryptomelane as a highly efficient electrocatalyst for the oxygen evolution reaction

In this study, cryptomelane-type (1D) MnO₂ was doped with boron powder by ball-milling in an inert organic solvent under various experimental conditions. The structural, thermal, morphological, and surface features of samples prepared by the ball-milling method were characterized by powder X-ray diffraction, Fourier transform infrared spectroscopy, thermogravimetric analysis, X-ray photoelectron spectroscopy, scanning and transmission electron microscopy, and surface measurements. The electrocatalytic oxygen evolution reaction (OER) performances of the samples were tested and compared with the bare cryptomelane to reveal the effect of boron doping into manganese oxide. It was found that boron particles transformed to trigonal BO₃ units in the cryptomelane structure via mechanical activation, and accordingly, the oxidation state of manganese in this structure relatively changed. The 0.25% B-doped cryptomelane sample prepared at 12 h grinding time exhibited the overpotential of 425 mV at a current density of 1 mAcm⁻² with a Tafel slope of ∼95 mV dec⁻¹. It showed a remarkable catalytic performance among the other electrocatalysts under neutral pH compared to bare cryptomelane. When the elemental boron doping exceeded 1%, the electrochemical performance dramatically decreased depending on the blocking of the Mn³⁺ active sites.     

Functionalized Co3O4 graphitic nanoparticles: A high performance electrocatalyst for the oxygen evolution reaction

We describe a novel synthesis technique for the production of graphitic carbon functionalized Co₃O₄ (G/Co₃O₄), which involves the rapid decomposition of cobalt nitrate in the presence of citric acid. Upon immobilization of the G/Co₃O₄ upon Screen-Printed macroElectrodes (G/Co₃O₄-SPEs) the G/Co₃O₄-SPEs were found to exhibit remarkable electrocatalytic properties towards the Oxygen Reduction Reaction (OER). A detailed investigation has been carried out on the influence that the graphitization of the citric acid has, during the course of preparation of Co₃O_4, upon the ability of the G/Co₃O₄ to catalyse the OER within alkaline conditions (1.0 M KOH). The graphitization of citric acid ensures the uniform distribution of Co₃O₄ and enhanced conductivity with maximal exposure of active sites, which are the key parameters to delivering enhanced electrochemical activity. The G/Co₃O₄-SPEs exhibits an overpotential of 304 mV (recorded at 10 mA cm⁻²), a Tafel slope of 110 mV dec⁻¹ and remain stable in its signal output (achievable current density) at varying temperatures (5–50 °C), and after 10 h of chronoamperometry in 1.0 M KOH. The G/Co₃O₄-SPE's OER activity was found to be superior to that of bulk and nano Co₃O₄. The results exhibited within this study will enable production of high-performance and environmentally benign electrocatalysts towards the OER for use within water splitting devices.     

MnxCo3-xO4 spinel oxides as efficient oxygen evolution reaction catalysts in alkaline media

The design of efficient electrocatalysts for oxygen evolution reaction (OER) is an essential task in developing sustainable water splitting technology for the production of hydrogen. In this work, manganese cobalt spinel oxides with a general formula of Mn_xCo_3-xO₄ (x = 0, 0.5, 1, 1.5, 2) were synthesised via a soft chemistry method. Non-equilibrium mixed powder compositions were produced, resulting in high electrocatalytic activity. The oxygen evolution reaction was evaluated in an alkaline medium (1 M KOH). It was shown that the addition of Mn (up to x ≤ 1) to the cubic Co₃O₄ phase results in an increase of the electrocatalytic performance. The lowest overpotential was obtained for the composition designated as MnCo₂O₄, which exhibited a dual-phase structure (∼30% Co₃O₄ + 70% Mn_1.4Co_1.6O₄): the benchmark current density of 10 mA cm⁻² was achieved at the relatively low overpotential of 327 mV. The corresponding Tafel slope was determined to be ∼79 mV dec⁻¹. Stabilities of the electrodes were tested for 25 h, showing degradation of the MnCo₂O₄ powder, but no degradation, or even a slight activation for other spinels.     

