Electrocatalytic Oxygen Evolution Reaction Research Articles

Advances in Spin‐Modulated Electrocatalysis of Oxygen Evolution Reaction

AbstractElectrochemical splitting of water for hydrogen generation has emerged as a potential strategy for transitioning towards renewable energy sources and mitigating the environmental impact of fossil fuel dependence. However, the efficiency of water splitting is mainly hindered by oxygen evolution reaction (OER) at the anode side, which involves kinetically sluggish four proton‐coupled electron‐transfer steps. Recent studies on OER demonstrate that a spin‐dependent mechanism governs the reaction kinetics, wherein the electronic exchange interactions in the catalytic activity of transition metals can provide a spin‐selective channel to filter out electron spins with the right orientation during the formation of O2. Maximizing efficiency and stability of such catalysts require optimization the geometric and electrical structures of transition metal systems. In addition, it is vital to understand the OER mechanism with spin considerations to be familiar with the connection between spin, charge, orbital, and lattice characteristics. This review focuses on current developments in understanding and the use of the spin‐related effect in the OER mechanism.

Constructing Co4(SO4)4 Clusters within Metal-Organic Frameworks for Efficient Oxygen Electrocatalysis.

Multinuclear metal clusters are ideal candidates to catalyze small molecule activation reactions involving the transfer of multiple electrons. However, synthesizing active metal clusters is a big challenge. Herein, on constructing an unparalleled Co4(SO4)4 cluster within porphyrin-based metal-organic frameworks (MOFs) and the electrocatalytic features of such Co4(SO4)4 clusters for the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) is reported. The reaction of CoII sulfate and metal complexes of tetrakis(4-pyridyl)porphyrin under solvothermal conditions afforded Co4-M-MOFs (M═Co, Cu, and Zn). Crystallographic studies revealed that these Co4-M-MOFs have the same framework structure, having the Co4(SO4)4 clusters connected by metalloporphyrin units through Co─Npyridyl bonds. In the Co4(SO4)4 cluster, the four CoII ions are chemically and symmetrically equivalent and are each coordinated with four sulfate O atoms to give a distorted cube-like structure. Electrocatalytic studies showed that these Co4-M-MOFs are all active for electrocatalytic OER and ORR. Importantly, by regulating the activity of the metalloporphyrin units, it is confirmed that the Co4(SO4)4 cluster is active for oxygen electrocatalysis. With the use of Co porphyrins as connecting units, Co4-Co-MOF displays the highest electrocatalytic activity in this series of MOFs by showing a 10mAcm-2 OER current density at 357mV overpotential and an ORR half-wave potential at 0.83V versus reversible hydrogen electrode (RHE). Theoretical studies revealed the synergistic effect of two proximal Co atoms in the Co4(SO4)4 cluster in OER by facilitating the formation of O─O bonds. This work is of fundamental significance to present the construction of Co4(SO4)4 clusters in framework structures for oxygen electrocatalysis and to demonstrate the cooperation between two proximal Co atoms in such clusters during the O─O bond formation process.

Role of Fe and Cr doped ZnO nanoparticles for electrocatalytic oxygen evolution reaction

Developing highly efficient catalysts for oxygen evolution reactions using abundant earth-rich and non-precious metals poses a critical and indispensable challenge. In this study, Fe: 1, 3, and 5% and Cr: 2% doped ZnO nanoparticles (NPs) were synthesized by employing a simple solution combustion method (SCM) for oxygen evaluation reaction (OER). Using a variety of methods, the synthesized transition metal-doped metal oxides were thoroughly examined. The electrochemical behavior of the Fe and Cr-doped ZnO electrodes in an alkaline solution was investigated through LSV, EIS, CV, and CA. The electrochemical studies showed that ZnO/Cr/Fe:5 (η = 305 mV and Tafel slop = 46 mV/dec) demonstrates significant oxygen evolution reaction (OER) activity under alkaline conditions. All prepared samples exhibit good stabilities for up to 10 h.

