Electrocatalysts For Oxygen Evolution Reaction Research Articles

Designing a Phenalenyl-Based Dinuclear Ni(II) Complex: An Electrocatalyst with Two Single Ni Sites for the Oxygen Evolution Reaction (OER).

A new dinuclear Ni(II) complex 1, [Ni2II(dtbh-PLY)2], is synthesized from 9-(2-(3,6-di-tert-butyl-2-hydroxybenzylidene)hydrazineyl)-1H-phenalen-1-one, dtbh-PLYH2 ligand, and structurally characterized by various analytical tools including the single-crystal X-ray diffraction (SCXRD) technique. In the solid state, both Ni(II) metal centers in complex 1 exist in a distorted square planar geometry and display the presence of rare Ni···H-C anagostic interactions to form a one-dimensional (1-D) linear motif in the supramolecular array. Complex 1 is further stabilized in the solid state by π-π-stacking interactions between the highly delocalized phenalenyl rings. The redox features of complex 1 have been analyzed by the cyclic voltammetry (CV) technique in solution as well as in the solid state, revealing the crucial involvement of both the Ni(II) metal centers for undergoing quasi-reversible oxidation reactions on the application of an anodic sweep. A complex 1-modified glassy carbon electrode, GC-1, is employed as an electrocatalyst for oxygen evolution reaction (OER) in 1.0 M KOH, giving an OER onset at 1.45 V, and very low OER overpotential, 300 mV vs the reversible hydrogen electrode (RHE) to reach 10 mA cm-2 current density. Furthermore, GC-1 displayed fast OER kinetics with a Tafel slope of 40 mV dec-1, a significantly lower Tafel slope value than those of previously reported molecular Ni(II) catalysts. In situ electrochemical experiments and postoperational UV-vis, Fourier transform infrared (FT-IR), scanning electron microscopy-energy-dispersive X-ray spectroscopy (SEM-EDS), and X-ray photoelectron spectroscopy (XPS) studies were performed to analyze the stability of the molecular nature of complex 1 and to gain reasonable insights into the true OER catalyst.

Mn-doped nickel-copper phosphides as oxygen evolution reaction electrocatalyst in alkaline seawater solution

Compared with traditional water electrolysis, electrolysis of seawater has larger resources and a brighter future. However, seawater contains more elements that have greater corrosive effects on electrodes; especially chloride ions (seawater contains more chloride ions) have the greatest impact. The existence of the corrosion problem creates greater difficulties in electrolyzing seawater, further limiting the efficiency of the electrocatalyst for electrolysis of seawater. In this paper, we report a Mn-doped Ni2P/Cu3P as an environmentally friendly monofunctional electrode for seawater electrolysis, which was made by a simple hydrothermal phosphatization operation method. The experimental results show that Mn-doped Ni2P/Cu3P presents overpotential of only 161 mV for oxygen evolution reaction (OER) at iR compensation of 90 and a current density of 10 mA cm−2. It has a small Tafel slope (25.15 mV dec−1) and a large capacitance (9.58 mF cm−2 on 1 × 1 nickel foam), which exceeds most reported oxygen evolution activities of non-precious metal-based electrocatalysts for electrolysis of alkaline seawater. The performance of Ni2P/Cu3P was probably significantly enhanced due to Mn doping by some characterization means. Through Density functional theory (DFT) analysis, it is known that the doping of Mn gives a large enhancement in the adsorption energy of water when Ni2P/Cu3P is electrolyzed with seawater. This paper provides train of thought for the exploration of excellent electrocatalysts for electrolysis of alkaline seawater.

Ultra-High Performance of In Situ Constructed Trimetallic (Pd, Fe, Co) Nanoparticles on Carbon Paper as an Electrocatalyst for Large Current Density Oxygen Evolution Reaction in Alkaline Seawater

Abstract Seawater electrocatalysis holds significant promise as a technology for hydrogen production. A simple and low-cost impregnation-hydrothermal and thermal reduction strategy was used to synthesis in-situ constructed three-dimensional porous trimetallic (Pd, Fe, and Co) anchored on a cheap and high-conducting carbon paper (CP) electrode for water electrolysis in alkaline media. The fabricated PdFeCo1−xONPs@CP electrode had superhydrophilic and superaerophobic properties, allowing for efficient removal of oxygen bubbles from the electrode surface due to the close interaction between the electrode and electrolyte. Furthermore, the synergistic effect of trimetallics and CP-fibers significantly increased OER intrinsic activity. PdFeCo1−xONPs@CP catalyst demonstrated critical low overpotentials of 220 and 300 mV, resulting in an extraordinarily high current density of 100 mA cm−2. For the full cell overall water splitting performance, cell overpotentials as low as 140 and 151 mV were needed to drive 10 mA cm-2 in seawater and alkaline solution electrolytes.

