Bifunctional Electrocatalysts Research Articles

Exploring Flower-Structured Bifunctional VCu Layered Double Hydroxide and its Nanohybrid with g-C3N4for Electrochemical and Photoelectrochemical Seawater Electrolysis.

Seawater electrolysis holds great promise for sustainable green hydrogen generation, but its implementation is hindered by high energy consumption and electrode degradation. Two dimensional (2D) layered double hydroxide (LDH) exhibits remarkable stability, high catalytic activity, and excellent corrosion resistance in the harsh electrolytic environment. The synergistic effect between LDH and seawater ions enhances the oxygen evolution reaction, enabling efficient and sustainable green hydrogen generation. Here, we report a synthesis of low cost, novel 2D Vanadium Copper (VCu) LDH first time in the series of LDH's as a highly efficient bifunctional electrocatalyst. The electrochemical (EC) and photoelectrochemical (PEC) study of VCu LDH and VCu LDH/Graphite Carbon Nitride (g-C3N4) nanohybrid was performed in 0.5 M H2SO4 (acidic), 1 M KOH (basic), 0.5 M NaCl (artificial seawater), 0.5 M NaCl + 1 M KOH (artificial alkaline seawater), real seawater and 1 M KOH + real seawater (alkaline real seawater) electrolyte medium. It was found that VCu LDH shows a remarkable lower overpotential of 72 mV hydrogen evolution reaction (HER) and 254 mV oxygen evolution reaction (OER) at current density of 10 mA/cm2 under alkaline real seawater electrolysis exhibiting bifunctional activity and also showing better stability.

Shifting the Oxygen-Evolution Reaction Pathway via Cation Engineering to Activate Lattice Oxygen in Metal-Organic Frameworks.

Metal-organic frameworks (MOFs) as promising electrocatalysts have been widely studied, but their performance is limited by conductivity and coordinating saturation. This study proposes a cationic (V) modification strategy and evaluates its effect on the electrocatalytic performance of CoFe-MOF nanosheet arrays. The optimal V-CoFe-MOF/NF electrocatalyst exhibits excellent oxygen-evolution reaction (OER)/hydrogen-evolution reaction (HER) performance (231 mV at 100 mA cm-2/86 mV at 10 mA cm-2) in alkaline conditions, with its OER durability exceeding 400 h without evident degradation. Furthermore, as a bifunctional electrocatalyst for water splitting, a small cell voltage is achieved (1.60 V at 10 mA cm-2). The practicability of the catalyst is further evaluated by membrane electrode assembly (MEA), showing outstanding activity (1.53 V at 10 mA cm-2) and long-term stability (at 300 mA cm-2). Moreover, our results reveal the apparent reconstruction properties of V-CoFe-MOF/NF in alkaline electrolytes, where the partially dissolved V promotes the formation of more active β-MOOH. The mechanism study shows the OER mechanism shifts to a lattice oxygen oxidation mechanism (LOM) after V doping, which directly avoids complex multistep adsorption mechanism and reduces reaction energy. This study provides a cation mediated strategy for designing efficient electrocatalysts.

Ruthenium Nanoclusters and Single Atoms on α-MoC/N-Doped Carbon Achieves Low-input/Input-free Hydrogen Evolution via Decoupled/Coupled Hydrazine Oxidation.

The hydrazine oxidation-assisted H2 evolution method promises low-input and input-free hydrogen production. However, developing high-performance catalysts for hydrazine oxidation (HzOR) and hydrogen evolution (HER) is challenging. Here, we introduce a bifunctional electrocatalyst α-MoC/N-C/RuNSA, merging ruthenium (Ru) nanoclusters (NCs) and single atoms (SA) into cubic α-MoC nanoparticles-decorated N-doped carbon (α-MoC/N-C) nanowires, through electrodeposition. The composite showcases exceptional activity for both HzOR and HER, requiring -80 mV and -9 mV respectively to reach 10 mA cm-2. Theoretical and experimental insights confirm the importance of two Ru species for bifunctionality: NCs enhance the conductivity, and its coexistence with SA balances the H adsorption for HER and facilitates the initial dehydrogenation during the HzOR. In the overall hydrazine splitting (OHzS) system, α-MoC/N-C/RuNSA excels as both anode and cathode materials, achieving 10 mA cm-2 at just 64 mV. The zinc hydrazine (Zn-Hz) battery assembled with α-MoC/N-C/RuNSA cathode and Zn foil anode can exhibit 96% energy efficiency, as well as temporary separation of hydrogen gas during the discharge process. Therefore, integrating Zn-Hz with OHzS system enables self-powered H2 evolution, even in hydrazine sewage. Overall, the amalgamation of NCs with SA achieves diverse catalytic activities for yielding multifold hydrogen gas through advanced cell-integrated-electrolyzer system.

