Ultrafine Co3O4 Nanoparticles within Nitrogen‐Doped Carbon Matrix Derived from Metal–Organic Complex for Boosting Lithium Storage and Oxygen Evolution Reaction

Transition metal oxides have recently received great attention for application in advanced lithium‐ion batteries (LIBs) and oxygen evolution reaction (OER). Herein, the ethylenediaminetetraacetic cobalt complex as a precursor to synthesize ultrafine Co₃O₄ nanoparticles encapsulated into a nitrogen‐doped carbon matrix (NC) composites is presented. The as‐prepared Co₃O₄/NC‐350 obtained by pyrolysis at 350 °C demonstrates superior rate performance (372 mAh g^?1 at 5.0 A g^?1) and high cycling stability (92% capacity retention after 300 cycles at 1.0 A g^?1) as anode for LIBs. When evaluated as an electrocatalyst for OER, the Co₃O₄/NC‐350 achieves an overpotential of 298 mV at a current density of 10 mA cm^?2. The NC‐encapsualted porous hierarchical structure assures fast and continuous electron transportation, high activity sites, and strong structural integrity. This works offers novel complex precursors for synthesizing transition metal–based electrodes for boosting electrochemical energy conversion and storage.     

Ni‐Fe Nitride Nanoplates on Nitrogen‐Doped Graphene as a Synergistic Catalyst for Reversible Oxygen Evolution Reaction and Rechargeable Zn‐Air Battery

Obtaining bifunctional electrocatalysts with high activity for the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) is a main hurdle in the application of rechargeable metal‐air batteries. Earth‐abundant 3d transition metal‐based catalysts have been developed for the OER and ORR; however, most of these are based on oxides, whose insulating nature strongly restricts their catalytic performance. This study describes a metallic Ni‐Fe nitride/nitrogen‐doped graphene hybrid in which 2D Ni‐Fe nitride nanoplates are strongly coupled with the graphene support. Electronic structure of the Ni‐Fe nitride is changed by hybridizing with the nitrogen‐doped graphene. The unique heterostructure of this hybrid catalyst results in very high OER activity with the lowest onset overpotential (150 mV) reported, and good ORR activity comparable to that for commercial Pt/C. The high activity and durability of this bifunctional catalyst are also confirmed in rechargeable zinc‐air batteries that are stable for 180 cycles with an overall overpotential of only 0.77 V at 10 mA^?2.     

Ultrathin Cobalt Oxide Layers as Electrocatalysts for High‐Performance Flexible Zn–Air Batteries

Synergistic improvements in the electrical conductivity and catalytic activity for the oxygen reduction reaction (ORR)/oxygen evolution reaction (OER) are of paramount importance for rechargeable metal–air batteries. In this study, one‐nanometer‐scale ultrathin cobalt oxide (CoO_x) layers are fabricated on a conducting substrate (i.e., a metallic Co/N‐doped graphene substrate) to achieve superior bifunctional activity in both the ORR and OER and ultrahigh output power for flexible Zn–air batteries. Specifically, at the atomic scale, the ultrathin CoO_x layers effectively accelerate electron conduction and provide abundant active sites. X‐ray absorption spectroscopy reveals that the metallic Co/N‐doped graphene substrate contributes to electron transfer toward the ultrathin CoO_x layer, which is beneficial for the electrocatalytic process. The as‐obtained electrocatalyst exhibits ultrahigh electrochemical activity with a positive half‐wave potential of 0.896 V for ORR and a low overpotential of 370 mV at 10 mA cm^?2 for OER. The flexible Zn–air battery built with this catalyst exhibits an ultrahigh specific power of 300 W g_cat ^?1, which is essential for portable devices. This work provides a new design pathway for electrocatalysts for high‐performance rechargeable metal–air battery systems.     

