An Efficient and Earth‐Abundant Oxygen‐Evolving Electrocatalyst Based on Amorphous Metal Borides

Cost‐effective and efficient oxygen‐evolving electrocatalysts are urgently required for energy storage and conversion technologies. In this work, an amorphous trimetallic boride nanocatalyst (Fe–Co–2.3Ni–B) prepared by a simple approach is reported as a highly efficient oxygen evolution reaction electrocatalyst. It exhibits an overpotential (η) of 274 mV to deliver a geometric current density (j_geo) of 10 mA cm^?2, a small Tafel slope of 38 mV dec^?1, and excellent long‐term durability at a mass loading of 0.3 mg cm^?2. The impressive electrocatalytic performance originates from the unique amorphous multimetal–metalloid complex nanostructure. From application's point of view, this work holds great promise as this process is simple and allows for large‐scale production of cheap, yet efficient, material.     

Single‐Atom to Single‐Atom Grafting of Pt1 onto FeN4 Center: Pt1@FeNC Multifunctional Electrocatalyst with Significantly Enhanced Properties

Nonprecious metal catalysts (NPMCs) Fe?N?C are promising alternatives to noble metal Pt as the oxygen reduction reaction (ORR) catalysts for proton‐exchange‐membrane fuel cells. Herein, a new modulation strategy is reported to the active moiety Fe?N₄ via a precise “single‐atom to single‐atom” grafting of a Pt atom onto the Fe center through a bridging oxygen molecule, creating a new active moiety of Pt₁?O₂?Fe₁?N₄. The modulated Fe?N?C exhibits remarkably improved ORR stabilities in acidic media. Moreover, it shows unexpectedly high catalytic activities toward oxygen evolution reaction (OER) and hydrogen evolution reaction (HER), with overpotentials of 310 mV for OER in alkaline solution and 60 mV for HER in acidic media at a current density of 10 mA cm^?2, outperforming the benchmark RuO₂ and comparable with Pt/C(20%), respectively. The enhanced multifunctional electrocatalytic properties are associated with the newly constructed active moiety Pt₁?O₂?Fe₁?N₄, which protects Fe sites from harmful species. Density functional theory calculations reveal the synergy in the new active moiety, which promotes the proton adsorption and reduction kinetics. In addition, the grafted Pt₁?O₂? dangling bonds may boost the OER activity. This study paves a new way to improve and extend NPMCs electrocatalytic properties through a precisely single‐atom to single‐atom grafting strategy.     

Ultrafine Pt Nanoparticle‐Decorated Pyrite‐Type CoS2 Nanosheet Arrays Coated on Carbon Cloth as a Bifunctional Electrode for Overall Water Splitting

To improve the utilization efficiency of precious metals, metal‐supported materials provide a direction for fabricating highly active and stable heterogeneous catalysts. Herein, carbon cloth (CC)‐supported Earth‐abundant CoS₂ nanosheet arrays (CoS₂/CC) are presented as ideal substrates for ultrafine Pt deposition (Pt‐CoS₂/CC) to achieve remarkable performance toward the hydrogen and oxygen evolution reactions (HER/OER) in alkaline solutions. Notably, the Pt‐CoS₂/CC hybrid delivers an overpotential of 24 mV at 10 mA cm^?2 and a mass activity of 3.89 A Pt_mg^?1, which is 4.7 times higher than that of commercial Pt/C, at an overpotential of 130 mV for catalyzing the HER. An alkali‐electrolyzer using Pt‐CoS₂/CC as a bifunctional electrode enables a water‐splitting current density of 10 mA cm^?2 at a low voltage of 1.55 V and can sustain for more than 20 h, which is superior to that of the state‐of‐the‐art Pt/C+RuO₂ catalyst. Further experimental and theoretical simulation studies demonstrate that strong electronic interaction between Pt and CoS₂ synergistically optimize hydrogen adsorption/desorption behaviors and facilitate the in situ generation of OER active species, enhancing the overall water‐splitting performance. This work highlights the regulation of interfacial and electronic synergy in pursuit of highly efficient and durable supported catalysts for hydrogen and oxygen electrocatalytic applications.     