Synergistic Ru/RuO2 heterojunctions stabilized by carbon coating as efficient and stable bifunctional electrocatalysts for acidic overall water splitting

Synergistic Ru/RuO2 heterojunctions stabilized by carbon coating as efficient and stable bifunctional electrocatalysts for acidic overall water splitting

Ruthenium Nanoclusters and Single Atoms on α‐MoC/N‐Doped Carbon Achieves Low‐input/Input‐free Hydrogen Evolution via Decoupled/Coupled Hydrazine Oxidation

The hydrazine oxidation‐assisted H2 evolution method promises low‐input and input‐free hydrogen production. However, developing high‐performance catalysts for hydrazine oxidation (HzOR) and hydrogen evolution (HER) is challenging. Here, we introduce a bifunctional electrocatalyst α‐MoC/N‐C/RuNSA, merging ruthenium (Ru) nanoclusters (NCs) and single atoms (SA) into cubic α‐MoC nanoparticles‐decorated N‐doped carbon (α‐MoC/N‐C) nanowires, through electrodeposition. The composite showcases exceptional activity for both HzOR and HER, requiring ‐80 mV and ‐9 mV respectively to reach 10 mA cm‐2. Theoretical and experimental insights confirm the importance of two Ru species for bifunctionality: NCs enhance the conductivity, and its coexistence with SA balances the H adsorption for HER and facilitates the initial dehydrogenation during the HzOR. In the overall hydrazine splitting (OHzS) system, α‐MoC/N‐C/RuNSA excels as both anode and cathode materials, achieving 10 mA cm‐2 at just 64 mV. The zinc hydrazine (Zn‐Hz) battery assembled with α‐MoC/N‐C/RuNSA cathode and Zn foil anode can exhibit 96% energy efficiency, as well as temporary separation of hydrogen gas during the discharge process. Therefore, integrating Zn‐Hz with OHzS system enables self‐powered H2 evolution, even in hydrazine sewage. Overall, the amalgamation of NCs with SA achieves diverse catalytic activities for yielding multifold hydrogen gas through advanced cell‐integrated‐electrolyzer system.

Fe-Doped Ni/Co-Based Selenide Hierarchical Nanosheet Arrays as Self-Supporting Bifunctional Electrocatalysts for Overall Water Splitting

Fe-Doped Ni/Co-Based Selenide Hierarchical Nanosheet Arrays as Self-Supporting Bifunctional Electrocatalysts for Overall Water Splitting

Hydroxide‐derived Nanostructures: Scalable Synthesis, Characterization, Properties and Potential Applications

AbstractMetal oxide nanostructures have received an increasing attention owing to their unique chemical and physical properties along with their widespread applications in various fields. In this article, we provide an overview of our recent discovery – christened Hydroxides‐Derived Nanostructures, or HDNs – in which we react hydroxide aqueous solutions (mostly tetramethylammonium hydroxide, TMAH) at temperatures < 100 °C and under atmospheric pressure with various metal‐containing precursors to scalably prepare novel metal oxide nanostructures. In one case, we converted a dozen commercial and earth abundant Ti‐containing powders such as binary carbides, nitrides, borides, among others, into new, one‐dimensional TiO2–based lepidocrocite (1DL) nanofilaments (NFs). Application‐wise, 1DLs show outstanding performance in a number of energy, environmental, and biomedical fields such as photo‐ and electrocatalysis, water splitting, lithium‐sulfur and lithium‐ion batteries, water purification, dye degradation, cancer therapy, and polymer composites. In addition to 1DL, the HDNs family encompasses other metal oxides nanostructures including magnetic Fe3O4 nanoparticles and MnO2 birnessite‐based crystalline two‐dimensional (2D) flakes. The latter showed promise as a bifunctional electrocatalyst for water oxidation and oxygen reduction, as well as cathodes in aqueous asymmetric supercapacitor and in an aqueous ammonium ion battery. Our developed recipe provides a new vista in the molecular self‐assembly synthesis of metal oxide nanomaterials that can advance the field with a library of novel nanostructures with substantial implications in a multitude of fields.This article is protected by copyright. All rights reserved

Machine Learning-Assisted Study of RENxC6-x-Doped Graphene as Potential Electrocatalysts for Oxygen Electrode Reactions.

