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.     

CoFe2O4 nanoparticles anchored on N/S co-doped mesoporous carbon spheres as efficient bifunctional electrocatalysts for oxygen catalytic reactions

The development of a promising bifunctional electrocatalyst for oxygen catalytic reactions such as the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is highly desirable owing to the sluggish kinetics that limit these reactions. In this study, CoFe₂O₄ nanoparticles anchored on nitrogen and sulfur co-doped mesoporous carbon spheres (CFO/NS-MCS) were prepared as nonprecious metal catalysts, using a facile pyrolysis and hydrothermal treatment process. The co-doping of N and S into the carbon spheres was achieved using thiourea, which played a key role in the bimetallic covalent coupling in the NS-MCS. The as-prepared CFO/NS-MCS exhibited a more promising ORR catalytic performance compared with that of commercial Pt/C, which was attributed to the presence of highly active sites. Remarkably, the CFO/NS-MCS catalysts also showed a high OER catalytic performance comparable with that of commercial RuO₂/C in the aspects of onset potential and Tafel slope, and showed a better durability for oxygen catalytic reactions in an alkaline solution. The approach indicated in this research can be applied to develop high-performance electrocatalysts for practical implementation in energy storage and conversion devices.     

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.     

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.     

One-step synthesis of Ni3S2 nanowires at low temperature as efficient electrocatalyst for hydrogen evolution reaction

Ni₃S₂ is an emerging cost-effective catalyst for hydrogen generation. However, a large amount of reported Ni₃S₂ was synthesized via multi-step approaches and few were fabricated based on the one-step strategies. Herein, we report a facile one-step low-temperature synthesis of Ni₃S₂ nanowires (NWs). In this strategy, a resin containing sulfur element is recommended as a sulfur resource to form Ni₃S₂ NWs. It presents a plausible explanation on the vapor–solid–solid (VSS) growth mechanism according to the results of this experiment and reported in literature that has been published. The Ni₃S₂ NW exhibits a potential ∼199 mV at 10 mA cm⁻² and the long-term durability over 30 h at 20 mA cm⁻² HER operation, better than other reported Ni₃S₂. More importantly, according to replace transition metal foam as the initial metal, other transition metal sulfide can be readily synthesized via this original approach.     

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.     

FeOOH/Ni heterojunction nanoarrays on carbon cloth as a robust catalyst for efficient oxygen evolution reaction

Developing catalysts based on transition metal-based materials for oxygen evolution reaction (OER), which are cheap and efficient, is one of the keys to increase the rate of electrolysis of water to produce hydrogen. Herein, we successfully synthesize iron hydr(oxy)oxide nano-arrays on carbon cloth (FeOOH@CC), and then metallic nickel is electrodeposited on its surface to fabricate FeOOH/Ni heterojunction nanoarrays. Notably, the optimal FeOOH/Ni heterojunction nanoarrays catalyst shows high electrocatalytic performance toward OER with a small overpotential of 257.8 mV at 50 mA cm⁻², a Tafel slope of 30.8 mV dec⁻¹ and outstanding long-term stability in alkaline media. The superior OER performance could be ascribed to the introducing of metallic nickel. The nickel in-situ grows on the surface of FeOOH, which not only can improve the conductivity of FeOOH, but also cooperate with FeOOH to form the FeOOH/Ni heterogeneous interfaces for further enhancing OER electrocatalytic activities. This work provides a simple and efficient strategy of interface engineering to fabricate oxyhydroxide/metal heterojunction nanoarrays as high-efficiency OER catalysts.     

Low-pressure-plasma-processed NiFe-MOFs/nickel foam as an efficient electrocatalyst for oxygen evolution reaction

A NiFe bimetallic metal organic framework (MOF) deposited on nickel foam and processed by low-pressure plasmas with 95%Ar+5%H₂, pure Ar, and 95%Ar+5%O₂ gases is used as an electrocatalyst for the oxygen evolution reaction. An alkaline solution (1 M KOH) with 95%Ar+5%H₂ plasma processed NiFe-MOFs/NF exhibits the best electrocatalytic performance with the lowest overpotential of 149 mV at a current density of 10 mA cm^?2 and a Tafel slope of 54 mV dec^?1. Furthermore, electrical impedance spectroscopy and cyclic voltammetry show that after 95%Ar+5%H₂ plasma treatment, the interfacial impedance greatly reduces, and the electrical double-layer capacitance slightly increased.     

