NiFe single atom catalysts anchored on carbon for oxygen evolution reaction

Single atom catalysts (SACs) can improve the efficiency of oxygen evolution reaction (OER). However, metal SACs anchored on carbon materials are relatively uncommon for the OER. In this paper, using carbon black as carrier, NiFe SACs are fabricated by one step pyrolysis method. When the weight ratio of Ni/Fe is lower than 5:3, NiFe@C exibits highly-dispersed SACs over carbon in addition to some Ni₃Fe alloy. The prepared NiFe@C 5:3 SACs showed excellent OER performance with an overpotential of 322 mV and 438 mV for current density of 10 mA/cm² and 100 mA/cm², respectively. The Tafel slope of NiFe@C 5:3 was as small as 87.6 mV/dec, indicating fast charge transfer of NiFe@C 5:3 during OER process, which was also confirmed by electrochemical impedance spectra with R_ct = 18.07 Ωcm². Meanwhile, NiFe@C 5:3 had the highest specific capacitance of 5 mF/cm² with good stability. This work provides a reference for designing electocatalyst material for efficient, stable and economical OER process.     

Cobalt-based composite films on electrochemically activated carbon cloth as high performance overall water splitting electrodes

An attractive approach to obtain effective and stable electrode for water electrolysis is to directly deposit the electrocatalyst on current collector surface. Herein, we show the influence of electrochemical activation of carbon cloth substrate on the morphology and electrocatalytic properties of bifunctional electrodes for both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). A simple one-step electrodeposition technique was applied to directly grow mixed Co-based films on electrochemically activated carbon cloth (EACC) surface. The produced films are composed of metallic Co, and largely amorphous CoO/Co(OH)₂ phases. Variation of Co²⁺ concentration in the solution for electrodeposition enabled tuning the composition of mixed films in order to achieve the optimal HER and OER electrocatalytic performance in 0.1 M KOH. The synthesized electrodes require the overpotentials of 195 mV for HER and 340 mV for OER to deliver the current density of 10 mA/cm². The results indicate that the facile oxidation of carbon cloth prior to the electrodeposition decreases the overpotential at 10 mA/cm² by 150 and 60 mV for HER and OER respectively, thus opening the perspective of improving the activity of carbon-based self-supported composite electrocatalytic electrodes for advanced energy conversion processes.     

Phosphate ions-functionalized and wettability-tuned nickel ferrite for boosted oxygen evolution performance

Nickel ferrite (NiFe₂O₄) has been explored as a promising oxygen evolution reaction (OER) electrocatalyst for water splitting owning to its earth-abundant and considerable water oxidation catalytic activity. Nevertheless, its practical electrocatalytic performance towards OER is still undesirable due to the sluggish OER kinetics and high overpotential gap on the water oxidation anode side. In this work, in order to enhance the electrochemical water oxidation performance of NiFe₂O₄, the surface of NiFe₂O₄ is functionalized with phosphate ions (Pi) by using a facile incipient impregnation and following calcination process. Results demonstrate that the OER properties of NiFe₂O₄ under alkaline conditions can be dramatically boosted by the surface Pi functionalization. In 1.0 M KOH solution, the resulting NiFe₂O₄-Pi on glassy carbon (GC) electrode demonstrates quite lower overpotential of 332 mV (10 mA/cm²) and Tafel slope of 57 mV/dec compared to that of pristine NiFe₂O₄ (443 mV@10 mA/cm² and 96 mV/dec), which is also better than that of commercial RuO₂ electrocatalysts (348 mV@10 mA/cm² and 80 mV/dec). Moreover, such electrocatalyst on nickel foam electrode also realizes superior OER durability to afford a current density of 70 mA/cm² at overpotential of only 300 mV for at least 28 h. The excellent electrocatalytic water oxidation activities of NiFe₂O₄-Pi can be attributed to the tuning electronic property and surface wettability by Pi ions functionalization. This work provides us a novel and effective approach to modify the photo-/electrocatalytic activity for transition metal oxides.     