Ruthenium‐Doped Cobalt–Chromium Layered Double Hydroxides for Enhancing Oxygen Evolution through Regulating Charge Transfer

Exploring the origin of transition metal (TM) lattice‐doped layered double hydroxides (LDHs) toward the oxygen evolution reaction (OER) plays a crucial role in engineering efficient electrocatalysts. Without understanding the physics behind the TM‐induced catalytic enhancements, it would be challenging to design the next generation of electrocatalysts. Herein, single Ru atoms are introduced into a CoCr LDHs lattice to improve activity. In 0.1 m KOH, CoCrRu LDHs require only 290 mV overpotential to drive to 10 mA cm^?2 and show a Tafel slope of 56.12 mV dec^?1. Electronic structure analyses based on density functional theory confirm that promoted OER activity originates from synergetic charge transfer among Ru, Cr, and Co elements. Specifically, Ru dopants can downshift d states of Co and enhance electron donation of Cr to oxygenates, which essentially breaks the scaling relation and achieves higher activity. This work provides insights into how single atomic Ru dopant tunes the electronic structures of its neighbor's active site Co and thus increases OER activities.     

Bimetallic Nickel‐Substituted Cobalt‐Borate Nanowire Array: An Earth‐Abundant Water Oxidation Electrocatalyst with Superior Activity and Durability at Near Neutral pH

There is an urgent demand to develop earth‐abundant electrocatalysts for efficient and durable water oxidation under mild conditions. A nickel‐substituted cobalt‐borate nanowire array is developed on carbon cloth (Ni‐Co‐Bi/CC) via oxidative polarization of NiCo₂S₄ nanoarray in potassium borate (K‐Bi). As a bimetallic electrocatalyst for water oxidation, such Ni‐Co‐Bi/CC is superior in catalytic activity and durability in 0.1 m K‐Bi (pH: 9.2), with a turnover frequency of 0.33 mol O₂ s^?1 at the overpotential of 500 mV and nearly 100% Faradaic efficiency. To drive a geometrical catalytic current density of 10 mA cm^?2, it only needs overpotential of 388 mV, 34 mV less than that for Co‐Bi/CC, outperforming reported non‐noble‐metal catalysts operating under benign conditions. Notably, its activity is maintained over 80 000 s. Density functional theory calculations suggest that the O* to OOH* conversion is the rate‐determining step and Ni substitution decreases the free energy on Co‐Bi from 2.092 to 1.986 eV.     

Transition‐Metal‐Doped RuIr Bifunctional Nanocrystals for Overall Water Splitting in Acidic Environments

The establishment of electrocatalysts with bifunctionality for efficient oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) in acidic environments is necessary for the development of proton exchange membrane (PEM) water electrolyzers for the production of clean hydrogen fuel. RuIr alloy is considered to be a promising electrocatalyst because of its favorable OER performance and potential for HER. Here, the design of a bifunctional electrocatalyst with greatly boosted water‐splitting performance from doping RuIr alloy nanocrystals with transition metals that modify electronic structure and binding strength of reaction intermediates is reported. Significantly, Co‐RuIr results in small overpotentials of 235 mV for OER and 14 mV for HER (@ 10 mA cm^?2 current density) in 0.1 m HClO₄ media. Therefore a cell voltage of just 1.52 V is needed for overall water splitting to produce hydrogen and oxygen. More importantly, for a series of M‐RuIr (M = Co, Ni, Fe), the catalytic activity dependence at fundamental level on the chemical/valence states is used to establish a novel composition‐activity relationship. This permits new design principles for bifunctional electrocatalysts.     

ZIF‐8/ZIF‐67‐Derived Co‐Nx‐Embedded 1D Porous Carbon Nanofibers with Graphitic Carbon‐Encased Co Nanoparticles as an Efficient Bifunctional Electrocatalyst

Herein, an approach is reported for fabrication of Co‐N_x‐embedded 1D porous carbon nanofibers (CNFs) with graphitic carbon‐encased Co nanoparticles originated from metal–organic frameworks (MOFs), which is further explored as a bifunctional electrocatalyst for both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Electrochemical results reveal that the electrocatalyst prepared by pyrolysis at 1000 °C (CoNC‐CNF‐1000) exhibits excellent catalytic activity toward ORR that favors the four‐electron ORR process and outstanding long‐term stability with 86% current retention after 40 000 s. Meanwhile, it also shows superior electrocatalytic activity toward OER, reaching a lower potential of 1.68 V at 10 mA cm^?2 and a potential gap of 0.88 V between the OER potential (at 10 mA cm^?2) and the ORR half‐wave potential. The ORR and OER performance of CoNC‐CNF‐1000 have outperformed commercial Pt/C and most nonprecious‐metal catalysts reported to date. The remarkable ORR and OER catalytic performance can be mainly attributable to the unique 1D structure, such as higher graphitization degree beneficial for electronic mobility, hierarchical porosity facilitating the mass transport, and highly dispersed CoN_xC active sites functionalized carbon framework. This strategy will shed light on the development of other MOF‐based carbon nanofibers for energy storage and electrochemical devices.     