In the application of renewable energy, the oxidation-reduction reaction (ORR) and oxygen evolution reaction (OER) are two crucial reactions. Single-atom catalysts (SACs) based on metal-doped graphene have been widely employed due to their high activity and high atom utilization efficiency. However, the catalytic activity is significantly influenced by different metals and local coordination, making it challenging to efficiently screen through either experimental or density functional theory (DFT) calculations. To address this issue, this study employed a combination of DFT calculations and machine learning (DFT-ML) to investigate rare earth-modified carbon-based (RENxC6-x) electrocatalysts. Based on computational data from 75 catalysts, we trained two ML models to capture the underlying patterns of physical properties and overpotential. Subsequently, the candidate catalysts were screened, leading to the discovery of four ORR catalysts, nine OER catalysts, and five bifunctional electrocatalysts, all of which were thoroughly validated for their stability. Lastly, by integrating the ML models with the SHAP analysis framework, we revealed the influence of atomic radius, Pauling electronegativity, and other features on the catalytic activity. Additionally, we analyzed the physicochemical properties of potential catalysts through DFT calculations. The revolutionary DFT-ML approach provides a crucial driving force for the design and synthesis of potential catalysts in subsequent studies.

Unique ping-pong daisy-like catalysts: Efficient overall hydrolysis catalysis driven by vanadium-doped Fe2P and Co3(PO4)2 nanosheet composites

Balancing catalytic activity and durability remains a challenge in the development of high performance, inexpensive and durable electrocatalysts. In this study, fully hydrolyzed composite catalyst V–Fe2P@Co3(PO4)2/NF with ping-pong daisy-like morphology was synthesized using conventional hydrothermal and chemical vapor deposition (CVD) processes. In alkaline electrolyte, V–Fe2P@Co3(PO4)2/NF showed excellent electrochemical performance, achieving a current density of 10 mA cm−2 when the driving overpotentials for the hydrogen production reaction (HER) and oxidation reaction (OER) were 56 mV and 178 mV, respectively. Meanwhile, V–Fe2P@Co3(PO4)2/NF demonstrated good durability in terms of both HER and OER stability. Furthermore, the driving voltage required for the electrolyser assembled with V–Fe2P@Co3(PO4)2/NF as the electrode is lower than that of the RuO2/NF||Pt/C/NF electrode, both of which have driving voltages of 1.503 and 1.562 V (10 mA cm−2), respectively. Meanwhile, it achieves a Faraday efficiency of 95%. This study offers a feasible solution towards synthesizing and applying bifunctional water decomposition electrocatalysts.

Dopant induced hollow Ni2P nanocrystals regulate dehydrogenation kinetics for highly efficient solar-driven hydrazine assisted H2 production

Replacing kinetically sluggish oxygen evolution reaction (OER) with a thermodynamically favorable hydrazine oxidation reaction (HzOR) to produce hydrogen has emerged as a more energy-efficient alternative than water splitting. However, the lack of promising bifunctional electrocatalysts hinders its scalable applications. Here, we report a colloidal synthesis of Mn-dopant induced hollow Ni2P nanocrystals (NCs) using a heat-up approach, which act as superior bifunctional electrocatalysts for both HzOR (55 mV at 10 mA/cm2) and hydrogen evolution reaction (HER, 192 mV at 50 mA/cm2). The two-electrode electrolyzer requires a low cell voltage of 59 mV to achieve 10 mA/cm2 and a current density of ∼ 50.4 mA/cm2 to reach 0.5 V. Theoretical studies unraveled that Mn-doping regulates the electronic structure of Ni2P and optimizes the H* adsorption/desorption and dehydrogenation kinetics. When integrated with a Si photovoltaic device, the bifunctional hollow Mn-doped Ni2P NCs enabled solar-driven hydrazine assisted H2 production with a ∼ 14.6 % efficiency.