Three-dimensional hierarchically porous iridium oxide-nitrogen doped carbon hybrid: An efficient bifunctional catalyst for oxygen evolution and hydrogen evolution reaction in acid

Active and durable acid medium electrocatalysts for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) are of critical importance for the development of proton exchange membrane (PEM) water electrolyser or Fuel cells. Herein, we report a facile method for the synthesis of 3D-hierarchical porous iridium oxide/N-doped carbon hybrid (3D-IrO₂/N@C) and its superior OER and HER activity in acid. In 0.5 M HClO₄, this catalyst exhibited remarkable activity towards OER with a low overpotential of 280 mV at 10 mA/cm² current density, a low Tafel slope of 45 mV/dec and ∼98% faradaic efficiency. The mass activity (MA) and turnover frequency (TOF) are found to be 833 mA/mg and 0.432 s⁻¹ at overpotential of 350 mV which are ∼32 times higher than commercial (comm.) IrO₂. The HER performance of this 3D-IrO₂/N@C is comparable with comm. Pt/C catalyst in acid. This 3D-IrO₂/N@C catalyst requires only 35 mV overpotential to reach a current density 10 mA/cm² with Tafel slope 31 mV/dec. Most importantly, chronoamperometric stability test confirmed superior stability of this catalyst towards HER and OER in acid. This 3D-IrO₂/N@C catalyst was applied as both cathode and anode for over-all water splitting and required only 1.55 V overpotential to achieve a current density of 10 mA/cm² in acid. The outstanding activity of the 3D-IrO₂/N@C catalyst can be attributed to a unique hierarchical porous network, high surface area, higher electron and mass transportation, synergistic interaction between IrO₂ and carbon support.     

Growth of nickel vacancy NiFe-LDHs on Ni(OH)2 nanosheets as highly efficient bifunctional electrocatalyst for overall water splitting

A bifunctional electrocatalyst was fabricated by in-situ vertical growth of Ni(OH)₂ nanosheets on nickel foam (NF), with subsequent accretion of nickel vacancy NiFe-LDHs (Ni^vacFe-LDHs) by two step hydrothermal method. It was exhibited to be a high-efficiency overall water splitting performance with good stability. The low over-potentials of 292, 330, and 376 mV were acquired when the current density was selected as 50, 100, and 200 mA/cm² for oxygen evolution reaction (OER) with a relatively low Tafel slope. It also achieved low over-potentials of 116 and 247 mV when the current densities were 10 and 200 mA/cm² for hydrogen evolution reaction (HER), and Tafel slope was estimated to be 95.87 mV/dec. For the overall water splitting, NF–Ni(OH)₂-Ni^vacFe-LDHs needed only a low overpotential (291 mV) to achieve 25 mA/cm² in 1 mol/L potassium hydroxide. The long-term testing of this electrode for 24 h chronopotentiometric test at 25 mA/cm² demonstrated very eminent stability.     

Electrodeposition of NiFe layered double hydroxide on Ni3S2 nanosheets for efficient electrocatalytic water oxidation

The oxygen evolution reaction (OER) plays a vital role in various energy conversion applications. Up to now, the highly efficient OER catalysts are mostly based on noble metals, such as Ir- and Ru-based catalysts. Thus, it is extremely urgent to explore the non-precious electrocatalysts with great OER performance. Herein, a simple electrodeposition combined with hydrothermal method is applied to synthesize a non-precious OER catalyst with a three-dimensional (3D) core-shell like structure and excellent OER performance. In our work, NiFe layered double hydroxide (LDH) was electrodeposited on Ni₃S₂ nanosheets on nickel foam (NF), which exhibits a better performance compared with RuO₂, and a low overpotential of 200 mV is needed to reach the current density of 10 mA/cm² in 1 M KOH. Notably, the Ni₃S₂/NiFe LDH only need an overpotential of 273 mV to reach the current density of 200 mA/cm².     