Large-area manganese oxide nanorod arrays as efficient electrocatalyst for oxygen evolution reaction

Large-area manganese oxide nanorod arrays (MnO₂ NRAs) have been directly grown vertically on Ti foil with a uniform length and diameter by a simple electrochemical method without any templates. The deposition temperature is one of the most important parameters for formation MnO₂ NRAs and at 25 °C no MnO₂ NRAs can be obtained. The results show that MnO₂ has high activity and good stability for oxygen evolution reaction (OER) and the structure of nanorod arrays pronounced enhances MnO₂ activity. The onset potential of MnO₂ NRAs is lower than that of Pt foil and lower 401 mV than that of MnO₂ film, indicating that the structure of MnO₂ NRAs shows an easy OER for water split. The MnO₂ NRAs may be of great potential in electrochemical water split.     

Controlled synthesis of NiCo2O4@Ni-MOF on Ni foam as efficient electrocatalyst for urea oxidation reaction and oxygen evolution reaction

Heterostructured materials with special interfaces and features give a unique character for much electrocatalytic process. In this work, the introduction of exogenous modifier Ni-MOF improved the reaction kinetics and morphology of the NiCo₂O₄@Ni-MOF/NF catalyst. As-obtained NiCo₂O₄@Ni-MOF/NF has excellent oxygen evolution reaction (OER) performance and urea oxidation reaction (UOR) performance. The catalyst need overpotential of 340 mV at a current density of 100 mA cm^?2 for OER and a potential of 1.31 V at the same current density for UOR. The Tafel slopes of NiCo₂O₄@Ni-MOF/NF is 38.34 and 15.33 mV dec^?1 for OER and UOR respectively, which is more superior than 78.58 and 66.73 mV dec^?1 of NiCo₂O₄/NF. The nanosheets microstructure is beneficial to the adsorption and transport of electrolyte and the presence of a large number of mesoporous channels can also accelerate gas release, and then improves activity of the catalyst. Density functional theory calculation demonstrate that NiCo₂O₄ plays a role in absorbing water, while the existence of in situ generated NiOOH can promote the electron transfer efficiency. It is synergies of NiCo₂O₄ and in situ generated NiOOH that enhance the decomposition of water on the surface of the NiCo₂O₄@Ni-MOF/NF. This investigation provides a new strategy for the application of spinel oxide and MOF materials.     

3D flower-like polypyrrole-derived N-doped porous carbon coupled cobalt oxide as efficient oxygen evolution electrocatalyst

For electrochemical splitting of water, highly active and non-precious metal electrocatalysts towards the oxygen evolution reaction (OER) are direly needed to address the cost and stability issues. Herein, polypyrrole (PPy) with 3D flower-like structure has been prepared to obtain N-doped porous carbon sheets (N–C) and to implant with cobalt oxides (Co₃O₄) via simple and cost-effective hydrothermal reaction. Benefitting from the 3D flower-like porous carbon structure, Co₃O₄/N–C demonstrates enlarged surface area replenished with more electrocatalytic active sites. What's more, Co₃O₄ nanoparticles are evenly dispersed onto the N-doped carbon surface which effectively prevents their aggregation and detachment. These exclusive structural features render amazing catalytic activity for Co₃O₄/N–C towards OER with an onset potential of ~1.31 V (vs RHE), low overpotential of 120 mV at 10 mA cm⁻² and a Tafel slope of only 33 mV dec⁻¹ in basic media. This work presents a simple approach to meet an ideal catalytic material with better morphology and advantageous properties for the possible energy and environmental applications.     

3D MnCo2O4@CoS nanoarrays with different morphologies as an electrocatalyst for oxygen evolution reaction