In-situ grown ternary metal hydroxides@3D oriented crumpled V2C MXene sheets for improved Electrocatalytic Oxygen Evolution Reaction

High valence multi transition metal hydroxides are greatly enriched with OER redox active sites due to strong synergy of heteroatomic nuclei. The efficiency of these redox active sites could be efficiently improved by coupling with highly conductive substrate. The advanced three-dimensional (3D) architecture and hydrophilic terminal functionalities of MXene (MX) considerably enhance the maximum utilization rate of anchored redox active sites by triggering the direct growth of these at MX substrate. Here-in, the freeze-dried 3D network of crumpled Vanadium-Carbide (V2C) MX sheets regulates the crystallization of in-situ grown NiFeCr multi transition metal hydroxides on MX scaffold through co-precipitation process. The XPS results suggest a synergistic chemical interaction of 3D MX scaffold with NiFeCr that modifies the electronic structure of the composite ensuring reduced charge transfer resistance. Besides, as found in FESEM morphological investigation, the well-dispersed NiFeCr multi-transition metal hydroxides are immobilized on open pores like structure of V2C-MX facilitate thoroughly accessible active sites. As a result, the NiFeCr@3D V2C-MX composite has shown an excellent electrocatalytic activity with an overpotential of 410 mV at a current density of 200 mA cm-2, Tafel slope of 100 mV dec in 1M KOH. Besides, the significant interaction between metallic centers and MXene support prevent detachment or agglomeration of active centers providing maximum interaction with the electrolytic ions, quick ionic OH- transportation, speedy and stable electron transfer channels thus ensure the long-term stability of NV-5MX during 53 h continuous operation of OER. Furthermore, we have utilized a more accurate value of half-cell standard reduction potential of the Hg/HgO electrode in the Nernst equation to represent all test voltages and to determine the overpotential values. In essence, this study features a facile approach for the confined growth of multi transition metal hydroxides in the presence of morphologically unique 3D crumpled V2C MXene architectures. Consequently, the increased OER reaction kinetics and improved stability of the synthesized composites are potentially due to synergistic interplay between well dispersed active sites and the conductive substrate.

Structural optimization: Ternary FeNiZn sulfide nanoparticles anchored on nanosheets to strengthen oxygen evolution reaction

Enhancing the activity of oxygen evolution reaction (OER) is crucial for improving the efficiency of electrochemical water splitting (EWS). The highly adjustable electronic structure and potential high conductivity of transition metal sulfides (TMSs) make them promising candidates for OER electrocatalysts. Herein, we have synthesized trimetallic sulfides Fe2Ni1Zn1–S(II) based on layered double hydroxides (LDHs) precursor employing a facile and efficient two-step solvothermal approach. Benefitting from the multi-metallic synergistic effect and the distinctive interfacial structure, Fe2Ni1Zn1–S(II) shows excellent electrocatalytic OER performance (η10 = 252 mV, Tafel slope = 64.2 mV∙dec−1). Meanwhile, it has outstanding stability (50 h) in 1 M KOH, which is better than RuO2 and many other metal sulfide electrocatalysts. Furthermore, it was found that the structure of the catalyst was still retained after OER test, which further verified its catalytic stability. This work supplies an effective route for the preparation of LDHs derived multi-metallic sulfides.

NiCo-LDH sheets and Ag3PO4 nanoparticles decorated on graphitic carbon nitride for efficient oxygen evolution reaction

Ternary heterostructure engineering enables highly efficient interfacial charge transfer, which can enhance the efficiency of electrocatalysts for the oxygen evolution reaction (OER), and has thus attracted widespread interest in electrocatalysis. NiCo-LDH/CN/AgPO was synthesized via ultrasonication and subjected to morphological analyses using X-ray diffraction, scanning electron microscopy, and (high-resolution) transmission electron microscopy. The synergistic effects in the ternary heterostructured NiCo-LDH/CN/AgPO nanocomposite comprising 2D nickel-cobalt layered double hydroxide (NiCo-LDH) and silver phosphate (Ag3PO4) nanospecies anchored on graphitic carbon nitride (g-C3N4) nanosheets will provide promising features as an electrode for the alkaline oxygen evolution reaction (OER). The NiCo-LDH/CN/AgPO heterostructure demonstrated exceptional electrocatalytic OER performance compared to AgPO/NiCo-LDH, AgPO/CN, and CN, achieving a low overpotential of 289mV for the OER at 10mAcm-2 in 1.0M KOH. This superior catalytic activity is attributed to the relatively large electroactive surface area, rapid charge transfer capability, and intimate interactions between the components. The innovative design and synthesis of the NiCo-LDH/CN/AgPO heterostructure provide significant potential for constructing electrocatalysts with superior efficacy in oxygen evolution reactions.