Chromium nitride/Cr coated 316L stainless steel as bipolar plate for proton exchange membrane fuel cell

Chromium nitride/Cr coating has been deposited on surface of 316L stainless steel to improve conductivity and corrosion resistance by physical vapor deposition (PVD) technology. Electrochemical behaviors of the chromium nitride/Cr coated 316L stainless steel are investigated in 0.05 M H₂SO₄ + 2 ppm F⁻ simulating proton exchange membrane fuel cell (PEMFC) environments, and interfacial contact resistance (ICR) are measured before and after potentiostatic polarization at anodic and cathodic operation potentials for PEMFC. The chromium nitride/Cr coated 316L stainless steel exhibits improved corrosion resistance and better stability of passive film either in the simulated anodic or cathodic environment. In comparison to 316L stainless steel with air-formed oxide film, the ICR between the chromium nitride/Cr coated 316L stainless steel and carbon paper is about 30 mΩ cm² that is about one-third of bare 316L stainless steel at the compaction force of 150 N cm⁻². Even stable passive films are formed in the simulated PEMFC environments after potentiostatic polarization, the ICR of the chromium nitride/Cr coated 316L stainless steel increases slightly in the range of measured compaction force. The excellent performance of the chromium nitride/Cr coated 316L stainless steel is attributed to inherent characters. The chromium nitride/Cr coated 316L stainless steel is a promising material using as bipolar plate for PEMFC.     

Chalcogenide nanocomposite electrodes grown by chemical etching of Ni-foam as electrocatalyst for efficient oxygen evolution reaction

We report on the synthesis of NiSSe nanocomposite by chemical etching of Ni-foam using simple solvothermal technique and investigated it as an electrocatalyst for the oxygen evolution reaction (OER). Different morphologies such as nanograins, branched mesh-like architecture, and agglomerated nanograins with nanoporous are obtained for NiSSe, NiSe, and NiS, respectively. The overpotentials of 247, 266, and 329 mV (vs RHE) are obtained to attain a current density of 30 mA cm⁻² for NiSSe, NiS, and NiSe nanocomposites, respectively. Interestingly, ternary nanocomposite reaches a high current density of 100 mA cm⁻² by operating only at an overpotential of 342 mV. The low Tafel slope of 175.7 mV dec⁻¹ reveals that the ternary nanocomposite consists of most favorable catalytic kinetics for mass and electron transport during the OER reaction. The improved catalytic performance of NiSSe nanocomposite is attributed to the synergy between electrochemcial surface area and improved electronic conductivity.     

Highly durable,Pt free and large-area Ni–B film synthesized by SILAR as a bifunctional electrode for electrochemical water splitting

A search for efficient, durable, large-area, and economic catalyst material for low-cost production of hydrogen and oxygen is currently a high priority in the field of electrocatalysis (EC). In view of this, a cost-effective, earth abundant, highly stable, Pt free, and large-area (8 cm × 8 cm) bifunctional Ni–B electrocatalyst is reported via simple and economic SILAR method. A highly porous surface of Ni–B film with high surface wettability indicated better electrochemical water-splitting properties for the films and is obtained at 100 cycles. A Low over-potential value to obtain HER (49 mV) and OER (340 mV) at 10 mA/cm² current suggested that they are comparable to the well-known Pt and RuO electrodes in alkaline medium (1M KOH), respectively. In actual water-splitting setup having Ni–B film (as cathode) and stainless steel (as anode), the hydrogen production of 612 ml/h is obtained at constant potential, which was enhanced by 18% i.e., 726 ml/h when a Ni–B film as both cathode and anode electrode was used. Both the electrodes are highly stable for over 15 days and interestingly they showed 7% increment in the EC performance.     