Ligand-Induced Electronic Structure Modulation of Self-Evolved Ni3S2 Nanosheets for the Electrocatalytic Oxygen Evolution Reaction.

Modulating the electronic structure of the electrocatalyst plays a vital role in boosting the electrocatalytic performance of the oxygen evolution reaction (OER). In this work, we introduced a one-step solvothermal method to fabricate 1,1-ferrocene dicarboxylic acid (FcDA)-decorated self-evolved nickel sulfide (Ni3S2) nanosheet arrays on a nickel foam (NF) framework (denoted as FcDA-Ni3S2/NF). Benefiting from the interconnected ultrathin nanosheet architecture, ligand dopants induced and facilitated in situ structural reconstruction, and the FcDA-decorated Ni3S2 (FcDA-Ni3S2/NF) outperformed its singly doped and undoped counterparts in terms of OER activity. The optimized FcDA-Ni3S2/NF self-supported electrode presents a remarkably low overpotential of 268 mV to achieve a current density of 10 mA cm-2 for the OER and demonstrates robust electrochemical stability for 48 h in a 1.0 M KOH electrolyte. More importantly, in situ electrochemical Raman spectroscopy reveals the generation of catalytically active oxyhydroxide species (NiOOH) derived from the surface construction during the OER of pristine FcDA-Ni3S2/NF, contributing significantly to its superior electrocatalytic performance. This study concerns the modulation of electronic structure through ligand engineering and may provide profound insight into the design of cost-efficient OER electrocatalysts.

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.

Metallic Ru─Ru Interaction in Ruthenium Oxide Enabling Durable Proton Exchange Membrane Water Electrolysis.

Developing efficient and robust electrocatalysts toward the oxygen evolution reaction (OER) is critical for proton exchange membrane water electrolysis (PEMWE). RuO2 possesses intrinsically high OER activity, but the concurrent electrochemical dissolution leads to rapid deactivation. Here a unique RuO2 catalyst containing metallic Ru─Ru interactions (m-RuO2) is reported, which maintains stability in practical PEMWE for 100h at 60 °C and 1 A cm-2. Experimental and theoretical investigations suggest that the presence of Ru─Ru interactions significantly increases the energy barrier for the formation of RuO2(OH)2, which is a key intermediate for Ru dissolution, and hence substantially mitigates the electrochemical corrosion of m-RuO2. Meanwhile, the Ru4d band center downshifts, accordingly, ensuring the high OER activity, and the participation of lattice oxygen in the OER is also suppressed at the Ru─Ru sites, further contributing to the enhanced durability. Interestingly, such enhanced stability is also dependent on the size of metallic Ru─Ru cluster, where the energy barrier is further increased for Ru3, but is decreased for Ru5. These results highlight the significance of local coordination structure modulation on the electrochemical stability of RuO2 and open a feasible avenue toward the development of robust OER electrocatalysts for high-performance PEMWE.

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.

Boron-incorporated IrO2-Ta2O5 coating as an efficient electrocatalyst for acidic oxygen evolution reaction

The Ir-based electrocatalysts for the acidic oxygen evolution reaction (OER) have demonstrated remarkable durability. Enhancing the Ir-based electrocatalytic activity still remains crucial owing to the scarcity of iridium. Here, a high-temperature sintering technique is employed to fabricate a boron (B)-incorporated IrO2-Ta2O5 coating with an almost perfect rutile-type crystal structure on a corrosion-resistant titanium substrate, ensuring exceptional stability for the acidic OER. The B-incorporated IrO2-Ta2O5 electrode fabricated in a mixed solution of 0.6 M H3BO3, exhibits an overpotential of 210 mV at a current density of 10 mA cm−2 and a lower Tafel slope of 34.2 mV dec−1 in a 0.5 M H2SO4 solution, which is far lower than the 272 mV overpotential and the 45.3 mV dec−1 of the IrO2-Ta2O5/Ti electrode. The electrode possesses a minimal potential increase even after undergoing continuous OER for 400 h at a high current density of 100 mA cm−2 in a 0.5 M H2SO4 solution. The incorporation of B species into IrO2-Ta2O5 effectively fine-tunes the electronic structure of Ir active sites, leading to a substantial enhancement of the intrinsic electrocatalytic activity. This study provides promising prospects for reducing the energy consumption of noble IrO2-based electrocatalysts in the practical application of electrochemical industry for the acidic OER.