High‐Performance Lithium‐Iodine Flow Battery

A cathode‐flow lithium‐iodine (Li–I) battery is proposed operating by the triiodide/iodide (I₃^?/I^?) redox couple in aqueous solution. The aqueous Li–I battery has noticeably high energy density (≈0.28 kWh kg^?1_cell) because of the considerable solubility of LiI in aqueous solution (≈8.2 m ) and reasonably high power density (≈130 mW cm^?2 at a current rate of 60 mA cm^?2, 328 K). In the operation of cathode‐flow mode, the Li–I battery attains high storage capacity (≈90% of the theoretical capacity), Coulombic efficiency (100% ± 1% in 2–20 cycles) and cyclic performance (>99% capacity retention for 20 cycles) up to total capacity of 100 mAh.     

Efficient Water Splitting Using a Simple Ni/N/C Paper Electrocatalyst

An efficient water splitting electrocatalyst is presented. Cheap and sustainable cellulose filter paper, infiltrated with nickel acetate as the nickel source, and phenanthroline as a ligand and nitrogen source are carbonized together. Nitrogen functionalities turn out to be crucial coordination sites for the supported Ni/NiO(OH) particles. This simple and scalable one step procedure leads to powders, but also to complete membranes made of ≈10 wt% Ni, supported on nitrogen functionalized carbon. The non‐noble catalyst shows a low onset potential (330 mV vs reversible hydrogen electrode), high current density (e.g., j > 25 mA cm^?­2 at η = 430 mV), excellent kinetics (Tafel slope of 44 mV dec^?1), and a very favorable stability (<5% decay after 10 h electrolysis) in the oxygen evolution. The performance is similar or even better compared to state‐of‐the‐art noble metal catalysts (e.g., IrO₂, Ir/C, Ru/C, and Pt/C). Because of the simple, cheap, and scalable preparation procedure the catalyst is highly promising for practical low price/tech applications. Interestingly, the system is also active in the hydrogen evolution reaction, leading to a promising bifunctional catalyst. The benchmark characteristics are η₁₀ = 390 mV for oxygen evolution and η₁₀ = 190 mV for hydrogen evolution, that is, an overall efficiency of 68% at 10 mA current density.     

Corrosion and Alloy Engineering in Rational Design of High Current Density Electrodes for Efficient Water Splitting

Alongside rare‐earth metals, Ni, Fe, Co, Cu are some of the critical materials that will be in huge demand thanks to growth in clean‐energy sector. Herein scrap stainless steel wires (SSW) from worn‐out tires are employed as a support material for catalyst integration in the hydrogen evolution reaction (HER). In addition, SSW by corrosion engineering is exercised as an in situ formed freestanding robust electrode for the oxygen evolution reaction (OER). By superficial corrosion of SSW, inherent active species are unmasked in the form of Ni/FeOOH nanocrystallites displaying efficient water oxidation by reaching 500 mA cm^?2 at low overpotential (η₅₀₀) of 287 mV in 1 m KOH. Similarly, cathode scrap SSW with active (alloy) coatings of MoNi₄ catalyzes the HER at η_‐200 = 77 mV, with a low activation energy (E_a = 16.338 kJ mol^?1) and high durability of 150 h. Promisingly, when used in industrial conditions, 5 m KOH, 343 K, these electrodes demonstrate abnormal activity by yielding high anodic and cathodic current density of 1000 mA cm^?2 at η = 233 mV and η = 161 mV, respectively. This work may inspire researchers to explore and reutilize high‐demand metals from scrap for addressing critical material shortfalls in clean‐energy technologies.     

Self‐Assemble and In Situ Formation of Ni1−xFexPS3 Nanomosaic‐Decorated MXene Hybrids for Overall Water Splitting