Facet-dependent electrocatalytic oxygen evolution of porous network structure Ni-Fe-O materials

Constructing unique crystal facets can increase active sites and enhance electronic structure for electrocatalysts towards the oxygen evolution reaction (OER). Here, we successfully achieved the transformation between the (311) and (222) facets of the NiFe2O4 catalysts by adjusting the ratio of Ni and Fe elements, and it was found that the activity in OER is enhanced with the exposure of (311) facet. The optimal catalyst shows a lower overpotential of 238 mV at 100 mA/cm2 current density and a small Tafel slope of 26.4 mV/dec. Furthermore, benefiting from the porous network structure, the unique super hydrophilic surface and the low-coordination Fe3+ atoms characteristic, the catalyst has an efficient mass transfer channel and fast charge transfer in the electrocatalytic OER process. More metal-O clusters were exposed on the (311) facet surface as the active site, which further improved the catalytic activity. This work presents a successful approach to creating highly active spinel catalysts through facet-engineering for electrocatalytic water splitting.

Effect of Transition Metals (Mn, Co, Ni, and Zn) in Size-Controlled Metal Ferrite Nanocrystals on the Electrocatalytic Oxygen Evolution Reaction

Effect of Transition Metals (Mn, Co, Ni, and Zn) in Size-Controlled Metal Ferrite Nanocrystals on the Electrocatalytic Oxygen Evolution Reaction

Oxygen evolution reaction activity of carbon aerogel supported Pd–Ni–Al catalysts synthesized by microwave irradiation method

The oxygen evolution reaction (OER) is a critical step for oxygen production during the electrochemical splitting of water. Effective OER catalysts support the development of clean energy technologies by increasing the energy efficiency of these processes. In this study, carbon aerogel (CA) was first synthesized as a catalyst support material using sol-gel, supercritical drying, and pyrolysis process. Then, mono-metallic (Pd/CA, Al/CA), bi-metallic (Pd–Al/CA, Pd–Ni/CA), and tri-metallic (Pd–Ni–Al/CA) catalysts were synthesized by microwave irradiation method. Inductively coupled plasma-mass spectrometry (ICP-MS), X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy have been made to examine the structural properties of the synthesized catalysts. Electrochemical analysis was carried out through cyclic voltammetry (CV), chronoamperometry, and electrochemical impedance spectroscopy (EIS) in alkaline media (1 M KOH: Methanol) to examine the effect of metal loading of CA support material towards OER performance. All the compositions showed excellent activity toward OER, among all Pd–Ni/CA catalysts showed the highest activity. The OER peak current increased remarkably up to 48 mA cm−2 with methanol addition, which signifies the substantial application of carbon aerogel supported-Pd-Ni-Al catalysts in direct methanol fuel cells (DMFCs). Pd–Ni/CA display high OER performance with maximum diffusion coefficient, Do (6.6 × 10−8 cm2 s−1) and heterogeneous rate constant, ko (4.706 × 10−4 cm s−1), and smaller value of Tafel slope (128 mV dec−1). Electrochemical studies predicted that all the prepared carbon aerogel supported-Pd-Ni-Al catalysts can be used as efficient catalysts for OER and other related electrocatalysis applications.

Toward Realistic Models of the Electrocatalytic Oxygen Evolution Reaction.