The current state of transition metal-based electrocatalysts (oxides, alloys, POMs, and MOFs) for oxygen reduction, oxygen evolution, and hydrogen evolution reactions

Climate change is showing its impacts now more than ever. The intense use of fossil fuels and the resulting CO2 emissions are mainly to blame, accentuating the need to develop further the available energy conversion and storage technologies, which are regarded as effective solutions to maximize the use of intermittent renewable energy sources and reduce global CO2 emissions. This work comprehensively overviews the most recent progress and trends in the use of transition metal-based electrocatalysts for three crucial reactions in electrochemical energy conversion and storage, namely, the oxygen evolution (OER), oxygen reduction (ORR), and hydrogen evolution (HER) reactions. By analyzing the state-of-the-art polyoxometalates (POMs) and metal-organic frameworks (MOFs), the performance of these two promising types of materials for OER, ORR, and HER is compared to that of more traditional transition metal oxides and alloy-based electrocatalysts. Both catalytic activity and stability are highly influenced by the adsorption energies of the intermediate species formed in each reaction, which are very sensitive to changes in the microstructure and chemical microenvironment. POMs and MOFs allow these aspects to be easily modified to fine-tune the catalytic performances. Therefore, their chemical tunability and versatility make it possible to tailor such properties to obtain higher electrocatalytic activities, or even to obtain derived materials with more compelling properties towards these reactions.

Shape–Preserved CoFeNi–MOF/NF Exhibiting Superior Performance for Overall Water Splitting across Alkaline and Neutral Conditions

This study reported a multi–functional Co0.45Fe0.45Ni0.9–MOF/NF catalyst for oxygen evolution reaction (OER), hydrogen evolution reaction (HER), and overall water splitting, which was synthesized via a novel shape–preserving two–step hydrothermal method. The resulting bowknot flake structure on NF enhanced the exposure of active sites, fostering a superior electrocatalytic surface, and the synergistic effect between Co, Fe, and Ni enhanced the catalytic activity of the active site. In an alkaline environment, the catalyst exhibited impressive overpotentials of 244 mV and 287 mV at current densities of 50 mA cm−2 and 100 mA cm−2, respectively. Transitioning to a neutral environment, an overpotential of 505 mV at a current density of 10 mA cm−2 was achieved with the same catalyst, showing a superior property compared to similar catalysts. Furthermore, it was demonstrated that Co0.45Fe0.45Ni0.9–MOF/NF shows versatility as a bifunctional catalyst, excelling in both OER and HER, as well as overall water splitting. The innovative shape–preserving synthesis method presented in this study offers a facile method to develop an efficient electrocatalyst for OER under both alkaline and neutral conditions, which makes it a promising catalyst for hydrogen production by water splitting.

N/P-doped NiFeV oxide nanosheets with oxygen vacancies as an efficient electrocatalyst for the oxygen evolution reaction.

Plasma treatment as an effective strategy can simultaneously achieve surface modification and heteroatom doping. Here, an N/P-doped NiFeV oxide nanosheet catalyst (N/P-NiFeVO) constructed by Ar/PH3 plasma treatment is used to drive the oxygen evolution reaction (OER). The introduction of V species leads to the formation of an ultrathin ordered nanostructure and exposure of more active sites. Compared to the 2D NiFeV LDH, the prepared N/P-NiFeVO by plasma treatment possesses multiple-valence Fe, V and Ni species, which regulate the intrinsic electronic structure and enable a superior catalytic activity for the OER in alkaline media. Specifically, the N/P-NiFeVO only require an overpotential of 273 mV to drive the current density of 100 mA cm-2. What's more, the electrode can maintain a stable current density in a long-term oxygen evolution reaction (∼120 h) under alkaline conditions. This work provides new insight for the rational design of mixed metal oxides for OER electrocatalysts.