Electrochemical aspects of Co3O4 nanorods supported on the cerium doped porous graphitic carbon nitride nanosheets as an efficient supercapacitor electrode and oxygen reduction reaction electrocatalyst

Herein, the electrochemical performance of Ce-PGCN,NS/Co₃O₄ as a metal-free ORR electrocatalyst and supercapacitor electrode was investigated. FESEM, TEM, BET, FTIR, XRD, EDX, FTIR, and Raman tests were used to characterize the synthesized electrocatalysts. For ORR measurements, voltammetry (CV, LSV, Choronoamperometry) and EIS tests were used to investigate the electrocatalytic activity of the electrocatalysts. And for supercapacitor measurements, the CV and GCD tests were conducted to examine the electrode's capacitance. The results of the voltammetry tests show that Ce-PGCN,NS/Co₃O₄ with an onset potential of −0.027 V, selecting four-electron pathway (n = 3.86), Tafel slope of 137 mV/dec, charge transfer of 570 Ω, and high durability in alkaline media (0.1 M KOH) show an excellent electrochemical performance as an ORR electrocatalyst and can be introduced as a promising substitution for commercial Pt/C catalysts. On the other hand, the results of CV in supercapacitor mode and GCD reveal that Ce-PGCN,NS/Co₃O₄ electrode with the specific capacitance of 789 F g⁻¹ at the current density of 1 A g⁻¹ and high stability in alkaline media (2 M KOH), have superior performance as a supercapacitor electrode than other electrode based on the g-C₃N₄. Also, it is observed that converting bulk g-C₃N₄ to PGCN,NS, doping Cerium atoms on the structure of the PGCN,NS, and adding Co₃O₄ nanorods impact the electrocatalytic activity of g-C₃N₄ positively.     

Free-standing carbon nanotubes as non-metal electrocatalyst for oxygen evolution reaction in water splitting

Oxygen evolution reaction (OER) has significant impact on the overall electrochemical water splitting. We introduce, for the first time, a facile approach towards the fabrication of versatile electrode composed of free-standing multiwalled carbon nanotubes (MWCNTs) as electrocatalyst for the water splitting reaction. Directly extracted MWCNTs as sheets from vertically grown arrays transferred over the glass substrate, are used without any post treatment as a working electrode for OER. Onset potential of 1.60 V was achieved for MWCNTs which is significantly reduced as compared to platinum based metal electrode (1.72 V) with excellent current density. No surface modification, metal-free nature, flexibility and low cost with excellent catalytic activity proved this material as a promising candidate for the replacement of metal based electrodes in electrochemical water splitting.     

Pt nanodendrites anchored on bamboo-shaped carbon nanofiber arrays as highly efficient electrocatalyst for oxygen reduction reaction

In order to improve the Pt utilization and enhance their catalytic performance in fuel cells, a novel composite electrode composed of single-crystalline Pt nanodendrites and support constructed by bamboo-shaped carbon nanofiber arrays (CNFAs) on carbon paper, is reported. This electrode is designed by growing vertically CNFAs on carbon paper via plasma enhanced chemical vapor deposition, followed by the direct synthesis of Pt nanodendrites using a simple surfactant-free aqueous solution method. Electron microscopy studies reveal that the Pt nanodendrites are uniformly high dispersed and anchored on the surface of CNFAs. Electrochemical measurements demonstrate that the resultant electrode exhibits higher electrocatalytic activity and stability for oxygen reduction reaction than commercial Pt/C catalyst, suggesting its potential application in fuel cells.     

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.     

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.     

