Efficient Oxygen Evolution Reaction Research Articles

Unveiling the potential of (CoFeNiMnCr)3O4 high-entropy oxide synthesized from CoFeNiMnCr high-entropy alloy for efficient oxygen-evolution reaction

AbstractElectrochemical water-splitting is a promising green technology for the production of hydrogen. One of the bottlenecks, however, is the oxygen evolution half-reaction (OER), which could be overcome with the development of a suitable electrocatalyst. Recently, non-noble metal, high-entropy oxides (HEO) have been investigated as potential OER electrocatalysts, but complex synthesis approaches that usually produce the material in powder form limit their wider utilization. Here, an innovative synthesis strategy of formulating a nanostructured (CoFeNiMnCr)3O4 HEO thin film on a CoFeNiMnCr high entropy alloy (HEA) using facile electrochemical and thermal treatment methods is presented. The CoFeNiMnCr HEA serves as exceptional support to be electrochemically treated in an ethylene glycol electrolyte with ammonium fluoride to form a rough and microporous structure with nanopits. The electrochemically treated CoFeNiMnCr HEA surface is more prone to oxidation during a low-temperature thermal treatment, leading to the growth of a spinel (CoFeNiMnCr)3O4 HEO thin film. The (CoFeNiMnCr)3O4 HEO exhibits a superior overpotential of 341 mV at 10 mA cm−2 and a Tafel slope of 50 mV dec−1 along with remarkable long-term stability in alkaline media. The excellent catalytic activity and stability for the OER can serve as a promising platform for the practical utilization of (CoFeNiMnCr)3O4 HEO. Graphical abstract

Carbon-Based Composites for Oxygen Evolution Reaction Electrocatalysts: Design, Fabrication, and Application

The four-electron oxidation process of the oxygen evolution reaction (OER) highly influences the performance of many green energy storage and conversion devices due to its sluggish kinetics. The fabrication of cost-effective OER electrocatalysts via a facile and green method is, hence, highly desirable. This review summarizes and discusses the recent progress in creating carbon-based materials for alkaline OER. The contents mainly focus on the design, fabrication, and application of carbon-based materials for alkaline OER, including metal-free carbon materials, carbon-based supported composites, and carbon-based material core–shell hybrids. The work presents references and suggestions for the rational design of highly efficient carbon-based OER materials.

Metal Doping Regulates Electrocatalysts Restructuring during Oxygen Evolution Reaction.

High-efficiency and low-cost catalysts for oxygen evolution reaction (OER) are critical for electrochemical water splitting to generate hydrogen, which is a clean fuel for sustainable energy conversion and storage. Among the emerging OER catalysts, transition metal dichalcogenides have exhibited superior activity compared to commercial standards such as RuO2, but inferior stability due to uncontrolled restructuring with OER. In this study, we create bimetallic sulfide catalysts by adapting the atomic ratio of Ni and Co in CoxNi1-xSy electrocatalysts to investigate the intricate restructuring processes. Surface-sensitive X-ray photoelectron spectroscopy and bulk-sensitive X-ray absorption spectroscopy confirmed the favorable restructuring of transition metal sulfide material following OER processes. Our results indicate that a small amount of Ni substitution can reshape the Co local electronic structure, which regulates the restructuring process to optimize the balance between OER activity and stability. This work represents a significant advancement in the development of efficient and noble metal-free OER electrocatalysts through a doping-regulated restructuring approach.

Self-Assembled Conjugated Coordination Polymer Nanorings: Role of Morphology and Redox Sites for the Alkaline Electrocatalytic Oxygen Evolution Reaction.