Herein, the authors present the development of novel 0D–2D nanohybrids consisting of a nickel‐based bimetal phosphorus trisulfide (Ni_1?xFe_xPS₃) nanomosaic that decorates on the surface of MXene nanosheets (denoted as NFPS@MXene). The nanohybrids are obtained through a facile self‐assemble process of transition metal layered double hydroxide (TMLDH) on MXene surface; followed by a low temperature in situ solid‐state reaction step. By tuning the Ni:Fe ratio, the as‐synthesized NFPS@MXene nanohybrids exhibit excellent activities when tested as electrocatalysts for overall water splitting. Particularly, with the initial Ni:Fe ratio of 7:3, the obtained Ni_0.7Fe_0.3PS₃@MXene nanohybrid reveals low overpotential (282 mV) and Tafel slope (36.5 mV dec^?1) for oxygen evolution reaction (OER) in 1 m KOH solution. Meanwhile, the Ni_0.9Fe_0.1PS₃@MXene shows low overpotential (196 mV) for the hydrogen evolution reaction (HER) in 1 m KOH solution. When integrated for overall water splitting, the Ni_0.7Fe_0.3PS₃@MXene || Ni_0.9Fe_0.1PS₃@MXene couple shows a low onset potential of 1.42 V and needs only 1.65 V to reach a current density of 10 mA cm^?2, which is better than the all noble metal IrO₂ || Pt/C electrocatalyst (1.71 mV@10 mA cm^?2). Given the chemical versatility of Ni_1?xFe_xPS₃ and the convenient self‐assemble process, the nanohybrids demonstrated in this work are promising for energy conversion applications.     

Atomic Fe‐Doped MOF‐Derived Carbon Polyhedrons with High Active‐Center Density and Ultra‐High Performance toward PEM Fuel Cells

A metalorganic gaseous doping approach for constructing nitrogen‐doped carbon polyhedron catalysts embedded with single Fe atoms is reported. The resulting catalysts are characterized using scanning transmission electron microscopy, X‐ray photoelectron spectroscopy, and X‐ray absorption spectroscopy; for the optimal sample, calculated densities of Fe–N_x sites and active N sites reach 1.75812 × 10¹³ and 1.93693 × 10¹⁴ sites cm^‐2, respectively. Its oxygen reduction reaction half‐wave potential (0.864 V) is 50 mV higher than that of 20 wt% Pt/C catalyst in an alkaline medium and comparable to the latter (0.78 V vs 0.84 V) in an acidic medium, along with outstanding durability. More importantly, when used as a hydrogen–oxygen polymer electrolyte membrane fuel cell (PEMFC) cathode catalyst with a catalyst loading as low as 1 mg cm^‐2 (compared with a conventional loading of 4 mg cm^‐2), it exhibits a current density of 1100 mA cm^‐2 at 0.6 V and 637 mA cm^‐2 at 0.7 V, with a power density of 775 mW cm^‐2, or 0.775 kW g^–1 of catalyst. In a hydrogen–air PEMFC, current density reaches 650 mA cm^‐2 at 0.6 V and 350 mA cm^‐2 at 0.7 V, and the maximum power density is 463 mW cm^‐2, which makes it a promising candidate for cathode catalyst toward high‐performance PEMFCs.     

Highly Efficient Oxygen Evolution by a Thermocatalytic Process Cascaded Electrocatalysis Over Sulfur‐Treated Fe‐Based Metal–Organic‐Frameworks

The oxygen evolution reaction (OER) is a bottleneck process for water splitting and finding highly efficient, durable, low‐cost, and earth‐abundant electrocatalysts is still a major challenge. Here a sulfur‐treated Fe‐based metal–organic‐framework is reported as a promising electrocatalyst for the OER, which shows a low overpotential of 218 mV at the current density of 10 mA cm^?2 and exhibits a very low Tafel slope of 36.2 mV dec^?1 at room temperature. It can work on high current densities of 500 and 1000 mA cm^?2 at low overpotentials of 298 and 330 mV, respectively, by keeping 97% of its initial activity after 100 h. Notably, it can achieve 1000 mA cm^?2 at 296 mV with a good stability at 50 °C, fully fitting the requirements for large‐scale industrial water electrolysis. The high catalytic performance can be attributed to the thermocatalytic processes of H⁺ capture by –SO₃ groups from *OH or *OOH species, which cascades to the electrocatalytic pathway and then significantly reduces the OER overpotentials.     