Boosting electrocatalytic hydrogen generation from water splitting with heterostructured MoS2/NiFe2O4 composite in alkaline media

Design and synthesis of earth-abundant and robust bifunctional electrocatalysts have been greatly sought for commercialization of the technology for clean and renewable energy and replacement of the energy equipment based on fossil fuels. In this work, a facile hydrothermal approach is used to synthesize MoS2/NiFe2O4-based nanocomposite as a novel electrocatalyst for alkaline water splitting. Surface analysis was conducted using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Benefiting from the synergy of lamellar MoS2 and crystalline NiFe2O4, the obtained MoS2/NiFe2O4 composite shows excellent hydrogen evolution reaction (η10 = 190 mV, η50 = 279 mV) and oxygen evolution reaction (OER) (η50 = 350 mV, η100 = 360 mV) activity with high TOF (0.01 s−1@190 mV for HER and 0.24 s−1 @360 mV for OER) and displays good electrochemical stability. Explicitly, the electrocatalyst requires a cell voltage of 1.69 V to drive overall water splitting at a current density of 10 mA cm−2. Density functional theory (DFT) results demonstrated that the MoS2/NiFe2O4 composite electrocatalyst has smaller hydrogen adsorption free energy (|ΔGH*|) than pristine MoS2 and NiFe2O4, which demonstrates the effective adsorption and cleavage of water on the catalyst surface. This work thus presents an approach for the synthesis and rational design of metal oxide/metal sulfide hybrids as an electrocatalyst with high performance for overall water splitting.

Heterogeneous Ni-Boride/Phosphide Anchored Amorphous B-C Layer for Overall Water Electrocatalysis.

The rational design of efficient and economical bifunctional electrocatalysts remained a challenge for overall water electrolysis. In this work, the Ni-boride/ phosphide particles anchored amorphous B-doped carbon layer with hierarchical porous characteristics in Ni foam (Ni3P/Ni3B/B-C/NF) was fabricated for overall water splitting. The Boroncarbide (B4C) power was filled and fixed in the NF interspace through the electroplating and electroless plating, and then annealed in vacuum high temperature. The amorphous B-C layer derived from the B4 C not only speeded up the electron transport, but also cooperate with Ni-boride/phosphide to enhance the electrocatalytic activity for HER and OER synergistically. Furthermore, the hierarchical porous architecture of Ni3P/Ni3B/B-C/NF increased space utilization to load more active materials. The self-supported Ni3P/Ni3B/B-C/NF electrode possessed a low overpotential of 212 and 280 mV to deliver 100 mA cm-2 for HER and OER, respectively, and high stability for 48 h. In particular, the electrolyzer constituted with the Ni3P/Ni3B/B-C/NF bifunctional electrocatalyst only required a voltage of 1.59 V at 50 mA cm-2 for water electrocatalysis under alkaline medium, and demonstrated long-term stability for 48 h. This study provides a new technical path for the development of bifunctional of transition metal borides to promote the application of hydrogen production from water splitting.

Electron Manipulation and Surface Reconstruction of Bimetallic Iron-Nickel Phosphide Nanotubes for Enhanced Alkaline Water Electrolysis.

Developing high-efficiency and stable bifunctional electrocatalysts for water splitting remains a great challenge. Herein, NiMoO4 nanowires as sacrificial templates to synthesize Mo-doped NiFe Prussian blue analogs are employed, which can be easily phosphorized to Mo-doped Fe2xNi2(1-x)P nanotubes (Mo-FeNiP NTs). This synthesis method enables the controlled etching of NiMoO4 nanowires that results in a unique hollow nanotube architecture. As a bifunctional catalyst, the Mo-FeNiP NTs present lower overpotential and Tafel slope of 151.3 (232.6) mV at 100 mA cm-2 and 76.2 (64.7) mV dec-1 for HER (OER), respectively. Additionally, it only requires an ultralow cell voltage of 1.47 V to achieve 10 mA cm-2 for overall water splitting and can steadily operate for 200 h at 100 mA cm-2. First-principles calculations demonstrate that Mo doping can effectively adjust the electron redistribution of the Ni hollow sites to optimize the hydrogen adsorption-free energy for HER. Besides, in situ Raman characterization reveals the dissolving of doped Mo can promote a rapid surface reconstruction on Mo-FeNiP NTs to dynamically stable (Fe)Ni-oxyhydroxide layers, serving as the actual active species for OER. The work proposes a rational approach addressed by electron manipulation and surface reconstruction of bimetallic phosphides to regulate both the HER and OER activity.