Electrocatalytic water splitting provides a sustainable method for storing intermittent energies, such as solar energy and wind, in the form of hydrogen fuel. However, the oxygen evolution reaction (OER), constituting the other half-cell reaction, is often considered the bottleneck in overall water splitting due to its slow kinetics. Therefore, it is crucial to develop efficient, cost-effective, and robust OER catalysts to enhance the water-splitting process. Transition-metal-based coordination polymers (CPs) serve as promising electrocatalysts due to their diverse chemical architectures paired with redox-active metal centers. Despite their potential, the rational use of CPs has faced obstacles including a lack of insights into their catalytic mechanisms, low conductivity, and morphology issues. Consequently, achieving success in this field requires the rational design of ligands and topological networks with the desired electronic structure. This study delves into the design and synthesis of three novel conjugated coordination polymers (CCPs) by leveraging the full conjugation of terpyridine-attached flexible tetraphenylethylene units as electron-rich linkers with various redox-active metal centers [Co(II), Ni(II), and Zn(II)]. The self-assembly process is tuned for each CCP, resulting in two distinct morphologies: nanosheets and nanorings. The electrocatalytic OER performance efficiency is then correlated with factors such as the nanostructure morphology and redox-active metal centers in alkaline electrolytes. Notably, among the three morphologies studied, nanorings for each CCP exhibit a superior OER activity. Co(II)-integrated CCPs demonstrate a higher activity between the redox-active metal centers. Specifically, the Co(II) nanoring morphology displays exceptional catalytic activity for OER, with a lower overpotential of 347 mV at a current density of 10 mA cm-2 and small Tafel slopes of 115 mV dec-1. The long-term durability is demonstrated for at least 24 h at 1.57 V vs RHE during water splitting. This is presumably the first proof that links the importance of nanostructure morphologies to redox-active metal centers in improving the OER activity, and it may have implications for other transdisciplinary energy-related applications.

Substantial Electrocatalytic Oxygen Evolution Performances of Activated Carbon-Decorated Vanadium Pentoxide Nanocomposites

Developing the ecofriendly and high-fidelity electrocatalysts for the oxygen evolution reaction (OER) is essential to foster effective production of environmentally friendly hydrogen. Herein, we fabricated the highly efficient OER electrocatalysts of the activated carbon-decorated vanadium pentoxide (AC-V2O5) nanocomposites using a facile hydrothermal technique. The AC-V2O5 nanocomposites displayed an aggregated structure of the AC nano-sheet-anchored orthorhombic V2O5 nanorods. When performing the OER process in an alkaline electrolyte at 10 mA/cm2, AC-V2O5 exhibited the low overpotential (~230 mV), small Tafel slope (~54 mV/dec), and excellent stability. These substantial OER performances of AC-V2O5 could be ascribed to the synergistic effects from both the electrochemically active V2O5 nanorods and the highly conductive AC nanosheets. The results infer that the AC-V2O5 nanocomposites possess a substantial aptitude as a high-performance OER electrocatalyst for production of the future green energy source—hydrogen.

IrO2 nanoparticles supported on submicrometer-sized TiO2 as an efficient and stable coating for oxygen evolution reaction

The sluggish kinetics of the oxygen evolution reaction (OER) refers to the major contributor to the energy losses in electrowinning of metals. Improving the stability in the long term and activity of the electrocatalyst for OER take on a critical significance in reducing the energy consumption. An efficient and stable OER electrode (named as Ti/SMST/IrO2 electrode) was prepared in this study by supporting IrO2 nanoparticles on the surface of the submicrometer-sized TiO2 (SMST) interlayer. The obtained results indicated that the IrO2 nanoparticles approximately 14 nm in size were supported onto the submicrometer-sized TiO2 particles’ surface and exhibited a cactus-like morphology. The Ti/SMST/IrO2 electrode with the SMST interlayer prepared at 450 °C exhibited the highest electrocatalytic activity in terms of OER for its largest active surface area. This electrode showed an overpotential of 350 mV at a current density of 50 mA cm−2 and displayed a remarkable electrochemical stability of 443 h at a high current density of 2 A cm−2 in H2SO4 solution without significant change in OER activity. The prepared Ti/SMST/IrO2 electrode with high electrocatalytic performance is considered one of the promising electrodes for OER.

Double oxygen evolution co-catalysts modified BiVO4 to boost photoelectrochemical water oxidation performance

Improving the kinetics of oxygen evolution is crucial for enhancing the performance of photoelectrochemical (PEC) water splitting. Herein, this study utilizes a chemical self-growth method to grow NiFe tannic acid complex (NFTA) and Co(OH)2 on the surface of BiVO4 photoanode (BiVO4/NFTA/Co). As a result, the synergistic effects of NFTA and Co(OH)2 layers promote the efficiency and stability of BiVO4 photoanode towards PEC water oxidation. The photocurrent density of the obtained BiVO4/NFTA/Co photoanode reaches 4.97 mA cm−2, which is significantly greater than those of BiVO4/NFTA (4.36 mA cm−2), BiVO4/Co (2.51 mA cm−2), BiVO4 (1.34 mA cm−2), respectively. Detailed analysis confirms that NFTA could provide an efficient way to hasten the transfer of photo-generated holes on the photoanode surface and diminish the surface charge transfer resistance. In other hand, Co(OH)2 could be served as a cocatalyst to accelerate charge transfer for efficient oxygen evolution reaction as well as a protective layer to maintain the long-term stability of NFTA on the surface of BiVO4 during water oxidation. Such double oxygen evolution co-catalysts decoration strategy paves an effective pathway to enhance the PEC water oxidation performance of BiVO4 photoanode.