Noble‐Metal‐Free Electrocatalysts for Oxygen Evolution

Oxygen evolution reaction (OER) plays a vital role in many energy conversion and storage processes including electrochemical water splitting for the production of hydrogen and carbon dioxide reduction to value‐added chemicals. IrO₂ and RuO₂, known as the state‐of‐the‐art OER electrocatalysts, are severely limited by the high cost and low earth abundance of these noble metals. Developing noble‐metal‐free OER electrocatalysts with high performance has been in great demand. In this review, recent advances in the design and synthesis of noble‐metal‐free OER electrocatalysts including Ni, Co, Fe, Mn‐based hydroxides/oxyhydroxides, oxides, chalcogenides, nitrides, phosphides, and metal‐free compounds in alkaline, neutral as well as acidic electrolytes are summarized. Perspectives are also provided on the fabrication, evaluation of OER electrocatalysts and correlations between the structures of the electrocatalysts and their OER activities.     

Metal–Organic‐Framework‐Derived Hybrid Carbon Nanocages as a Bifunctional Electrocatalyst for Oxygen Reduction and Evolution

The oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are cornerstone reactions for many renewable energy technologies. Developing cheap yet durable substitutes of precious‐metal catalysts, especially the bifunctional electrocatalysts with high activity for both ORR and OER reactions and their streamlined coupling process, are highly desirable to reduce the processing cost and complexity of renewable energy systems. Here, a facile strategy is reported for synthesizing double‐shelled hybrid nanocages with outer shells of Co‐N‐doped graphitic carbon (Co‐NGC) and inner shells of N‐doped microporous carbon (NC) by templating against core–shell metal–organic frameworks. The double‐shelled NC@Co‐NGC nanocages well integrate the high activity of Co‐NGC shells into the robust NC hollow framework with enhanced diffusion kinetics, exhibiting superior electrocatalytic properties to Pt and RuO₂ as a bifunctional electrocatalyst for ORR and OER, and hold a promise as efficient air electrode catalysts in Zn–air batteries. First‐principles calculations reveal that the high catalytic activities of Co‐NGC shells are due to the synergistic electron transfer and redistribution between the Co nanoparticles, the graphitic carbon, and the doped N species. Strong yet favorable adsorption of an OOH* intermediate on the high density of uncoordinated hollow‐site C atoms with respect to the Co lattice in the Co‐NGC structure is a vital rate‐determining step to achieve excellent bifunctional electrocatalytic activity.     

Active Sites Intercalated Ultrathin Carbon Sheath on Nanowire Arrays as Integrated Core–Shell Architecture: Highly Efficient and Durable Electrocatalysts for Overall Water Splitting

The development of active bifunctional electrocatalysts with low cost and earth‐abundance toward oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) remains a great challenge for overall water splitting. Herein, metallic Ni₄Mo nanoalloys are firstly implanted on the surface of NiMoO_x nanowires array (NiMo/NiMoO_x ) as metal/metal oxides hybrid. Inspired by the superiority of carbon conductivity, an ultrathin nitrogen‐doped carbon sheath intercalated NiMo/NiMoO_x (NC/NiMo/NiMoO_x ) nanowires as integrated core–shell architecture are constructed. The integrated NC/NiMo/NiMoO_x array exhibits an overpotential of 29 mV at 10 mA cm^?2 and a low Tafel slope of 46 mV dec^?1 for HER due to the abundant active sites, fast electron transport, low charge‐transfer resistance, unique architectural structure and synergistic effect of carbon sheath, nanoalloys, and oxides. Moreover, as OER catalysts, the NC/NiMo/NiMoO_x hybrids require an overpotential of 284 mV at 10 mA cm^?2. More importantly, the NC/NiMo/NiMoO_x array as a highly active and stable electrocatalyst approaches ≈10 mA cm^?2 at a voltage of 1.57 V, opening an avenue to the rational design and fabrication of the promising electrode materials with architecture structures toward the electrochemical energy storage and conversion.     