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.

Floret assembly of NiCo2O4@Tailored nanostructured carbon support for oxygen evolution reaction in alkaline medium

The oxygen evolution reaction (OER) is a bottleneck in overall water splitting due to the involvement of the four-electron process and requires a high overpotential. This hinders the stability and durability of electrocatalysts over a longer period. Herein, we report flower-like NiCo2O4 decorated on carbon nanostructures synthesized using a one-pot wet chemical method as an OER electrocatalyst in an alkaline medium. The catalytic activities were characterized by various electrochemical measurements including linear sweep voltammetry (LSV), cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and turnover frequency (TOF). 90 % NiCo2O4@rGO/f-MWCNT demonstrated a higher OER activity compared to stand-alone NiCo2O4, 90 % NiCo2O4@rGO, 90 % NiCo2O4@f-MWCNT and 80 % NiCo2O4@rGO/f-MWCNT.

Oxygen Radical Coupling on Short-Range Ordered Ru Atom Arrays Enables Exceptional Activity and Stability for Acidic Water Oxidation.

The discovery of efficient and stable electrocatalysts for oxygen evolution reaction (OER) in acid is vital for the commercialization of the proton-exchange membrane water electrolyzer. In this work, we demonstrate that short-range Ru atom arrays with near-ideal Ru-Ru interatomic distances and a unique Ru-O hybridization state can trigger direct O*-O* radical coupling to form an intermediate O*-O*-Ru configuration during acidic OER without generating OOH* species. Further, the Ru atom arrays suppress the participation of lattice oxygen in the OER and the dissolution of active Ru. Benefiting from these advantages, the as-designed Ru array-Co3O4 electrocatalyst breaks the activity/stability trade-off that plagues RuO2-based electrocatalysts, delivering an excellent OER overpotential of only 160 mV at 10 mA cm-2 in 0.5 M H2SO4 and outstanding durability during 1500 h operation, representing one of the best acid-stable OER electrocatalysts reported to date. 18O-labeled operando spectroscopic measurements together with theoretical investigations revealed that the short-range Ru atom arrays switched on an oxide path mechanism (OPM) during the OER. Our work not only guides the design of improved acidic OER catalysts but also encourages the pursuit of short-range metal atom array-based electrocatalysts for other electrocatalytic reactions.

Seamless construction of self-supporting nanoporous FeCoZn alloy as one highly efficient electrocatalyst for oxygen evolution reaction in alkaline media

Exploring high-efficient and economical electrocatalyst for oxygen evolution reaction (OER) is critical for the electrocatalytic water splitting technology to hydrogen production. Herein, we report a hierarchical nanoporous FeCoZn alloys with different Fe/Co atomic ratios in-situ constructed on bimodal porous NiZn intermetallic and Ni heterojunction over nickel foam (FeCoZn/NF) through a scalable electroplating-annealing-etching strategy. The synergistic effect between multi-elements, multiple interface coupling, and self-supporting seamless porous architecture is beneficial for enhancing the number of active sites but also promoting efficient mass transport and electron transfer. FeCoZn/NF exhibits the superior electrocatalytic activity toward OER with a low overpotential of 440 mV at 1004 mA cm−2 and small Tafel slope of 84.8 mV dec−1. The as-made sample also shows exceptional long-term catalytic stability in alkaline media with 1.0 M KOH of remained under the overpotential of 350 mV for 100 h. Besides, the combined FeCoZn/NF and Pt/C/NF for overall water splitting needs the cell potential of 1.481 V at 10 mA cm−2, along with long-term stability. This work provides implications for the design and preparation of highly active non-noble metal-based multiple alloy electrocatalysts.

Multiwall carbon nanotubes supported Rhenium doped Co3O4 as an efficient electrocatalyst for water oxidation in alkaline medium