Coupling interface constructions of flower-like structure MoSe2–NiWSe2 for efficient oxygen evolution reaction and urea oxidation reaction

Because of its low thermodynamic voltage, the electrocatalytic urea oxidation reaction (UOR) is an effective way to replace the sluggish oxygen evolution reaction (OER) and address the issue of urea-rich water pollution. Herein, we have synthesized MoSe2–NiWSe2 with spherical nanoflower structure consisting of MoSe2 nanosheets and NiWSe2 nanosheets crisscrossed longitudinally and transversely. The results show that the prepared MoSe2–NiWSe2 has a significant competitive advantage in the UOR and OER. With 10 mA cm−2, a mere 200 mV overpotential was required, indicating high OER catalytic activity. MoSe2–NiWSe2-driven UOR might operate at a comparatively low potential of 1.36 V (10 mA cm−2). The overpotential did not significantly alter after 40 h of continuous operation, suggesting it possesses high UOR stability. A built-in electric field that aids in controlling the adsorption and oriented distribution of urea molecules and thus promotes the oxidative properties of water and urea forms at the interface of MoSe2 and NiWSe2, where the difference in electronegativity between the elements Mo and Ni induces self-driven charge transfer and interfacial coupling effects. This work offers a method for creating catalysts that produce more oxygen and clean up urea-rich water contamination.

Novel amorphous FeOOH-modified Co9S8 nanosheets with enhanced catalytic activity in oxygen evolution reaction

Efficient oxygen evolution reaction (OER) is vital for water electrolysis and advanced hydrogen energy production. However, the sluggish kinetics of this reaction require significant overpotentials, leading to high energy consumption. Therefore, developing OER electrocatalysts with exceptional performance and long-term durability is crucial for enhancing the energy efficiency and cost-effectiveness of the hydrogen production process. In this research, novel FeOOH/Co9S8 catalysts were prepared through a two-step hydrothermal reaction followed by one-step electrodeposition on nickel foam for an alkaline OER. The as-obtained catalysts possessed abundant non-homogeneous interfaces between FeOOH and Co9S8 nanosheets, conducive to optimized coordination environments of Fe and Co sites by redistributing interfacial charges. This synergy strengthened the chemisorption of oxygenated intermediates, leading to accelerated reaction kinetics, abundant active sites, and enhanced OER performance. The optimized electrocatalyst FeOOH/Co9S8-15 achieved a current density of 10 mA cm−2 at an overpotential of 248 mV and good stability for over 140 h. This study presents a novel approach for producing compelling and durable alkaline dielectric OER electrocatalysts, which will be helpful in the future manufacturing of advanced energy devices.

A highly-stable and low-energy-barrier photoelectrocatalyst (NiFe-LDH@Ti-MOF) for water splitting at high current densities via breaking the atomic structure symmetry

There is a flurry of interest in enhancing the stability and efficiency of photoelectrocatalysts in water splitting at high current densities. In the present study, nickel–iron layered double hydroxide (NiFe-LDH) was decorated with MIP-177-LT (Ti-metal organic framework (MOF)) to fabricate a heteroatom electrocatalyst (NiFe-LDH@Ti-MOF). The overpotentials of the oxygen evolution reaction (OER) turned out to be very low: 199 and 232 mV at current densities of 200 and 600 mA cm−2, in that order. Then, current densities of 1,000 mA cm−2 were applied to the modified electrode over a long period of 800 h, and this generated a higher stability than that of the commercial IrO2. Further, its mass activity proved ∼2 and 7 times as high as those of IrO2 and NiFe-LDH, in that order. Furthermore, for water splitting, the produced photoelectrocatalyst obtained a current density of 1,000 mA cm−2 using only 1.6 V, and this performance remained changeless for 800 h, which can be considered the most superb performance ever reported. The experimental characterization revealed that during the process of doping Ti-MOF on NiFe-LDH, symmetry breaking takes place in the atomic structure of the LDH surface, which increases the active sites in the photoelectrocatalyst. The presence of oxygen in the Ti-MOF active sites improves the efficiency of OER at high current densities and also contributes to the higher stability of multiple heteroatomic interfaces for water splitting. The propounded strategy enables the generation of oxygen and hydrogen from water splitting at high current densities on an industrial scale by changing the symmetry of the atomic structure of heteroatomic photocatalysts.