Nitrogen‐Doped Graphene‐Encapsulated Nickel–Copper Alloy Nanoflower for Highly Efficient Electrochemical Hydrogen Evolution Reaction

Development of high‐performance and low‐cost nonprecious metal electrocatalysts is critical for eco‐friendly hydrogen production through electrolysis. Herein, a novel nanoflower‐like electrocatalyst comprising few‐layer nitrogen‐doped graphene‐encapsulated nickel–copper alloy directly on a porous nitrogen‐doped graphic carbon framework (denoted as Ni_x Cu_y @ NG‐NC) is successfully synthesized using a facile and scalable method through calcinating the carbon, copper, and nickel hydroxy carbonate composite under inert atmosphere. The introduction of Cu can effectively modulate the morphologies and hydrogen evolution reaction (HER) performance. Moreover, the calcination temperature is an important factor to tune the thickness of graphene layers of the Ni_x Cu_y @ NG‐NC composites and the associated electrocatalytic performance. Due to the collective effects including unique porous flowered architecture and the synergetic effect between the bimetallic alloy core and graphene shell, the Ni₃Cu₁@ NG‐NC electrocatalyst obtained under optimized conditions exhibits highly efficient and ultrastable activity toward HER in harsh environments, i.e., a low overpotential of 122 mV to achieve a current density of 10 mA cm^?2 with a low Tafel slope of 84.2 mV dec^?1 in alkaline media, and a low overpotential of 95 mV to achieve a current density of 10 mA cm^?2 with a low Tafel slope of 77.1 mV dec^?1 in acidic electrolyte.     

Constructing Pure Phase Tungsten‐Based Bimetallic Carbide Nanosheet as an Efficient Bifunctional Electrocatalyst for Overall Water Splitting

Carbides are commonly regarded as efficient hydrogen evolution reaction (HER) catalysts, but their poor oxygen evolution reaction (OER) catalytic activities seriously limit their practical application in overall water splitting. Here, vertically aligned porous cobalt tungsten carbide nanosheet embedded in N‐doped carbon matrix (Co₆W₆C@NC) is successfully constructed on flexible carbon cloth (CC) as an efficient bifunctional electrocatalyst for overall water splitting via a facile metal–organic framework (MOF) derived method. The synergistic effect of Co and W atoms effectively tailors the electron state of carbide, optimizing the hydrogen‐binding energy. Thus Co₆W₆C@NC shows an enhanced HER performance with an overpotential of 59 mV at a current density of ?10 mA cm^?2. Besides, Co₆W₆C@NC easily in situ transforms into tungsten actived cobalt oxide/hydroxide during the OER process, serving as OER active species, which provides an excellent OER activity with an overpotential of 286 mV at a current density of ?10 mA cm^?2. The water splitting device, by applying Co₆W₆C@NC as both the cathode and anode, requires a low cell voltage of 1.585 V at 10 mA cm^?2 with the great stability in alkaline solution. This work provides a feasible strategy to fabricate bimetallic carbides and explores their possibility as bifunctional catalysts toward overall water splitting.     

Polyaniline Derived N‐Doped Carbon‐Coated Cobalt Phosphide Nanoparticles Deposited on N‐Doped Graphene as an Efficient Electrocatalyst for Hydrogen Evolution Reaction

The development of highly efficient and durable non‐noble metal electrocatalysts for the hydrogen evolution reaction (HER) is significant for clean and renewable energy research. This work reports the synthesis of N‐doped graphene nanosheets supported N‐doped carbon coated cobalt phosphide (CoP) nanoparticles via a pyrolysis and a subsequent phosphating process by using polyaniline. The obtained electrocatalyst exhibits excellent electrochemical activity for HER with a small overpotential of ?135 mV at 10 mA cm^?2 and a low Tafel slope of 59.3 mV dec^?1 in 0.5 m H₂SO₄. Additionally, the encapsulation of N‐doped carbon shell prevents CoP nanoparticles from corrosion, exhibiting good stability after 14 h operation. Moreover, the as‐prepared electrocatalyst also shows outstanding activity and stability in basic and neutral electrolytes.     