The electrocatalytic oxygen evolution reaction (OER) supplies the protons and electrons needed to transform renewable electricity into chemicals and fuels. However, the OER is kinetically sluggish; it operates at significant rates only when the applied potential far exceeds the reversible voltage. The origin of this overpotential is hidden in a complex mechanism involving multiple electron transfers and chemical bond making/breaking steps. Our desire to improve catalytic performance has then made mechanistic studies of the OER an area of major scientific inquiry, though the complexity of the reaction has made understanding difficult. While historically, mechanistic studies have relied solely on experiment and phenomenological models, over the past twenty years ab initio simulation has been playing an increasingly important role in developing our understanding of the electrocatalytic OER and its reaction mechanisms. In this Review we cover advances in our mechanistic understanding of the OER, organized by increasing complexity in the way through which the OER is modeled. We begin with phenomenological models built using experimental data before reviewing early efforts to incorporate ab initio methods into mechanistic studies. We go on to cover how the assumptions in these early ab initio simulations─no electric field, electrolyte, or explicit kinetics─have been relaxed. Through comparison with experimental literature, we explore the veracity of these different assumptions. We summarize by discussing the most critical open challenges in developing models to understand the mechanisms of the OER.

Ir-Doped Core-Shell Hollow Heterogeneous Nanospindles for Electrocatalytic Oxygen Evolution Reaction.

By utilizing Metal-organic framework (MOF) materials as a base, constructing electrocatalysts with heterogeneous structures offers advantages for catalyzing water splitting. In this study, a hollow heterogeneous nanocatalyst, Ir-MIL-88A@NiFe-LDHs, was prepared by growing a layered double hydroxides (LDHs) shell on MIL-88A substrate. The catalyst shows excellent oxygen evolution reaction (OER) performance in a 1.0 M KOH solution, requiring only 217 mV overpotential to achieve a current density of 10 mA cm-2 with a Tafel slope of 62.18 mV dec-1, indicating significant electrocatalytic performance and reaction kinetics characteristics. Furthermore, long-term OER testing also demonstrates the catalyst's outstanding stability. Emphasizing the interfacial interaction between MOF and LDHs, as well as the synergistic effect among Ni, Fe, and Ir elements, the study highlights how these factors collaboratively control the local electronic structure of the hollow Ir-MIL-88A@NiFe-LDHs, resulting in an efficient MOF-derived electrocatalyst.

An efficient and robust noble-metal-free self-standing bifunctional water electrolysis catalyst: Co3S4@Ex.NiFe-LDH for alkaline water electrolysis

Electrolysis of water integrated with the renewable energy as input source can contribute significantly in the production of green hydrogen, a clean and versatile energy carrier. In water electrolyzer, the hydrogen evolution reaction (HER) at the cathode must act synchronously with the oxygen evolution reaction (OER) at the anode to effectively accomplish total water-splitting. The performance of an electrolyzer is often limited by the low performance of anode and it is important to develop an electrocatalyst which can efficiently perform both HER and OER. Ni and Fe based layered-double-hydroxides (LDHs) have gained a lot of interest owing to their outstanding OER electrocatalytic activity, however they are known to have poor HER performance. To enhance the overall water splitting efficiency of the LDHs, we present a simple approach of preparing a heterojunction of LDH with cobalt sulphide. The bifunctional electroactivity of the designed electrocatalyst Co3S4@Ex.NiFe-LDH, worked efficiently in both HER and OER electrocatalysis. Chalcogenides known for HER, not only improves the HER performance of the composites but also found to reduce the charge transfer resistance. Obtained results showed that when it comes to the OER performance, the recommended catalyst shadows the state of art catalyst RuO2. Additionally, the catalyst has outstanding activity and stability, achieving a current density of around −120 mA/cm2 over a six-day period. The electrolyzer composed of both anode and cathode designated as Co3S4@Ex.NiFe-LDH||Co3S4@Ex.NiFe-LDH only needs a low voltage input of 1.49 V to achieve a total water splitting reaction at required current density of 10 mA/cm2, showing efficacy at the low voltage input. Experimental observations showed Co3S4@Ex.NiFe-LDH performs better than Pt/C–RuO2 in alkaline water electrolysis. The electrolyzer can continuously produce hydrogen at 50 mA/cm2 for more than a week period; indicating its potential for long-term application.

Fabrication of Fe-Zr, Co-Zr, and Ni-Zr Catalysts to Boost CNTs Synthesis from Plastic Wastes and the Electrocatalytic Oxygen Evolution Reaction.