Hydrothermal Synthesis of Monolithic Co3Se4 Nanowire Electrodes for Oxygen Evolution and Overall Water Splitting with High Efficiency and Extraordinary Catalytic Stability

Cobalt selenide has been proposed to be an effective low‐cost electrocatalyst toward the oxygen evolution reaction (OER) due to its well‐suited electronic configuration. However, pure cobalt selenide has by far still exhibited catalytic activity far below what is expected. Herein, this paper for the first time reports the synthesis of new monoclinic Co₃Se₄ thin nanowires on cobalt foam (CF) via a facile one‐pot hydrothermal process using selenourea. When used to catalyze the OER in basic solution, the conditioned monolithic self‐supported Co₃Se₄/CF electrode shows an exceptionally high catalytic current of 397 mA cm^?2 at a low overpotential (η) of 320 mV, a small Tafel slope of 44 mV dec^?1, a turnover frequency of 6.44 × 10^?2 s^?1 at η = 320 mV, and excellent electrocatalytic stability at various current densities. Furthermore, an electrolyzer is assembled using two symmetrical Co₃Se₄/CF electrodes as anode and cathode, which can deliver 10 and 20 mA cm^?2 at low cell voltages of 1.59 and 1.63 V, respectively. More significantly, the electrolyzer can operate at 10 mA cm^?2 over 3500 h and at 100 mA cm^?2 for at least 2000 h without noticeable degradation, showing extraordinary operational stability.     

One‐Step Controllable Synthesis of Catalytic Ni4Mo/MoOx/Cu Nanointerfaces for Highly Efficient Water Reduction

Currently, in addition to the electroactive non‐noble metal water‐splitting electrocatalysts, a scalable synthetic route and simple activity enhancement strategy is also urgently needed. In particular, the well‐controlled synthesis of the well‐recognized metal–metal nanointer face in a single step remains a key challenge. Here, the synthesis of Cu‐supported Ni₄Mo nanodots on MoO_x nanosheets (Ni₄Mo/MoO_x) with controllable Ni₄Mo particle size and d‐band structure is reported via a facile one‐step electrodeposition process. Density functional theory (DFT) calculations reveal that the active open‐shell effect from Ni‐3d‐band optimizes the electronic configuration. The Cu‐substrate enables the surface Ni–Mo alloy dots to be more electron‐rich, forming a local connected electron‐rich network, which boosts the charge transfer for effective binding of O‐related species and proton–electron charge exchange in the hydrogen evolution reaction. The Cu‐supported Ni₄Mo/MoO_x shows an ultralow overpotential of 16 mV at a current density of 10 mA cm^?2 in 1 m KOH, demonstrating the smallest overpotential, at loadings as low as 0.27 mg cm^?2, among all non‐noble metal catalysts reported to date. Moreover, an overpotential of 105 mV allows it to achieve a current density of 250 mA cm^?2 in 70 °C 30% KOH, a remarkable performance for alkaline hydrogen evolution with competitive potential for applications.     

High‐Performance Hydrogen Evolution by Ru Single Atoms and Nitrided‐Ru Nanoparticles Implanted on N‐Doped Graphitic Sheet

The most efficient electrocatalyst for the hydrogen evolution reaction (HER) is a Pt‐based catalyst, but its high cost and nonperfect efficiency hinder wide‐ranging industrial/technological applications. Here, an electrocatalyst of both ruthenium (Ru) single atoms (SAs) and N‐doped‐graphitic(G_N)‐shell‐covered nitrided‐Ru nanoparticles (NPs) (having a Ru‐N_x shell) embedded on melamine‐derived G_N matrix { 1 : [Ru(SA)+Ru(NP)@RuN_x@G_N]/G_N}, which exhibits superior HER activity in both acidic and basic media, is presented. In 0.5 m H₂SO₄/1 m KOH solutions, 1 shows diminutive “negative overpotentials” (?η = |η| = 10/7 mV at 10 mA cm^?2, lowest ever) and high exchange current densities (4.70/1.96 mA cm^?2). The remarkable HER performance is attributed to the near‐zero free energies for hydrogen adsorption/desorption on Ru(SAs) and the increased conductivity of melamine‐derived G_N sheets by the presence of nitrided‐Ru(NPs). The nitridation process forming nitrided‐Ru(NPs), which are imperfectly covered by a G_N shell, allows superb long‐term operation durability. The catalyst splits water into molecular oxygen and hydrogen at 1.50/1.40 V (in 0.1 m HClO₄/1 m KOH), demonstrating its potential as a ready‐to‐use, highly effective energy device for industrial applications.     