Topotactic Transformations in an Icosahedral Nanocrystal to Form Efficient Water‐Splitting Catalysts

Designing high‐performance, precious‐metal‐based, and economic electrocatalysts remains an important challenge in proton exchange membrane (PEM) electrolyzers. Here, a highly active and durable bifunctional electrocatalyst for PEM electrolyzers based on a rattle‐like catalyst comprising a Ni/Ru‐doped Pt core and a Pt/Ni‐doped RuO₂ frame shell, which is topotactically transformed from an icosahedral Pt/Ni/Ru nanocrystal, is reported. The RuO₂‐based frame shell with its highly reactive surfaces leads to a very high activity for the oxygen evolution reaction (OER) in acidic media, reaching a current density of 10 mA cm^?2 at an overpotential of 239 mV, which surpasses those of previously reported catalysts. The Pt dopant in the RuO₂ shell enables a sustained OER activity even after a 2000 cycles of an accelerated durability test. The Pt‐based core catalyzes the hydrogen evolution reaction with an excellent mass activity. A two‐electrode cell employing Pt/RuO₂ as the electrode catalyst demonstrates very high activity and durability, outperforming the previously reported cell performances.     

Ambient Fast Synthesis and Active Sites Deciphering of Hierarchical Foam‐Like Trimetal–Organic Framework Nanostructures as a Platform for Highly Efficient Oxygen Evolution Electrocatalysis

Metal–organic frameworks (MOFs) have attracted tremendous interest due to their promising applications including electrocatalysis originating from their unique structural features. However, it remains a challenge to directly use MOFs for oxygen electrocatalysis because it is quite difficult to manipulate their dimension, composition, and morphology of the MOFs with abundant active sites. Here, a facile ambient temperature synthesis of unique NiCoFe‐based trimetallic MOF nanostructures with foam‐like architecture is reported, which exhibit extraordinary oxygen evolution reaction (OER) activity as directly used catalyst in alkaline condition. Specifically, the (Ni₂Co₁)_0.925Fe_0.075‐MOF‐NF delivers a minimum overpotential of 257 mV to reach the current density of 10 mA cm^?2 with a small Tafel slope of 41.3 mV dec^?1 and exhibits high durability after long‐term testing. More importantly, the deciphering of the possible origination of the high activity is performed through the characterization of the intermediates during the OER process, where the electrochemically transformed metal hydroxides and oxyhydroxides are confirmed as the active species.     

Reducing the Barrier Energy of Self‐Reconstruction for Anchored Cobalt Nanoparticles as Highly Active Oxygen Evolution Electrocatalyst

It is crucial for leaping forward renewable energy technology to develop highly active oxygen evolution reaction (OER) catalysts with fast OER kinetics, and the novel design of high‐performance catalysts may come down to unveiling the origin of high catalytic behavior. Herein, a new class of heterogeneous OER electrocatalyst (metallic Co nanoparticles anchored on yttrium ruthenate pyrochlore oxide) is provided for securing fast OER kinetics. In situ X‐ray absorption spectroscopy (in situ XAS) reveals that fast OER kinetics can be achieved by the harmonious catalytic synergy of a pyrochlore oxide support to Co nanoparticles. By the facile oxidation of yttrium (A‐site) and ruthenium (B‐site) cations, the pyrochlore oxide support helps to expel the electrons generated from the catalytic behavior of Co to the inner layers of the support, facilitating the electrostatic adsorption of OH^? ions and reducing the barrier energy for the formation of CoOOH intermediates. This work affords the rational design of transition metal nanoparticles anchored on pyrochlore oxide heterogeneous catalysts and the fundamental insight of catalytic origin associated with self‐reconstruction of OER electrocatalysts.     

Ruthenium Nanoparticles on Cobalt‐Doped 1T′ Phase MoS2 Nanosheets for Overall Water Splitting

2D MoS₂ nanostructures have recently attracted considerable attention because of their outstanding electrocatalytic properties. The synthesis of unique Co–Ru–MoS₂ hybrid nanosheets with excellent catalytic activity toward overall water splitting in alkaline solution is reported. 1T′ phase MoS₂ nanosheets are doped homogeneously with Co atoms and decorated with Ru nanoparticles. The catalytic performance of hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is characterized by low overpotentials of 52 and 308 mV at 10 mA cm^?2 and Tafel slopes of 55 and 50 mV decade^?1 in 1.0 m KOH, respectively. Analysis of X‐ray photoelectron and absorption spectra of the catalysts show that the MoS₂ well retained its metallic 1T′ phase, which guarantees good electrical conductivity during the reaction. The Gibbs free energy calculation for the reaction pathway in alkaline electrolyte confirms that the Ru nanoparticles on the Co‐doped MoS₂ greatly enhance the HER activity. Water adsorption and dissociation take place favorably on the Ru, and the doped Co further catalyzes HER by making the reaction intermediates more favorable. The high OER performance is attributed to the catalytically active RuO₂ nanoparticles that are produced via oxidation of Ru nanoparticles.     