The acceleration of the active phase transition of NiCoFe hydroxide by Ta doping to achieve Long-Time seawater electrolysis at Ampere-Level current density

Considering the regional distribution of freshwater resources, acquiring hydrogen by seawater electrolysis has lower cost and feasibility. NiCoFe-based materials have been widely studied due to their excellent catalytic oxidation performance in freshwater. However, the large amount of chloride ions in seawater will severely erode the catalytic site and greatly reduce the catalyst's lifetime. In this paper, a two-dimensional nanosheet quaternary metal hydroxide electrode composed of Ni, Co, Fe, and Ta elements was synthesized via a facile one-step hydrothermal method for efficient oxygen evolution reaction (OER) in seawater electrolysis. Structural characterization and in-situ test revealed that the incorporation of Ta not only optimized the electronic structure of the catalyst but also accelerated the formation of the γ-NiOOH phase, making the active phase is protected from being attacked by Cl- ions during the formation process, enhancing its OER activity while achieving extended durability. The catalyst was operated at an ampere-level of 1 A cm-2 for over one month (800 h), and no significant degradation was observed. This work provides a promising strategy for developing cost-effective, efficient, and stable catalysts for challenging applications in seawater electrolysis.

Fluorine-decoration induced deep reconstruction of iron cobalt oxide for high-efficiency oxygen evolution reaction

The oxygen evolution reaction (OER) is a pivotal process in water electrolysis systems, yet developing cost-effective and highly active OER electrocatalysts from earth-abundant materials through straightforward methods remains a formidable challenge. In this study, FeCo oxides and their fluorides are synthesized using a one-step room-temperature process followed by fluorination with fluorine gas. We compared the OER performance of Fe, Co, and FeCo oxides and investigated the impact of fluorine doping on their physical properties and OER efficiency. Results revealed that the FeCo–O bimetallic oxide exhibited an overpotential of 370 mV in an alkaline electrolyte at a current density of 10 mA/cm2, significantly surpassing the performance of monometallic Fe–O (1 V) and Co–O (467 mV). Fluorine modification markedly enhanced the OER activity of these materials, with Fe-OF at 570 mV, Co-OF at 330 mV, and FeCo-OF at 285 mV. Notably, FeCo-OF demonstrated a stable overpotential lower than commercial RuO2 (289 mV) during a continuous 12 h OER test. Electrochemical analyses and spectral characterizations indicated that fluorine ion electronic regulation facilitated efficient electrocatalytic active sites in the spent FeCo-OF catalyst through in situ self-reconstruction, leading to its stable and superior OER performance. Density functional theory (DFT) calculations confirmed that fluorine modification of the bimetallic oxides decreased the O* Gibbs free energy from 4.86 to 2.44 eV, thereby enhancing the kinetics of the OER reaction.

WO3-x as an activation medium to prompt overall water splitting of NiFe-based electrocatalyst

The efficient oxygen evolution reaction (OER) is crucial for various electrochemical processes, especially for overall water splitting (OWS). In this study, we focus on the utilization of WO3-x as an activation medium to enhance the OER performance of NiFe-based electrocatalysts. Firstly, we synthesize WO3-x nanowires supported on nickel foam (NF) and then incorporate NiFe on WO3-x nanowires by a simple hydrothermal method. The WO3-x self-supported NiFe (Oxy)hydroxide (denoted as NiFe-W-O/NF) shows a three-dimensional stereostructure composed of ultrathin nanosheets (∼ 4.0 nm). This unique structure provides a large open surface for fuller diffusion of the electrolyte while exposing more active sites. The electronic interaction of tri-centers of NiFeW accelerates the surface reconstruction process of γ-NiOOH and FeOOH, which are converted into the main active species in a short time. The electrochemical measurements confirm that the NiFe-W-O/NF has low OER overpotentials (233 mV at 10 mA cm−2, 298 mV at 100 mA cm−2) and excellent stability (100 h in total) in 1 M KOH electrolyte. In addition, the NiFe-W-O/NF || NiFe-W-O/NF battery also exhibits a low cell voltage (1.52 V at 10 mA cm−2) with a stable lifetime (50 h) under alkaline conditions. These results highlight the great potential of NiFe-W-O/NF for practical applications.