The efficient conversion of plastic wastes to high-value carbon materials like carbon nanotubes (CNTs) is one important issue about the rational recycling, reduction, and reuse of solid wastes. Herein, Fe-, Co-, and Ni-Zr catalysts were prepared and used for CNTs synthesis from polyethylene (PE) waste via a two-stage reaction system. At the same time, the effects of the PE/catalyst ratio and reaction temperature on CNTs synthesis have been studied. Compared with Co-Zr and Ni-Zr, Fe-Zr exhibited the best activity in CNTs synthesis from PE, and it achieved the highest CNTs yield of 806.3 mg/g (per gram of Fe-Zr) at 800 °C with a PE/catalyst ratio of 4. Furthermore, the obtained Fe-Zr/CNTs composite exhibited a low overpotential of 267 mV for the electrocatalytic oxygen evolution reaction (OER) at 20 mA/cm2 in 1 M KOH electrolyte solution, which was 21 mV lower than commercial RuO2 (288 mV) and 50 mV lower than Fe-Zr (317 mV). It was deduced that the in situ growth of CNTs reduced the charge transfer resistance and improved the electron transport efficiency of the Fe-Zr/CNTs composite, leading to superior activity in the electrocatalytic OER. This work provided detailed information for the preparation of the metal/CNTs composite from plastic wastes, which contributed positively to alleviate the environment and energy crisis.

Three-dimensional pine-tree-like bimetallic sulfide with maximally exposed active sites by secondary structural restructuring for efficient electrocatalytic OER

Developing efficient, low-cost and bifunctional catalysts with predominant durability for the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) is an extraordinary challenge in the preparation of green hydrogen energy by electrochemical water splitting. Three-dimensional (3D) transition metal compounds have become a research hotspot as OER electrocatalysts, which can replace noble metal oxides such as RuO2 and IrO2 to reduce application costs. Herein, we synthesized a novel three-dimensional pine-tree-like bimetallic sulfide arrays on nickel foam (FeCoS/NF) using various optimization strategies such as morphology optimization, in situ growth and introduction of heterogeneous structures. The as-synthesized FeCoS/NF electrocatalyst only requires relatively low overpotential of 156 mV to achieve a current density of 20 mA cm−2 for OER, with a Tafel slope of only 37 mV dec−1. It also has a small charge transfer resistance, an electrochemical surface area and good electrochemical stability in alkaline electrolytes. The excellent performance of FeCoS/NF can be attributed to the synergistic effect and amorphous phase of FeCoS as well as the well-defined pine-tree-like array architecture with a large surface area, abundant active sites, and sufficient gas and electrolyte diffusion channels.

Nanocomposite engineering: Tailoring MXene/Cobalt oxide for efficient electrocatalytic hydrogen and oxygen evolution reactions

Electrocatalytic water splitting has become a significant method of hydrogen production to overcome the energy scarcity and increased rate of pollution caused by the extreme consumption of fossil fuels. Pure cobalt oxide is a potential option for electrocatalytic water splitting due to its higher OER activity but lacks stability, conductivity, and active sites which impair its electrocatalytic performance. In this study, Ti3C2Tx/Co3O4 nanocomposite is synthesized to address the previously noted difficulties along with detailed study of both combinations in three different ratios (1:1, 1:2, 2:1). The outcomes demonstrated that the combination of Ti3C2Tx and Co3O4 in the ratio 1:2 outperformed the component materials in terms of electrocatalytic activity with the lowest overpotential of 270 mV at 50 mA cm‐2−2 for the oxygen evolution reaction (OER), having the least Tafel slope (85 mV dec−1) and Ti3C2Tx/Co3O4 in the ratio 2:1 showed overpotential of 235 mA cm−2, with lowest Tafel slope of 97 mV dec−1 which is the lowest among all electrodes for hydrogen evolution reaction (HER). In Ti3C2Tx MXene with increased O functional group providing adsorption site for hydrogen enables HER in a faster rate. While cobalt oxide enables charge transfer to electronegative MXene which in turn result in stability of the electrocatalyst. In the case of OER, Ti3C2Tx/Co3O4 (1:2) shows the better performance as Co centres act as the active sites for OER while MXene has the role of support matrix for the Co3O4 nanoparticles and prevent aggregation. By choosing these two particular composites, Ti3C2Tx/Co3O4 (2:1) as cathode and Ti3C2Tx/Co3O4 (1:2) as anode overall water splitting was done. For total electrolysis, a potential of 1.73 V was required to provide a current density of 10 mA cm−2 with satisfactory stability. Thus, the produced material is a promising contender for producing green hydrogen in the future.