Co/Mo2C composites for efficient hydrogen and oxygen evolution reaction

Non-precious transition metal electrocatalysts with high catalytic performance and low cost enable the scalable and sustainable production of hydrogen energy through water splitting. In this work, based on the polymerization of CoMoO₄ nanorods and pyrrole monomer, a heterointerface of carbon-wrapped and Co/Mo₂C composites are obtained by thermal pyrolysis method. Co/Mo₂C composites show considerable performance for both hydrogen and oxygen evolution in alkaline media. In alkaline media, Co/Mo₂C composites show a small overpotential, low Tafel slope, and excellent stability for water splitting. Co/Mo₂C exhibits a small overpotential of 157 mV for hydrogen evolution reaction and 366 mV for oxygen evolution reaction at current density of 10 mA cm⁻², as well as a low Tafel slope of 109.2 mV dec⁻¹ and 59.1 mV dec⁻¹ for hydrogen evolution reaction and oxygen evolution reaction, respectively. Co/Mo₂C composites also exhibit an excellent stability, retaining 94% and 93% of initial current value for hydrogen evolution reaction and oxygen evolution reaction after 45,000 s, respectively. Overall water splitting via two-electrode water indicates Co/Mo₂C can hold 91% of its initial current after 40,000 s in 1 M KOH.     

Facile one-pot synthesis of binder-free nano/micro structured dendritic cobalt activated nickel sulfide: a highly efficient electrocatalyst for oxygen evolution reaction

Reasonable design and preparation of non-noble metal electrocatalysts with predominant catalytic activity and long-term stability for oxygen evolution reaction (OER) are essential for electrocatalytic water splitting. Ni foam (NF) is highlighted for its 3D porous structure, impressive conductivity and large specific surface area. Herein, nano/micro structured dendritic cobalt activated nickel sulfide grown on 3D porous NF (Co–Ni₃S₂/NF) has been successfully synthesized by one-step hydrothermal method. Due to the ingenious incorporation of Co, Co–Ni₃S₂/NF electrode shows auspicious electrocatalytic performance for OER compared with Ni₃S₂/NF electrode. As a result, Co–Ni₃S₂/NF needs overpotential of only 274 and 459 mV at current density of 10 and 50 mA cm⁻², respectively, while Ni₃S₂/NF requires overpotential of 344 and 511 mV. At potential of 2.0 V (vs. RHE), Co–Ni₃S₂/NF displays current density of 191 mA cm⁻², while Ni₃S₂/NF just attains current density of only 135 mA cm⁻². Moreover, Co–Ni₃S₂/NF demonstrates excellent stability for uninterrupted OER in alkaline electrolyte. The strategy of designing and preparing cobalt activated nickel sulfide grown on NF renders a magnificent prospect for the development of metal-sulfide-based oxygen evolution catalysts with excellent electrocatalytic performances.     

Uniform cobalt grafted on vanadium nitride as a high efficient oxygen evolution reaction catalyst

The rational design of highly effective and low-cost catalysts for oxygen evolution reaction (OER) is of prime importance for the development of water splitting. However, the activity of electrocatalysts still needs enhancement to satisfy the practical application. Herein, we report Co nanoparticles grafted on vanadium nitride (VN) surface via in situ phase separation method by nitriding Co₂V₂O₇ precursor. Benefiting the advantages of abundant active sites of Co, high conductivity and corrosion resistance of VN, the Co/VN achieves incredibly high activity and durability for OER with a low overpotential of 320 mV at a current density of 10 mV cm^?2 with a small Tafel slope of 50.4 mV dec^?1 and long-term stability. In addition, the in situ Raman further reveals the synergistic effect of Co and VN. Significantly, this study may enrich our knowledge and it can be extended to prepare other interconnected framework structures for the development of OER catalysts.     