Co-doped NiFe carbonate hydroxide hydrate nanosheets with edge effect constructed from spent lithium-ion battery ternary cathodes for oxygen evolution reaction

The recycling of spent lithium-ion batteries (LIBs) has received increasing attention for environment and resource reclamation. Converting LIBs wastes into high-efficiency catalysts is a win-win strategy for realizing resource reclamation and addressing sustainable energy challenges. Herein, we developed a simple method to upcycle spent-LIBs cathode powder into Co-doped NiFe carbonate hydroxide hydrate (Co/NFCH-FF) as a low-cost and efficient oxygen evolution reaction (OER) electrocatalyst. The optimized Co/NFCH-FF electrode appears very competitive OER performances with low overpotentials of 201 and 249 mV at 10 and 100 mA cm−2, respectively, a small Tafel slope of 48.4 mV dec−1, and a high long-term stability. Moreover, we reveal that the existence of Co atoms leads to the formation of a crystalline/amorphous (c/a) interface at the Co/NFCH nanosheet edge, inducing the nanosheets possess a unique edge effect to enhance electric fields and accumulate hydroxide ions (OH–) at the edge during the OER process. Benefiting from edge effect, Co/NFCH-FF shows outstanding intrinsic activity. Furthermore, Co atoms as dopants stabilize the electronic structure of Co/NFCH-FF, enabling Co/NFCH-FF to exhibit excellent catalytic stability. This work provides an effective strategy for converting the end-life LIBs to high-performance multicomponent OER electrocatalysts and proposes new insights into the mechanism of enhanced catalytic activity of Co/NFCH.

Grain‐Boundary‐Rich RuO2 Porous Nanosheet for Efficient and Stable Acidic Water Oxidation

RuO2 has been considered as the most likely acidic oxygen evolution reaction (OER) catalyst to replace IrO2, but its performance, especially long‐term stability under harsh acidic conditions, is still unacceptable. Here, we propose a grain boundary (GB) engineering strategy by fabricating the ultrathin porous RuO2 nanosheet with abundant of grain boundaries (GB‐RuO2) as an efficient acid OER catalyst. The involvement of GB induces significant tensile stress and creates an unsaturated coordination environment, effectively optimizing the adsorption of intermediates and stabilizing active site structure during OER process. Notably, the GB‐RuO2 not only exhibits a low overpotential (η10= 187 mV) with an ultra‐low Tafel slope (34.5 mV dec‐1), but also steadily operates for over 550 h in 0.1 M HClO4. Quasi in situ/operando methods confirm that the improved stability is attributed to GB preventing Ru dissolution and greatly inhibiting the lattice oxygen oxidation mechanism (LOM). A proton exchange membrane water electrolysis (PEMWE) using the GB‐RuO2 catalyst operates a low voltage of 1.669 V at 2 A cm‐2 and operates stably for 100 h at 100 mA cm‐2.

Grain-Boundary-Rich RuO2 Porous Nanosheet for Efficient and Stable Acidic Water Oxidation.

RuO2 has been considered as the most likely acidic oxygen evolution reaction (OER) catalyst to replace IrO2, but its performance, especially long-term stability under harsh acidic conditions, is still unacceptable. Here, we propose a grain boundary (GB) engineering strategy by fabricating the ultrathin porous RuO2 nanosheet with abundant of grain boundaries (GB-RuO2) as an efficient acid OER catalyst. The involvement of GB induces significant tensile stress and creates an unsaturated coordination environment, effectively optimizing the adsorption of intermediates and stabilizing active site structure during OER process. Notably, the GB-RuO2 not only exhibits a low overpotential (η10= 187 mV) with an ultra-low Tafel slope (34.5 mV dec-1), but also steadily operates for over 550 h in 0.1 M HClO4. Quasi in situ/operando methods confirm that the improved stability is attributed to GB preventing Ru dissolution and greatly inhibiting the lattice oxygen oxidation mechanism (LOM). A proton exchange membrane water electrolysis (PEMWE) using the GB-RuO2 catalyst operates a low voltage of 1.669 V at 2 A cm-2 and operates stably for 100 h at 100 mA cm-2.