Nickel-hydroxide decorated trimanganese-tetroxide nanorods supported on graphene as bifunctional electrocatalyst for metal–air batteries

Manganese oxide, such as Mn3O4, is one of promising material as electrocatalyst in air–cathode for metal–air battery due to low cost, high catalytic activity and good stability. Although pure Mn3O4 material exhibits excellent catalytic activity to ORR, it is severely limited by its intrinsically low conductivity and high over-potential toward OER. In this work, the hybrid materials of nickel-hydroxide-decorated nanorods of trimanganese-tetroxide supported on reduced-graphene have been prepared by one-step hydrothermal method. The composite materials are used as bifunctional cathode catalysts to ORR/OER, and investigated by the technologies of rotating disk electrode and metal–air batteries. The results indicate that the hybrid material of Mn-Ni/rGO use as catalyst in air–cathode for Al/Zn–air battery has good catalytic activity. Based on analysis of scanning electron microscope and X-ray photoelectron spectroscopy, the composite material shows good performance owing to the improvement of conductivity supported on graphene, more Mn4+ on the surface of hybrid material, the coexistence of Mn3+/Mn4+ redox couple, and the synergism between nickel-hydroxide and graphene.

A Bifunctional Electrocatalyst of Flower-Like Cr-Doped CoP/Fe2P Microsphere for Efficient Overall Water Splitting

Abstract Developing efficient, low-price non-noble metal-based electrocatalysts for overall water splitting in alkaline medium remains a formidable challenge. In our work, Cr-doped CoP/Fe2P (Cr-CoP/Fe2P) flower-like microsphere was synthesized through a simple hydrothermal and phosphating process. The resulting Cr-CoP/Fe2P electrocatalyst shows significantly enhanced oxygen evolution reaction performance (262 mV @ 10 mA cm-2) and has a satisfactory hydrogen evolution reaction performance (114 mV @ 10 mA cm-2), coupled with favorable stability in an alkaline medium. Furthermore, when assembling Cr-CoP/Fe2P into an electrolytic cell, the two-electrode system can provide a current density of 10 mA cm-2 at a voltage of 1.61 V. At high current density, the performance of the electrolytic cell composed of Cr-CoP/Fe2P is superior to that of noble metal catalyst electrode pair. Electronic structure analysis and various characterizations confirm that Cr doping and the formation of CoP/Fe2P heterogeneous interfaces redistribute the electron densities of the active sites, enlarge the specific surface area, and enhance the aerophobicity of the catalysts, thereby improving the electrocatalytic property. This work provides a referable method for engineering highly efficient and stable non-noble polymetallic phosphides, which serve as bifunctional electrocatalyst for overall water splitting.

Multifunctional carbon armor: Synchronously improving oxygen reaction kinetics, mass transfer dynamics, and robustness of transition metal alloy based hybrid catalyst

Construction of robust protective cover on delicate active sites is a frequently-used scheme to enhance the durability of air-cathode catalyst working in harsh environment, thus the lifespan of rechargeable Zinc-air batteries (ZABs). Paradoxically, this would degrade the activity due to the constricted accessibility of active sites to reactants. Herein, carbon nanotubes with abundant mesoporous defects and Fe-N4 species were elaborately designed to be multifunctional protective armor to encapsulate Ni3Fe nano-alloys (Ni3Fe@CNTs/Fe-N4) for bifunctional oxygen electrocatalyst. In/ex-situ spectroscopy analysis and theoretical calculations reveal that the constructed mesoporous carbon defects effectively facilitate the multiphase mass transfer and the oxygen evolution reaction kinetics via strong electrons coupling with packaged Ni3Fe nano-alloys. Meanwhile, the synchronously introduced Fe-N4 moieties could serve as oxygen reduction active sites. Thus, the obtained Ni3Fe@CNTs/Fe-N4 hybrid electrocatalyst simultaneously exhibits remarkable bifunctional catalytic activity (E1/2=0.86/Ej=10=1.59 V vs RHE) and durability over 450 h in the chronoamperometric test at 1.59 V, endowing the assembled Zn-air batteries (ZABs) with a high power density (150 mW cm−2) and lifespan (307 h), much better than that employing benchmark Pt/C+RuO2 mixed catalyst. This work demonstrates an innovative design route for the multifunctional armor to concurrently enhance the durability, activity and robustness of air-cathode-catalyst for ZABs.