Polyoxometalate‐Derived Ultrasmall Pt2W/WO3 Heterostructure Outperforms Platinum for Large‐Current‐Density H2 Evolution

Platinum (Pt)‐based catalysts with high Pt utilization efficiency for efficient H₂ evolution are attracting extensive attention to meet the issues of energy exhaustion and environmental pollution. Herein, a one‐step electrochemical method is demonstrated to construct ultrafine heterostructure Pt₂W/WO₃ on reduced graphene oxide (RGO) by injecting multielectrons into the Preyssler anion [NaP₅W₃₀O₁₁₀]^14? to codeposit with anodic deliquescent Pt cations. The resulting Pt₂W/WO₃/RGO shows much higher performance than that of commercial Pt catalysts for large‐current‐density H₂ evolution, which can deliver a large current density of 500 mA cm^?2 with an overpotential of only 394 mV, much lower than that of 20% Pt/C (578 mV). Comparisons with control experiments and density functional theory (DFT) calculations both suggest that the much enhanced activity can be mainly attributed to the synergistic cooperation of different components to drive fast and continuous hydrogen desorption on Pt₂W/WO₃/RGO, while it could not run normally for 20% Pt/C under similar conditions due to the formation of huge bubbles on the electrode surface. The effective integration of high catalytic activity and hydrogen desorption ability into a single material can yield advanced materials for large‐current‐density H₂ evolution with remarkable stability.     

Rational Design of Core@shell Structured CoSx@Cu2MoS4 Hybridized MoS2/N,S‐Codoped Graphene as Advanced Electrocatalyst for Water Splitting and Zn‐Air Battery

A novel hybrid of small core@shell structured CoS_x@Cu₂MoS₄ uniformly hybridizing with a molybdenum dichalcogenide/N,S‐codoped graphene hetero‐network (CoS_x@Cu₂MoS₄‐MoS₂/NSG) is prepared by a facile route. It shows excellent performance toward the oxygen reduction reaction (ORR), oxygen evolution reaction (OER), and hydrogen evolution reaction (HER) in alkaline medium. The hybrid exhibits rapid kinetics for ORR with high electron transfer number of ≈3.97 and exciting durability superior to commercial Pt/C. It also demonstrates great potential with remarkable stability for HER and OER, requiring low overpotential of 118.1 and 351.4 mV, respectively, to reach a current density of 10 mA cm^?2. An electrolyzer based on CoS_x@Cu₂MoS₄‐MoS₂/NSG produces low cell voltage of 1.60 V and long‐term stability, surpassing a device of Pt/C + RuO₂/C. In addition, a Zn‐air battery using cathodic CoS_x@Cu₂MoS₄‐MoS₂/NSG catalyst delivers a high cell voltage of ≈1.44 V and a power density of 40 mW cm^?2 at 58 mA cm^?2, better than the state‐of‐the‐art Pt/C catalyst. These achievements are due to the rational combination of highly active core@shell CoS_x@Cu₂MoS₄ with large‐area and high‐porosity MoS₂/NSG to produce unique physicochemical properties with multi‐integrated active centers and synergistic effects. The outperformances of such catalyst suggest an advanced candidate for multielectrocatalysis applications in metal‐air batteries and hydrogen production.     

High‐Performance Trifunctional Electrocatalysts Based on FeCo/Co2P Hybrid Nanoparticles for Zinc–Air Battery and Self‐Powered Overall Water Splitting