Cadmium sulfide embedded Prussian Blue as highly active bifunctional electrocatalyst for water-splitting process

Hydrogen production by water-splitting has limited commercial application as substantial amount of energy is required for the favorable kinetics of the process. We present an interface engineering strategy for constructing a bifunctional electrode material for an efficient water splitting process. Designed cadmium sulphide and Prussian blue nanorods (CdS-NRs@PBNPs) heterostructures acts as bifunctional electrocatalyst improved water splitting performance, for both HER and OER. For HER, the optimized hybrid CdS-NRs@PBNPs (1:1) showed significantly a low overpotentials of 126 mV and 181 mV at current densities of 10 mA cm^?2 and 20 mA cm^?2 respectively. For OER it displays an overpotential of 250 mV and 316 mV at current densities of 10 mA cm^?2 and 20 mA cm^?2. Additionally, the CdS-NRs@PBNPs (1:1) has demonstrated long-term stability. The hybrid's enhanced OER and HER activity is attributable to a synergetic impact between CdS-NRs and PBNPs, as well as the active site modification due to the presence of Cadmium and iron in the hybrid.     

Novel 3-D urchin-like Ni– Co–W porous nanostructure as efficient bifunctional superhydrophilic electrocatalyst for both hydrogen and oxygen evolution reactions

Fabrication of an electrocatalyst with remarkable electrocatalytic activity for both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is important for the production of hydrogen energy. In this study, Ni–Co–W alloy urchin-like nanostructures were fabricated by binder-free and cost-effective electrochemical deposition method at different applied current densities and HER and OER electrocatalytic activity was studied. The results of this study showed that the microstructure and morphology are strongly influenced by the electrochemical deposition parameters and the best electrocatalytic properties are obtained at the electrode created at the 20 mA.cm⁻²applied current density. The optimum electrode requires −66 mV and 264 mV, respectively, for OER and HER reactions for delivering the 10 mA cm⁻² current density. The optimum electrode also showed negligible potential change after 10 h electrolysis at 100 mA cm⁻², which means remarkable electrocatalytic stability. In addition, when this electrode used as a for full water splitting, it required only 1.58 V to create a current density of 10 mA cm⁻². Such excellent electrocatalytic activity and stability can be related to the high electrochemical active surface area, being binder-free, high intrinsic electrocatalytic activity and hydrophilicity. This study introduces a simple and cost-effective method for fabricating of effective electrodes with high electrocatalytic activity.     

Effect of iron on Ni–Mo–Fe composite as a low-cost bifunctional electrocatalyst for overall water splitting

By increasing demand for hydrogen and oxygen gas for energy and industrial applications, designing a cheap, high-efficiency, and bifunctional electrocatalyst for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) seems necessary. For this purpose Ni–Mo–Fe as a bifunctional electrocatalyst was synthesized by one-step electrodeposition. From this electrocatalyst with optimal composition and current density, a small overpotential of 65, 161 mV for delivering 10, 100 mA/cm² on HER in alkaline media was achieved. As-fabricated electrode exhibited 344,408 mV for delivering 10, 100 mA/cm² in OER. Furthermore, this electrocatalyst shows high stability and negligible degradation in overpotential for HER and OER under long term stability tests in alkaline media. The notable function of As-fabricated Ni–Mo–Fe is due to the synergism effect between Ni, Mo, and Fe element and binder-free structure. Owing to the high-performance and high-stability of Ni–Mo–Fe electrocatalyst under Hydrogen and Oxygen evolution reactions is a candidate for industrial uses in the alkaline electrolyzer.     

Accelerated oxygen evolution kinetics on NiFeAl-layered double hydroxide electrocatalysts with defect sites prepared by electrodeposition

NiFe layered double hydroxides (LDHs) is considered to be one of the LDHs electrocatalyst materials with the best electrocatalytic oxygen evolution properties. However, its poor conductivity and inherently poor electrocatalytic activity are considered to be the limiting factors inhibiting the electrocatalytic properties for oxygen evolution reaction (OER). The amorphous NiFeAl-LDHs electrocatalysts were prepared by electrodeposition with nickel foam as the support, and the D-NiFeAl-LDHs electrocatalyst with defect sites was then obtained by alkali etching. The mechanism of catalysts with defect sites in OER was analyzed. The ingenious defects can selectively accelerate the adsorption of OH⁻, thus enhancing the electrochemical activity. The D-NiFeAl-LDHs electrocatalyst had higher OER electrocatalytic activity than NiFe-LDHs electrocatalyst: its accelerated OER kinetics were mainly due to the introduction of iron and nickel defects in NiFeAl-LDHs nanosheets, which effectively adjusted the surface electronic structure and improved OER electrocatalytic performance. There was only a low overpotential of 262 mV with the current density of 10 mA cm⁻², and the Tafel slope was as low as 41.67 mV dec⁻¹. The OER electrocatalytic performance of D-NiFeAl-LDHs was even better than those of most of the reported NiFe-LDHs electrocatalysts.     