Designing Highly Efficient and Long‐Term Durable Electrocatalyst for Oxygen Evolution by Coupling B and P into Amorphous Porous NiFe‐Based Material

Oxygen evolution reaction (OER) is of great significance for hydrogen production via water electrolysis, which, however, demands development of highly active, durable, and cost‐effective electrocatalysts in order to stride into a renewable energy era. Herein, highly efficient and long‐term durable OER by coupling B and P into an amorphous porous NiFe‐based electrocatalyst is reported, which possesses an amorphous porous metallic bulk structure and high corrosion resistance, and overcomes the issues associated with currently used catalyst nanomaterials. The PB codoping in the activated NiFePB (a‐NiFePB) delocalizes both Fe and Ni at Fermi energy level and enhances p–d hybridization as simulated by density functional theory calculations. The harmonized electronic structure and unique porous framework of the a‐NiFePB consequently improve the OER activity. The activated NiFePB thus exhibits an extraordinarily low overpotential of 197 mV for harvesting 10 mA cm^?2 OER current density and 233 mV for reaching 100 mA cm^?2 under chronopotentiometry condition, with the Tafel slope harmoniously conforming to 34 mV dec^?1. Impressive long‐term stability of this new catalyst is evidenced by only limited activity decay after 1400 h operation at 100 mA cm^?2. This work strategically directs a way for heading up a promising energy conversion alternative.     

α‐Ni(OH)2 Originated from Electro‐Oxidation of NiSe2 Supported by Carbon Nanoarray on Carbon Cloth for Efficient Water Oxidation

Development of effective oxygen evolution reaction (OER) electrocatalysts has been intensively studied to improve water splitting efficiency and cost effectiveness in the last ten years. However, it is a big challenge to obtain highly efficient and durable OER electrocatalysts with overpotentials below 200 mV at 10 mA cm^?2 despite the efforts made to date. In this work, the successful synthesis of supersmall α‐Ni(OH)₂ is reported through electro‐oxidation of NiSe₂ loaded onto carbon nanoarrays. The obtained α‐Ni(OH)₂ shows excellent activity and long‐term stability for OER, with an overpotential of only 190 mV at the current density of 10 mA cm^?2, which represents a highly efficient OER electrocatalyst. The excellent activity could be ascribed to the large electrochemical surface area provided by the carbon nanoarray, as well as the supersmall size (≈10 nm) of α‐Ni(OH)₂ which possess a large number of active sites for the reaction. In addition, the phase evolution of α‐Ni(OH)₂ from NiSe₂ during the electro‐oxidation process was monitored with in situ X‐ray absorption fine structure (XAFS) analysis.     

Self‐Supportive Mesoporous Ni/Co/Fe Phosphosulfide Nanorods Derived from Novel Hydrothermal Electrodeposition as a Highly Efficient Electrocatalyst for Overall Water Splitting

Low cost and highly efficient bifuctional catalysts for overall water electrolysis have drawn considerable interests over the past several decades. Here, rationally synthesized mesoporous nanorods of nickel–cobalt–iron–sulfur–phosphorus composites are tightly self‐supported on Ni foam as a high‐performance, low cost, and stable bifunctional electrocatalyst for water electrolysis. The targeted designing and rational fabrication give rise to the nanorod‐like morphology with large surface area and excellent conductivity. The NiCoFe‐PS nanorod/NF can reach 10 mA cm^?2 at a small overpotential of 195 mV with a Tafel slope of 40.3 mV dec^?1 for the oxygen evolution reaction and 97.8 mV with 51.8 mV dec^?1 for the hydrogen evolution reaction. Thus, this bifunctional catalyst shows low potentials of 1.52 and 1.76 V at 10 and 50 mA cm^?2 toward overall water splitting with excellent stability for over 200 h, which are superior to most non‐noble metal‐based bifunctional electrocatalysts recently. This work provides a new strategy to fabricate multiple metal‐P/S composites with the mesoporous nanorod‐like structure as bifunctional catalysts for overall water splitting.