Self-supported low-crystallinity CoFe layered double hydroxide nanospheres on monolayer Ti3C2 electrode for oxygen evolution reaction

The electrocatalytic oxygen evolution reaction is a crucial means to support the conversion and storage of the sustainable renewable energy. Low-crystallinity can offer short-range structural ordering and high active site density. In this work, an efficient self-supported oxygen evolution reaction (OER) electrocatalyst, cobalt iron layered double hydroxide (LDH) grown on Ti3C2 modified nickel foam (NF) heterostructure anode (CoFe-LDH/Ti3C2/NF) was prepared using electrodeposition. The exceptional electrocatalytic OER performance is ensured by in situ decorating monolayer Ti3C2/NF (s-Ti3C2/NF) with low-crystallinity CoFe nanospheres. By harnessing the low crystallinity, well-chosen composition and reasonable heterostructure, the overpotential of CoFe-LDH/Ti3C2/NF decreases to 246 mV at a current density of 10 mA·cm−2 in alkaline media. After 3000 cyclic voltammograms cycles, the ignorable increase in overpotential of 14 mV suggest the excellent long circular stability. Moreover, an accelerated reaction kinetics is implied by the smaller Tafel slope (28.76 mV·dec−1) and higher double-layer specific capacitance (2.33 mF·cm−2), which surpassed the counterparts CoFe-LDH grown on NF (CoFe-LDH/NF) and s-Ti3C2/NF. This work paves a new way to fabricate the low-crystallinity materials for electrocatalysis and energy storage.

Simultaneous Interface Engineering and Phase Tuning of CeO2-Decorated Catalysts for Boosted Oxygen Evolution Reaction.

Heterogeneous catalysts have attracted extensive attention among various emerging catalysts for their exceptional oxygen evolution reaction (OER) capabilities, outperforming their single-component counterparts. Nonetheless, the synthesis of heterogeneous materials with predictable, precise, and facile control remains a formidable challenge. Herein, a novel strategy involving the decoration of catalysts with CeO2 is introduced to concurrently engineer heterogeneous interfaces and adjust phase composition, thereby enhancing OER performance. Theoretical calculations suggest that the presence of ceria reduces the free energy barrier for the conversion of nitrides into metals. Supporting this, the experimental findings reveal that the incorporation of rare earth oxides enables the controlled phase transition from nitride into metal, with the proportion adjustable by varying the amount of added rare earth. Thanks to the role of CeO2 decoration in promoting the reaction kinetics and fostering the formation of the genuine active phase, the optimized Ni3FeN/Ni3Fe/CeO2-5% nanoparticles heterostructure catalyst exhibits outstanding OER activity, achieving an overpotential of just 249mV at 10mAcm-2. This approach offers fresh perspectives for the conception of highly efficient heterogeneous OER catalysts, contributing a strategic avenue for advanced catalytic design in the field of energy conversion.

High-entropy MnCoCuZnAlSe2 nanosheet arrays for highly efficient alkaline oxygen evolution reaction

The oxygen evolution reaction is the primary obstacle in the electrochemical breakdown of water; whereas transition metal selenides exhibit remarkable OER activity, their stability is compromised by the oxidative dissolution of selenium. The high-entropy materials can provide a feasible strategy to solve this problem due to their multi-element synergy and entropy stabilization effect. Here, we designed novel high-entropy MnCoCuZnAlSe2 electrocatalysts with ultra-low overpotential (190 mV@10 mA cm−2) and exceptional endurance (500 h@10 mA cm−2), which outperform other selenide and IrO2 catalysts. The high entropy effect was experimentally confirmed to inhibit selenium dissolution and improve the stability of transition metal selenides. Calculations using Density Functional Theory suggest that cobalt is actually MnCoCuZnAlSe2's true active center. The extraordinary OER properties of high-entropy selenides offer great opportunities for the design of ideal catalysts for practical applications.

Designing asymmetrical TMN4 sites via phosphorus or sulfur dual coordination as high-performance electrocatalysts for oxygen evolution reaction

The development ofhighly efficient oxygen evolution reaction (OER) catalysts based on more cost-effective and earth-abundant elements is of great significance and still faces a huge challenge. In this work, a series of transition metal (TM)embedding a newly-defined monolayer carbon nitride phase is theoretically profiled and constructed as a catalytic platform for OER studies. Typically, a four-step screening strategy was proposed to rapidly identified high performance candidates and the coordination structure and catalytic performance relationship was thoroughly analyzed. Moreover, the eliminating criterion was established to condenses valid range based on the Gibbs free energy of OH*. Our results reveal that the as-constructed 2FeCN/P exhibits superior activity toward OER with an ultralow overpotential of 0.25 V, at the same time, the established 3FeCN/S configuration performed well as abifunctional OER/ORR electrocatalysis with extremely low overpotential ηOER/ηORR of 0.26/0.48 V. Overall, this work provides an effective framework for screening advanced OER catalysts, which can also be extended to other complex multistep catalytic reactions.