Molybdenum carbide coated 316L stainless steel for bipolar plates of proton exchange membrane fuel cells

Superior corrosion resistance and high electrical conductivity are crucial to the metallic bipolar plates towards a wider application in proton exchange membrane fuel cells. In this work, molybdenum carbide coatings are deposited in different thicknesses onto the surface of 316 L stainless steel by magnetron sputtering, and their feasibility as bipolar plates is investigated. The microstructure characterization confirms a homogenous, compact and defectless surface for the coatings. The anti-corrosion performance improves with the increase of the coating thickness by careful analysis of the potentiodynamic and potentiostatic data. With the adoption of a thin chromium transition layer and coating of a ∼1052 nm thick molybdenum carbide, an excellent corrosion current density of 0.23 μA cm⁻² is achieved, being approximately 3 orders of magnitude lower than that of the bare stainless steel. The coated samples also show a low interfacial contact resistance down to 6.5 mΩ cm² in contrast to 60 mΩ cm² for the uncoated ones. Additionally, the hydrophobic property of the coatings’ surface is beneficial for the removal of liquid water during fuel cell operation. The results suggest that the molybdenum carbide coated stainless steel is a promising candidate for the bipolar plates.     

Improved anticorrosion properties and electrical conductivity of 316L stainless steel as bipolar plate for proton exchange membrane fuel cell by lower temperature chromizing treatment

The lower temperature chromizing treatment is developed to modify 316L stainless steel (SS 316L) for the application of bipolar plate in proton exchange membrane fuel cell (PEMFC). The treatment is performed to produce a coating, containing mainly Cr-carbide and Cr-nitride, on the substrate to improve the anticorrosion properties and electrical conductivity between the bipolar plate and carbon paper. Shot peening is used as the pretreatment to produce an activated surface on stainless steel to reduce chromizing temperature. Anticorrosion properties and interfacial contact resistance (ICR) are investigated in this study. Results show that the chromized SS 316L exhibits better corrosion resistance and lower ICR value than those of bare SS 316L. The chromized SS 316L shows the passive current density about 3E−7 A cm⁻² that is about four orders of magnitude lower than that of bare SS 316L. ICR value of the chromized SS 316L is 13 mΩ cm² that is about one-third of bare SS 316L at 200 N cm⁻² compaction forces. Therefore, this study clearly states the performance advantages of using chromized SS 316L by lower temperature chromizing treatment as bipolar plate for PEMFC.     

Controllable synthesis of one-dimensional NiS2 nanotube and nanorod arrays on nickel foams for efficient electrocatalytic water splitting

One-dimensional NiS₂ nanotube arrays and nanorod arrays are controllably grown on Ni foam surface. The electrocatalytic test shows that the NiS₂ nanotube arrays require competitive overpotentials of 209 mV for HER and 367 mV for OER (to achieve a current density of 50 mA/cm²), respectively, which are much lower than the NiS₂ nanorod arrays and other NiS₂ nanostructures reported before. Specifically, the NiS₂ nanotube arrays can be employed as an efficient bi-functional catalyst for overall water splitting, with a low cell voltage (1.58 V) to deliver a current density of 10 mA/cm². The outstanding performance can be attributed to the special structural characteristics of nanotubes, which have high specific surface areas along with abundant active sites. The present study not only enriches the morphology of NiS₂ nanostructures for highly efficient electrocatalytic reaction, but also provides an interesting self-assembly path for the synthesis of one-dimensional NiS₂ nanostructures.     