Efficient Hydrogen Evolution Electrocatalyst: MoN/Ni3N/NF Coupled with Methanol Oxidation Reaction for Formate Production in Alkaline Media

Abstract Electrocatalytic water splitting for hydrogen production is promising, but its practical application is limited by the sluggish kinetics of the anodic oxygen evolution reaction (OER) and the less valuable oxygen by-product. Hence, replacing OER with a thermodynamically favorable methanol oxidation reaction (MOR) and coupling with value-added formate generation on the anode is an energy-saving and effective scheme. In this work, we report a self-supporting bifunctional electrocatalyst MoN/Ni3N/NF, which exhibits excellent hydrogen evolution reaction catalytic activity and stability, requiring overpotentials of only 18 and 68 mV to reach current densities of −10 and −100 mA cm−2, respectively. Moreover, the catalyst’s performance minimally deteriorates after long-standing chronopotentiometry measurements (−100 mA cm−2@150h). When MOR is used instead of OER, the required potential drops by 200 mV to 1.38 V at a current density of 100 mA cm−2 and MoN/Ni3N/NF also demonstrates splendid catalytic stability towards OER and MOR. Finally, a two-electrode system employing MoN/Ni3N/NF as a bifunctional electrocatalyst only requires a cell voltage of 1.40, 1.68 V to achieve current densities of 10 and 100 mA cm−2, respectively. The coupled electrolyzer also exhibits high faradaic efficiency for producing cathodic H2 (100%) and anodic formate (90%).

Iron Triad-Based Bimetallic M–N–C Nanomaterials as Highly Active Bifunctional Oxygen Electrocatalysts

Iron Triad-Based Bimetallic M–N–C Nanomaterials as Highly Active Bifunctional Oxygen Electrocatalysts

Unique sandwich-cookie-like nanosheet array heterojunction bifunctional electrocatalyst towards efficient overall water/seawater splitting

Construction of multi-component heterostructures is an effective strategy for electrocatalysts to improve both the hydrogen evolution reaction (HER) at the cathode and the oxygen evolution reaction (OER) activity at the anode. Herein, an efficient bifunctional electrocatalyst towards overall water/seawater splitting (OW/SS) is reported with strategy of heterostructure construction (ruthenium/nickel phosphorus) on nickel hydroxide (Ni(OH)2). With the unique hydrolysis layer (Ni(OH)2), the processes of H2O hydrolysis and the adsorption/desorption of H*/O-containing intermediates (OH, O, OOH) were greatly boosted by Ru and P sites, which acted as the catalytic active centers of OER and HER, respectively. In addition, the electronic structure reconfiguration was realized through the strong interaction between multi-interfaces. For alkaline HER at the current density of 10 mA cm−2, the overpotential of Ru-P-Ni(OH)2/NF (denoted as RNPOH/NF) was 98 mV, whereas just 230 mV of overpotential was essential to stimulate alkaline OER at the current density of 20 mA cm−2. Specifically, as a bifunctional electrocatalyst towards overall water splitting, RNPOH/NF deserves cell voltages of 1.7/1.92 V and 1.75/1.94 V, respectively, to activate current densities of 50/100 mA cm−2 in alkaline water/seawater systems, together with a good durability of 12 h. This work contributes insights to the development of bifunctional electrocatalysts for overall water/seawater splitting.

Boosting oxygen/hydrogen evolution catalysis via ruthenium doping in perovskite oxide for efficient alkaline water splitting

Recently, perovskite oxides have acquired a rapidly growing research interest in energy storage and conversion systems, especially the electrolysis of water. Rational doping is an extremely effective strategy to enhance the hydrogen evolution reaction/oxygen evolution reaction (HER/OER) of the perovskite oxides. Herein, a series of novel bi-functional electrocatalysts were synthesized by doping Ru in SrFeO3-δ perovskite oxide (SrFe1-xRuxO3-δ, x = 0, 0.15, 0.30, 0.45) which exhibit remarkable enhancements of HER/OER activities and long-term stabilities in the alkaline solution (1.0 M KOH). Among them, SrFe0.7Ru0.3O3-δ (SFR30) shows the best electrocatalytic activities for overall water splitting, exhibiting low overpotentials for HER (∼41 mV) and OER (∼334 mV) at −10 and 10 mA cm−2, respectively, generating current densities of 10 mA cm−2 in alkaline electrolytic cell using the potential of 1.58 V. In addition, the SFR30 electrocatalyst exhibits remarkable stability which can be operated continuously for 96 h without significant delay. Density functional theory (DFT) calculations indicate that Ru doping can effectively modulate the adsorption of intermediates on the active sites to achieve excellent electrocatalytic performance. Many new prospects have been opened for the development of bi-functional electrocatalysts for overall water splitting.