Currently, it is still a significant challenge to simultaneously boost various reactions by one electrocatalyst with high activity, excellent durability, as well as low cost. Herein, hybrid trifunctional electrocatalysts are explored via a facile one‐pot strategy toward an efficient oxygen reduction reaction (ORR), oxygen evolution reaction (OER), and hydrogen evolution reaction (HER). The catalysts are rationally designed to be composed by FeCo nanoparticles encapsuled in graphitic carbon films, Co₂P nanoparticles, and N,P‐codoped carbon nanofiber networks. The FeCo nanoparticles and the synergistic effect from Co₂P and FeCo nanoparticles make the dominant contributions to the ORR, OER, and HER activities, respectively. Their bifunctional activity parameter (?E) for ORR and OER is low to 0.77 V, which is much smaller than those of most nonprecious metal catalysts ever reported, and comparable with state‐of‐the‐art Pt/C and RuO₂ (0.78 V). Accordingly, the as‐assembled Zn–air battery exhibits a high power density of 154 mW cm^?2 with a low charge–discharge voltage gap of 0.83 V (at 10 mA cm^?2) and excellent stability. The as‐constructed overall water‐splitting cell achieves a current density of 10 mA cm^?2 (at 1.68 V), which is comparable to the best reported trifunctional catalysts.     

Earth‐Abundant Iron Diboride (FeB2) Nanoparticles as Highly Active Bifunctional Electrocatalysts for Overall Water Splitting

Developing efficient, durable, and earth‐abundant electrocatalysts for both hydrogen and oxygen evolution reactions is important for realizing large‐scale water splitting. The authors report that FeB₂ nanoparticles, prepared by a facile chemical reduction of Fe²⁺ using LiBH₄ in an organic solvent, are a superb bifunctional electrocatalyst for overall water splitting. The FeB₂ electrode delivers a current density of 10 mA cm^?2 at overpotentials of 61 mV for hydrogen evolution reaction (HER) and 296 mV for oxygen evolution reaction (OER) in alkaline electrolyte with Tafel slopes of 87.5 and 52.4 mV dec^?1, respectively. The electrode can sustain the HER at an overpotential of 100 mV for 24 h and OER for 1000 cyclic voltammetry cycles with negligible degradation. Density function theory calculations demonstrate that the boron‐rich surface possesses appropriate binding energy for chemisorption and desorption of hydrogen‐containing intermediates, thus favoring the HER process. The excellent OER activity of FeB₂ is ascribed to the formation of a FeOOH/FeB₂ heterojunction during water oxidation. An alkaline electrolyzer is constructed using two identical FeB₂‐NF electrodes as both anode and cathode, which can achieve a current density of 10 mA cm^?2 at 1.57 V for overall water splitting with a faradaic efficiency of nearly 100%, rivalling the integrated state‐of‐the‐art Pt/C and RuO₂/C.     

Engineered MoSe2‐Based Heterostructures for Efficient Electrochemical Hydrogen Evolution Reaction

2D transition metal‐dichalcogenides are emerging as efficient and cost‐effective electrocatalysts for the hydrogen evolution reaction (HER). However, only the edge sites of their trigonal prismatic phase show HER‐electrocatalytic properties, while the basal plane, which is absent of defective/unsaturated sites, is inactive. Herein, the authors tackle the key challenge of increasing the number of electrocatalytic sites by designing and engineering heterostructures composed of single‐/few‐layer MoSe₂ flakes and carbon nanomaterials (graphene or single‐wall carbon nanotubes) produced by solution processing. The electrochemical coupling between the materials that comprise the heterostructure effectively enhances the HER‐electrocatalytic activity of the native MoSe₂ flakes. The optimization of the mass loading of MoSe₂ flakes and their electrode assembly via monolithic heterostructure stacking provides a cathodic current density of 10 mA cm^?2 at overpotential of 100 mV, a Tafel slope of 63 mV dec^?1, and an exchange current density (j₀) of 0.203 µA cm^?2. In addition, thermal and chemical treatments are exploited to texturize the basal planes of the MoSe₂ flakes (through Se‐vacancies creation) and to achieve in situ semiconducting‐to‐metallic phase conversion, respectively, thus they activate new HER‐electrocatalytic sites. The as‐engineered electrodes show a 4.8‐fold enhancement of j₀ and a decrease in the Tafel slope to 54 mV dec^?1.     