Lanthanum‐Nickel‐Based Mixed‐Oxide‐Coated Nickel Electrodes for the OER Electrocatalysis

ABSTRACTThe anodic oxygen evolution reaction (OER) remains a bottleneck for electrocatalytic water splitting due to its sluggish kinetics and, thus, high overpotentials. This limits water electrolysis as a key technology for the generation of hydrogen as a sustainable alternative to fossil fuels. For alkaline water splitting, perovskite phases (ABO3) with earth‐abundant first‐row transition‐metals have emerged as a promising material class for OER electrocatalysts. Among these, LaNiO3 has been found to exhibit high intrinsic OER activity. To increase catalyst utilization, a high surface area of the catalyst is desirable and can be achieved by impregnation of porous templates. In this work, La–Ni‐based oxides were prepared via impregnation of activated carbon and subsequent heating, combining precursor calcination and template removal into one step. The phase structure of the samples is analyzed via powder X‐ray diffractometry, and the morphology is determined by scanning electron microscopy. The synergistic effect of B‐site mixing iron as well as A‐site mixing strontium into LaNiO3 is studied and found to increase its OER activity, confirming the activity‐enhancing effect of Fe in Ni‐based OER electrocatalysts. To allow for facile technical application of the catalysts, the electrodes are prepared by coating a perovskite ink onto Ni‐metal as industrially relevant substrates, followed by calcination.

Lanthanum‐Nickel‐Based Mixed‐Oxide‐Coated Nickel Electrodes for the OER Electrocatalysis

ABSTRACTThe anodic oxygen evolution reaction (OER) remains a bottleneck for electrocatalytic water splitting due to its sluggish kinetics and, thus, high overpotentials. This limits water electrolysis as a key technology for the generation of hydrogen as a sustainable alternative to fossil fuels. For alkaline water splitting, perovskite phases (ABO3) with earth‐abundant first‐row transition‐metals have emerged as a promising material class for OER electrocatalysts. Among these, LaNiO3 has been found to exhibit high intrinsic OER activity. To increase catalyst utilization, a high surface area of the catalyst is desirable and can be achieved by impregnation of porous templates. In this work, La–Ni‐based oxides were prepared via impregnation of activated carbon and subsequent heating, combining precursor calcination and template removal into one step. The phase structure of the samples is analyzed via powder X‐ray diffractometry, and the morphology is determined by scanning electron microscopy. The synergistic effect of B‐site mixing iron as well as A‐site mixing strontium into LaNiO3 is studied and found to increase its OER activity, confirming the activity‐enhancing effect of Fe in Ni‐based OER electrocatalysts. To allow for facile technical application of the catalysts, the electrodes are prepared by coating a perovskite ink onto Ni‐metal as industrially relevant substrates, followed by calcination.

Atomic-Layer IrOx Enabling Ligand Effect Boosts Water Oxidation Electrocatalysis.