Influence of fluoride ions on corrosion performance of 316L stainless steel as bipolar plate material in simulated PEMFC anode environments

Corrosion performance of 316L stainless steel as a bipolar plate material in proton exchange membrane fuel cell (PEMFC) is studied under different simulated PEMFC anode conditions. Solutions of 1 × 10⁻⁵ M H₂SO₄ with a wide range of different F⁻ concentrations at 70 °C bubbled with hydrogen gas are used to simulate the PEMFC anode environments. Electrochemical methods, both potentiodynamic and potentiostatic, are employed to study the corrosion behavior. Scanning electron microscope (SEM) and atomic force microscope (AFM) are used to examine the surface morphology of the specimen after it is potentiostatic polarized in simulated PEMFC anode environments. X-ray photoelectron spectroscopy (XPS) analysis is used to identify the compositions and the depth profile of the passive film formed on the 316L stainless steel surface after it is polarized in simulated PEMFC anode environments. Mott–Schottky measurements are used to characterize the semiconductor passive films. The results of potentiostatic analyses show that corrosion currents increase with F⁻ concentrations. SEM examinations show that no localized corrosion occurs on the surface of 316L stainless steel and AFM measurement results indicate that the surface topography of 316L stainless steel becomes slightly rougher after polarized in solutions with higher concentration of F⁻. From the results of XPS analysis and Mott–Schottky measurements, it is determined that the passive film formed on 316L stainless steel is a single layer n-type semiconductor.     

Facile modified polyol synthesis of FeCo nanoparticles with oxyhydroxide surface layer as efficient oxygen evolution reaction electrocatalysts

The oxygen evolution reaction (OER) at anode requires high overpotential and is still challenging. The metallic core-oxyhydroxide layer structure is an efficient method to lower an overpotential. We synthesized Fe rich FeCo core-Co rich FeCo oxyhydroxide layer with a different particle size of 173 nm, 225 nm, and 387 nm (FeCo 173, 225, 387) through a difference in the reduction rate of Fe/Co precursors using facile modified polyol synthesis. To investigate the effect of conductivity, CoFe₂O₄ nanoparticles of 80–130 nm were synthesized. Among samples, FeCo 173 showed remarkable catalytic performance of 316 mV at a current density of 10 mA/cm² in 0.1 M KOH compared to RuO₂ (408 mV), FeCo 225 (323 mV), FeCo 387 (334 mV), CoFe₂O₄ (382 mV). Moreover, FeCo 173 showed good stability for 60,000 s while RuO₂ showed a gradual increase in overpotential to maintain 10 mA/cm² after 15,000 s in chronopotentiometry. The excellent performance was attributed to Fe-rich metallic core, a small amount of Fe doping into CoOOH, and the synergic effect between the active site of Co rich FeCoOOH and conductive Fe rich metallic core. Following this result, it shows that the use of such FeCo electrodes has advantages in the production of hydrogen via electrochemical water oxidation.     

Polypyrrole assisted synthesis of nanosized iridium oxide for oxygen evolution reaction in acidic medium

The application of electrochemical water splitting process in acidic medium is restricted by the lack of highly efficient and stable oxygen evolution reaction (OER) electrocatalyst. In this work, we report a facile soft template method to synthesize nanosized iridium oxide for electrocatalytic OER in acidic medium. The fabrication process involves thermal treatment of iridium complex and polypyrrole in air. The compositions and structures of the resulting catalytic materials are significantly influenced by the annealing temperature. The nanostructured iridium oxide synthesized at optimal 450 °C exhibits low overpotential (291.3 ± 6 mV) to reach 10 mA/cm² current density towards OER, which is better than the commercial iridium oxide. Further investigation indicates that nanosized iridium oxide synthesized at 450 °C has high electrochemical active surface area to expose abundant accessible active sites, which can accelerate the OER rate. This method can also provide new guidance to prepare other metal oxide nanoparticles for various applications.