Single‐Atom to Single‐Atom Grafting of Pt1 onto Fe?N4 Center: Pt1@Fe?N?C Multifunctional Electrocatalyst with Significantly Enhanced Properties

Nonprecious metal catalysts (NPMCs) Fe? N? C are promising alternatives to noble metal Pt as the oxygen reduction reaction (ORR) catalysts for proton‐exchange‐membrane fuel cells. Herein, a new modulation strategy is reported to the active moiety Fe? N₄ via a precise “single‐atom to single‐atom” grafting of a Pt atom onto the Fe center through a bridging oxygen molecule, creating a new active moiety of Pt₁? O₂? Fe₁? N₄. The modulated Fe? N? C exhibits remarkably improved ORR stabilities in acidic media. Moreover, it shows unexpectedly high catalytic activities toward oxygen evolution reaction (OER) and hydrogen evolution reaction (HER), with overpotentials of 310 mV for OER in alkaline solution and 60 mV for HER in acidic media at a current density of 10 mA cm^?2, outperforming the benchmark RuO₂ and comparable with Pt/C(20%), respectively. The enhanced multifunctional electrocatalytic properties are associated with the newly constructed active moiety Pt₁? O₂? Fe₁? N₄, which protects Fe sites from harmful species. Density functional theory calculations reveal the synergy in the new active moiety, which promotes the proton adsorption and reduction kinetics. In addition, the grafted Pt₁? O₂? dangling bonds may boost the OER activity. This study paves a new way to improve and extend NPMCs electrocatalytic properties through a precisely single‐atom to single‐atom grafting strategy.     

Superb Alkaline Hydrogen Evolution and Simultaneous Electricity Generation by Pt‐Decorated Ni3N Nanosheets

The development of efficient hydrogen evolution reaction electrocatalysts is critical to the realization of clean hydrogen fuel production, while the sluggish kinetics of the Volmer‐step substantially restricts the catalyst performances in alkali electrolyzers, even for noble metal catalysts such as Pt. Here, a Pt‐decorated Ni₃N nanosheet electrocatalyst is developed to achieve a top performance of hydrogen evolution in alkaline conditions. Possessing a high metallic conductivity and an atomic‐thin semiconducting hydroxide surface, the Ni₃N nanosheets serve as not only an efficient electron pathway without the hindrance of Schottky barriers, but also provide abundant active sites for water dissociation and generation of hydrogen intermediates, which are further adsorbed on the Pt surface to recombine to H₂. The Pt‐decorated Ni₃N nanosheet catalyst exhibits a hydrogen evolution current density of 200 mA cm^?2 at an overpotential of 160 mV versus reversible hydrogen electrode, a Tafel slope of ≈36.5 mV dec^?1, and excellent stability of 82.5% current retention after 24 h of operation. Moreover, a hybrid cell consisting of a Pt‐decorated Ni₃N nanosheet cathode and a Li‐metal anode is assembled to achieve simultaneous hydrogen evolution and electricity generation, exhibiting >60 h long‐term hydrogen evolution reaction stability and an output voltage ranging from 1.3 to 2.2 V.     

Active Edge Sites Engineering in Nickel Cobalt Selenide Solid Solutions for Highly Efficient Hydrogen Evolution

An effective multifaceted strategy is demonstrated to increase active edge site concentration in Ni_0.33Co_0.67Se₂ solid solutions prepared by in situ selenization process of nickel cobalt precursor. The simultaneous control of surface, phase, and morphology result in as‐prepared ternary solid solution with extremely high electrochemically active surface area (C _dl = 197 mF cm^?2), suggesting significant exposure of active sites in this ternary compound. Coupled with metallic‐like electrical conductivity and lower free energy for atomic hydrogen adsorption in Ni_0.33Co_0.67Se₂, identified by temperature‐dependent conductivities and density functional theory calculations, the authors have achieved unprecedented fast hydrogen evolution kinetics, approaching that of Pt. Specifically, the Ni_0.33Co_0.67Se₂ solid solutions show a low overpotential of 65 mV at ?10 mV cm^?2, with onset potential of mere 18 mV, an impressive small Tafel slope of 35 mV dec^?1, and a large exchange current density of 184 µA cm^?2 in acidic electrolyte. Further, it is shown that the as‐prepared Ni_0.33Co_0.67Se₂ solid solution not only works very well in acidic electrolyte but also delivers exceptional hydrogen evolution reaction (HER) performance in alkaline media. The outstanding HER performance makes this solid solution a promising candidate for mass hydrogen production.