An in situ formed IrOx (x ≤ 2) layer driven by anodic bias serves as the essential active site of Ir-based materials for oxygen evolution reaction (OER) electrocatalysis. Once being confined to atomic thickness, such an IrOx layer possesses both a favorable ligand effect and maximized active Ir sites with a lower O-coordination number. However, limited by a poor understanding of surface reconstruction dynamics, obtaining atomic layers of IrOx remains experimentally challenging. Herein, we report an idea of material design using intermetallic IrVMn nanoparticles to induce in situ formation of an ultrathin IrOx layer (O-IrVMn/IrOx) to enable the ligand effect for achieving superior OER electrocatalysis. Theoretical calculations predict that a strong electronic interaction originating from an orderly atomic arrangement can effectively hamper the excessive leaching of transition metals, minimizing vacancies for oxygen coordination. Linear X-ray absorption near edge spectra analysis, extended X-ray absorption fine structure fitting outcomes, and X-ray photoelectron spectroscopy collectively confirm that Ir is present in lower oxidation states in O-IrVMn/IrOx due to the presence of unsaturated O-coordination. Consequently, the O-IrVMn/IrOx delivers excellent acidic OER performances with an overpotential of only 279 mV at 10 mA cm-2 and a high mass activity of 2.3 A mg-1 at 1.53 V (vs RHE), exceeding most Ir-based catalysts reported. Moreover, O-IrVMn/IrOx also showed excellent catalytic stability with only 0.05 at. % Ir dissolution under electrochemical oxidation, much lower than that of disordered D-IrVMn/IrOx (0.20 at. %). Density functional theory calculations unravel that the intensified ligand effect optimizes the adsorption energies of multiple intermediates involved in the OER and stabilizes the as-formed catalytic IrOx layer.

Mesoporous graphene-supported nanostructured nickel telluride for efficient electrocatalytic oxygen evolution reaction

The electrocatalytic oxygen evolution reaction (OER) imposes significant constraints on the operational overpotential of electrochemical energy devices, such as water electrolyzers, metal-air batteries, and fuel cells. However, the sluggish kinetics of OER reactions hinder these applications, which has prompted efforts to design more effective electrocatalysts. In this study, we have synthesized NiTe via in-situ growth into mesoporous graphene (MG), with varying nominal weight percentages (5- wt%, 10- wt%, and 15- wt%) of NiTe. The resulting NiTe/MG nanohybrids displayed hexagonally structured NiTe nanoparticles with a predominant (101) surface that promotes the OER kinetics. The wrinkled 3D mesoporous graphene scaffold facilitated the attachment and dispersion of NiTe particles of nanoscale on its surface, preventing their agglomeration. The porous characteristics of the MG significantly increased the high surface area of the NiTe/MG nanohybrids (583–671 m2 g−1), promoting enhanced accessibility of active sites and mass transport beneficial for the OER. Moreover, the altered electronic structure of the NiTe in the MG nanohybrid indicates enhancing O2 desorption during the OER. The optimized composition of the 10 wt% NiTe-loaded MG nanohybrid electrocatalyst demonstrates superior OER activity compared to other nanohybrids. It exhibits a small overpotential of 250 mV at 10 mA cm−2, a low Tafel slope of 63 mV dec−1 and maintained stability in 1 M KOH (pH = 14) as the electrolyte for a prolonged period. This enhanced OER activity is ascribed to the synergistic effect of MG’s high conductivity and the improved intrinsic activity of NiTe within the nanohybrid structure.

Surface reconstruction and entropy engineering of Ni(OH)2 nanosheets for enhanced electrocatalytic performances of oxygen evolution reaction in alkaline seawater

Hydrogen production via electrochemical splitting of seawater is highly desirable but still facing great challenges. Herein, we report the facile preparation of medium-entropy oxyhydroxides on Ni(OH)2 nanosheets via surface reconstruction and entropy engineering strategies, achieving enhanced electrocatalytic activity and stability for oxygen evolution reaction (OER) in alkaline seawater. The electrochemical oxidation is conducted on Ni(OH)2 nanosheets to create abundant reactive oxygen (reactive-O) atoms on the reconstructed surface, thus forming a reactive-O enriched surface on Ni(OH)2 (NiOx/Ni(OH)2). Additionally, cations are incorporated onto the reconstructed surface of NiOx/Ni(OH)2 via an electrodeposition method, forming the medium-entropy oxyhydroxides on Ni(OH)2 nanosheets ((FeCoCrNi)Ox/Ni(OH)2). Benefiting from the composition and structure advantages, the resulting (FeCoCrNi)Ox/Ni(OH)2@NF demonstrates obviously enhanced performances for OER electrocatalysis, with an overpotential of 239 mV at the current density of 10 mA cm−2 and a low Tafel slope of 24.66 mV dec−1 in 1.0 M KOH + 0.5 M NaCl solution. Furthermore, it exhibits exceptional durability for OER electrocatalysis in alkaline seawater, maintaining over 90.7 % of the OER current density after 100 h.