Ir-doped Co3O4 as efficient electrocatalyst for acidic oxygen evolution reaction

Oxygen evolution reaction (OER) is an important bottleneck for large-scale acidic water splitting applications due to its sluggish reaction kinetics. Therefore, the development of highly active, stable, and inexpensive electrocatalysts for OER remains a challenge. Herein, we develop the iridium doped Co₃O₄ (Ir–Co₃O₄) with low Ir content of 2.88 wt% for efficient acidic OER. Considering systemic characterizations, it is probably concluded that Ir can be uniformly doped into the lattice of Co₃O₄ and induce a certain distortion. The electrochemical results reveal that Ir–Co₃O₄ nanoparticles demonstrate significantly enhanced electrocatalytic OER activity and stability in 0.5 M H₂SO₄ solution compared with pure Co₃O₄, in which the overpotential at the current density of 10 mA cm⁻² decreases from 382 mV to 225 mV and the value of Tafel slope decreases from 101.7 mV dec⁻¹ to 64.1 mV dec⁻¹. Besides, Ir–Co₃O₄ exhibits excellent electrocatalytic durability for continuous 130 h's test without any activity attenuation. Moreover, this work provides a kind of high-performance acidic OER electrocatalyst for the development of hydrogen energy.     

Carbon supported nickel phosphide as efficient electrocatalyst for hydrogen and oxygen evolution reactions

Hydrogen production through water splitting is an efficient and green technology for fulfilling future energy demands. Carbon nanotubes (CNT) supported Ni₂P has been synthesized through a simpler hydrothermal method. Ni₂P/CNT has been employed as efficient electrocatalysts for hydrogen and oxygen evolution reactions in acidic and alkaline media respectively. The electrocatalyst has exhibited low overpotential of 137 and 360 mV for hydrogen and oxygen evolution reactions respectively at 10 mA cm^?2. Lower Tafel slopes, improved electrochemical active surface area, enhanced stability have also been observed. Advantages of carbon support in terms of activity and stability have been described by comparing with unsupported electrocatalyst.     

Promoted oxygen evolution reaction efficiency by Ni3S2/WO3 nanocomposite anchored over rGO

To develop a high-efficient catalyst for oxygen evolution reaction (OER), creating high current densities at low overpotentials is highly desirable. Herein, an effective and low cost catalyst based on anchoring Ni₃S₂/WO₃ nanocomposite over the reduced graphene oxide (rGO) was hydrothermaly synthesized and characterized using spectroscopic and microscopic techniques, and its electrochemical parameters as a suitable OER electrocatalyst in alkaine media at surface of nickel foam (NF) was studied. Electrochemical measurements showed that, anchored Ni₃S₂/WO₃ on rGO increased ionic conductivity, surface area, active sites of electrocatalyst, decreased the charge transfer resistance and exhibit the overpotential of 280 mV to reach 50 mA cm^?2, with a Tafel slope of ～48 mV/dec and good stability for the OER in comparison to other tested composites. As a result, this catalyst can work at high and low current densities for a long time.     

Cu2S/Ni3S2 ultrathin nanosheets on Ni foam as a highly efficient electrocatalyst for oxygen evolution reaction

It is an inevitable choice to find efficient and economically-friendly electrocatalysts to reduce the high overpotential of oxygen evolution reaction (OER), which is the key to improve the energy conversion efficiency of water splitting. Herein, we synthesized Cu₂S/Ni₃S₂ catalysts on nickel foam (NF) with different molar ratios of Ni/Cu by a simple two-step hydrothermal method. Cu₂S/Ni₃S₂-0.5@NF (CS/NS-0.5@NF) effectively reduces the overpotential of OER, displaying small overpotentials (237 mV@100 mA cm^?2 and 280 mV@500 mA cm^?2) in an alkaline solution, along with a low Tafel slope of 44 mV dec^?1. CS/NS-0.5@NF also presents an excellent durability at a relatively high current density of 100 mA cm^?2 for 100 h. The excellent performance is benefited by the prominent structural advantages and desirable compositions. The nanosheet has a high electrochemical active surface area and the porous structure is conducive to electrolyte penetration and product release. This work provides an economically-friendly Cu-based sulfide catalyst for effective electrosynthesis of OER.