The recent trends for the development of efficient and low cost transition metal (TMs) based anode catalysts for water splitting is crucial and important. Even though, research is continuously progressing in different directions to design catalyst; however, catalytic OER (oxygen evolution reaction) activity has remained insufficient. Till now, various transition metal oxides (TMOs) have been used as efficient and cost-effective electrocatalyst for the oxygen evolution reaction. The catalytic performance of TMOs could be enhanced by doping with the metal, which increases the catalyst's charge transfer and electronic conductivity. Decoration of TMOs with the multi-wall carbon nanotube (MWCNT) further improves catalytic activity by providing numerous active sites. Here, Co3O4/MWCNT and Rhenium (Re) doped Co3O4/MWCNT composite were prepared by simple hydrothermal process and used as electrocatalyst for OER in alkaline medium. Different concentrations of Re (0.05mmol, 0.1mmol, 0.2mmol, 0.3mmol) were doped and it was observed that the electrochemical results of the 0.2mmol Re doped Co3O4/ MWCNT (R0.2CO) was most efficient electrocatalyst which offers the OER overpotential of 298mV/dec to attain the 10mAcm−2 current density, lower Tafel slope (70mV/dec), higher value of turn over frequency (0.95), lower value of the charge transfer resistance (3.10Ω) and good stability, demonstrating the better OER catalytic activity as compared to un-doped Co3O4/MWCNT (R0.0CO) catalyst. The investigated catalyst R0.2CO is more efficient catalyst than most of the reported similar type of catalysts and offers comparable electrocatalytic activity with benchmark electrocatalyst RuO2.

Co3O4 derived ZnO: An effective electrocatalyst for oxygen evolution reaction in alkaline media

The growing accessibility of hydrogen and renewable energy sources has led to a rising significance of cobalt oxide (Co3O4)-based electrocatalysts in the context of effective electrochemical water splitting. Among two-half cell reactions, oxygen evolution reaction (OER) is more complicated and sluggish in behaviour. We present a composite material based on cobalt oxide-derived zinc oxide (Co3O4@ZnO) prepared through a wet chemical technique to overcome this challenge. The as-prepared materials are analyzed for crystallinity, morphology, and chemical bonding through X-ray diffraction (XRD), scanning electron microscopy (SEM) equipped with energy dispersive spectroscopy (EDS), high resolution transmission electron spectroscopy (HRTEM), and Fourier transform infrared (FTIR) spectroscopy, respectively. The optimized electrocatalyst reveals higher electrochemical performance for OER with an overpotential value of 262 mV at 10 mA/cm2 current density, Tafel slope value of 59 mV/dec, and charge transfer resistance (Rct) of 72 Ω. Moreover, the electrochemical active surface area (ECSA) is calculated as 320 cm2. Notably, the desired electrocatalyst shows the stability of 50 h at 10 and 20 mA/cm2 current densities. The as-prepared catalyst (Co3O4@ZnO) with effective electrochemical features can be a potential candidate for energy conversion applications toward a sustainable society.

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.

Metalation-Induced Triazine-Based Covalent Organic Framework as a High Performance Electrocatalyst for Oxygen and Hydrogen Evolution Reactions

Metalation-Induced Triazine-Based Covalent Organic Framework as a High Performance Electrocatalyst for Oxygen and Hydrogen Evolution Reactions

Triple-Function Mn Regulation of NiFe (oxy)hydroxide for Oxygen Evolution Reaction

Transition metal (oxy)hydroxides are potential oxygen evolution reaction (OER) electrocatalysts; however, simultaneously modulating multiple factors to enhance their performance is a grand challenge. Here, we report an incorporating heteroatom strategy via one-step hydrothermal approach to adjust more than one factor of Mn-doped NiFe (oxy)hydroxide (Mn-NiFeOOH/LDH) heterojunction. Mn doping regulates heterojunction morphology (reducing nanoparticles and becoming thinner and denser nanosheets), Ni/Fe ratio and valence states (Ni2+, Ni3+, and Ni3+Δ) of Ni ions. The former could effectively increase surface active sites, and the latter two reduce the content of Fe in the Mnx-NiFeOOH/LDH heterojunction, enabling more Ni2+ convert to Ni3+/3+Δ that have higher intrinsic OER activity. As a result, the first-rank Mn-NiFeOOH/LDH with ultra-low overpotential of 185 mV@20 mA cm−2 and 296 mV@500 mA cm−2, and the improved OER performance are outdo to those of commercial RuO2 catalyst for OER. Moreover, the Mn-NiFeOOH/LDH affords the earliest initial potential (1.392 V vs. RHE), corresponds to a recorded low overpotential (162 mV). Based on the density functional theory (DFT), Mn dopants can alter intermediate adsorption energy and effectively decrease OOH*’s energy barrier. This research exhibits a feasible strategy to design low cost electrocatalysts and provide new possibilities for future industrialization.