The efficiency and stability of electrocatalysts are the key factors for measuring oxygen evolution reaction. In this work, the MnCo₂O₄ structure assembled from well-arranged nanowires or nanosheet arrays has been grown vertically on nickel foam by in-situ hydrothermal method. Interestingly, different morphology of MnCo₂O₄ can be easily regulated by adding NH₄F to a mixed solvent to achieve conversion from nanowires to nanosheets. In addition, further synthesis of unique three-dimensional hierarchical core/shell MnCo₂O₄@CoS nanowires or nanosheets arrays was performed primarily by electrochemical deposition. Both MnCo₂O₄@CoS-7 cycles nanowires and MnCo₂O₄@CoS-7 cycles nanosheets exhibit high efficiency and long-lasting stability for the oxygen oxidation reaction. The lower overpotential of only 280 mV and 270 mV at 20 mA cm⁻² for the MnCo₂O₄@CoS-7 cycles nanowires and MnCo₂O₄@CoS-7 cycles nanosheets were obtained with lower Tafel slopes of 139. 19 mV dec⁻¹ and 131.81 mV dec⁻¹ in 1.0 M potassium hydroxide respectively comparing with our other MnCo₂O₄@CoS catalysts. The results demonstrate that the crystal morphology of MnCo₂O₄@CoS does not significantly influence their electrocatalytic activity in water oxidation reactions by comparing nanostructured MnCo₂O₄@CoS nanowires and MnCo₂O₄@CoS nanosheets. The high catalytic activity of the MnCo₂O₄@CoS nanoarrays is attributed to the possession of more active sites, larger specific surface area, abundant oxygen vacancy, and fast electron transport rate. Not only that, the durability of the MnCo₂O₄@CoS nanoarrays is also excellent after continuous oxygen evolution test of 1000 cycles. The results of XRD, SEM and XPS show that MnCo₂O₄@CoS-7 cycles nanowires and MnCo₂O₄@CoS-7 cycles nanosheets materials can be used as a highly efficient and stable catalyst for oxygen evolution reaction.     

Three-dimensional Co3O4@NiCo2O4 nanoarrays with different morphologies as electrocatalysts for oxygen evolution reaction

Oxygen evolution reaction is one of the key factors restricting the whole process of electrolysis of water. In this paper, hydrothermal and calcination method are used to in situ grow Co₃O₄@NiCo₂O₄ on nickel foam (NF). The formation of Co₃O₄@NiCo₂O₄ nanostructures depends on the different hydrothermal time, which further results in the different growth mechanism of Co₃O₄@NiCo₂O₄ nanostructures. The result shows that Co₃O₄@NiCo₂O₄-8h, as a catalytic material, could play a synergistic role to largely accelerate the electron transfer process and could be efficiently and persistently used in oxygen evolution reaction. The oxygen evolution reaction activity of Co₃O₄@NiCo₂O₄-8h material is significantly improved compared with Co₃O₄, Co₃O₄@NiCo₂O₄-6h and Co₃O₄@NiCo₂O₄-10 h. When the current density is 50 mA cm⁻², the overpotential is only 290 mV for Co₃O₄@NiCo₂O₄-8h material. The enhanced activity Co₃O₄@NiCo₂O₄-8h is attributed to more active site exposure, rapid charge transfer and synergistic catalysis of Co₃O₄ and NiCo₂O₄. This work provides a new idea for the development of efficient, stable and environmentally friendly hybrid catalysts.     

Manganese oxide with different morphology as efficient electrocatalyst for oxygen evolution reaction

Three-dimensional (3D) manganese oxides consisted of tetragonal phase Mn₃O₄ and α-MnO₂ with different morphology have been directly grown vertically on Ti foil by a simple electrochemical method without any template and used as the catalysts for oxygen evolution reaction (OER). The results show that manganese oxides with different morphology show high activity and good stability for OER and the manganese oxide (MnO_x) nanowire arrays obtained at 70 °C show higher activity and better stability than MnO_x with cotton wool structure and MnO_x nanosheet arrays.     

In-situ generated P-doped NiCo2O4 nanosheet arrays with rapid charge transfer for efficient oxygen evolution reaction in alkaline solution

Exploring highly efficient electrocatalysts (OER) is critical for oxygen evolution reaction. Herein, for the first time, P-doped NiCo₂O₄ nanosheet arrays generated on nickel foam (namely P–NiCo₂O₄/NF) were constructed via a feasible protocol. Notably, the etching treatment can open the internal structure of ZIF-67 to offer more electrocatalytically active surface area, and obtained NiCo₂O₄ showed great electrocatalytic performance in OER. The introduction of P can effectively reduce the charge transfer resistance of NiCo₂O₄ and boost OER kinetics. More importantly, doping P not only improved the hydrophilicity of NiCo₂O₄, but also reduced its surface potentials, which provided convenience for the adsorption of OH⁻ over P–NiCo₂O₄/NF electrode. As expected, the P–NiCo₂O₄/NF electrode with good long-term durability displayed excellent performance for OER in alkaline solution, and an overpotential of 121.6 mV was achieved at a current density of 10 mA/cm². To sum up, current work can provide a meaningful reference to prepare electrocatalyst for efficient OER.     

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.