Ni Strongly Coupled with Mo2C Encapsulated in Nitrogen‐Doped Carbon Nanofibers as Robust Bifunctional Catalyst for Overall Water Splitting

It is urgently required to develop highly efficient and stable bifunctional non‐noble metal electrocatalysts for both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) for water splitting. In this study, a facile electrospinning followed by a post‐carbonization treatment to synthesize nitrogen‐doped carbon nanofibers (NCNFs) integrated with Ni and Mo₂C nanoparticles (Ni/Mo₂C‐NCNFs) as water splitting electrocatalysts is developed. Owing to the strong hydrogen binding energy on Mo₂C and high electrical conductivity of Ni, synergetic effect between Ni and Mo₂C nanoparticles significantly promote both HER and OER activities. The optimized hybrid (Ni/Mo₂C(1:2)‐NCNFs) delivers low overpotentials of 143 mV for HER and 288 mV for OER at a current density of 10 mA cm^?2. An alkaline electrolyzer with Ni/Mo₂C(1:2)‐NCNFs as catalysts for both anode and cathode exhibits a current density of 10 mA cm^?2 at a voltage of 1.64 V, which is only 0.07 V larger than the benchmark of Pt/C‐RuO₂ electrodes. In addition, an outstanding long‐term durability during 100 h testing without obvious degradation is achieved, which is superior to most of the noble‐metal‐free electrocatalysts reported to date. This work provides a simple and effective approach for the preparation of low‐cost and high‐performance bifunctional electrocatalysts for efficient overall water splitting.     

Molybdenum Disulfide/Nitrogen‐Doped Reduced Graphene Oxide Nanocomposite with Enlarged Interlayer Spacing for Electrocatalytic Hydrogen Evolution

Facile design of low‐cost and highly active catalysts from earth‐abundant elements is favorable for the industrial application of water splitting. Here, a simple strategy to synthesize an ultrathin molybdenum disulfide/nitrogen‐doped reduced graphene oxide (MoS₂/N‐RGO‐180) nanocomposite with the enlarged interlayer spacing of 9.5 Å by a one‐step hydrothermal method is reported. The synergistic effects between the layered MoS₂ nanosheets and N‐doped RGO films contribute to the high activity for hydrogen evolution reaction (HER). MoS₂/N‐RGO‐180 exhibits the excellent catalytic activity with a low onset potential of ?5 mV versus reversible hydrogen elelctrode (RHE), a small Tafel slope of 41.3 mV dec^?1, a high exchange current density of 7.4 × 10^?4 A cm^?2, and good stability over 5 000 cycles under acidic conditions. The HER performance of MoS₂/N‐RGO‐180 nanocomposite is superior to the most reported MoS₂‐based catalysts, especially its onset potential and exchange current density. In this work, a novel and simple method to the preparation of low‐cost MoS₂‐based electrocatalysts with the extraordinary HER performance is presented.     

Benchmarking the Activity,Stability, and Inherent Electrochemistry of Amorphous Molybdenum Sulfide for Hydrogen Production

Anodically electrodeposited amorphous molybdenum sulfide (AE‐MoS_x) has attracted significant attention as a non‐noble metal electrocatalyst for its high activity toward the hydrogen evolution reaction (HER). The [Mo₃S₁₃]^2? polymer‐based structure confers a high density of exposed sulfur moieties, widely regarded as the HER active sites. However, their intrinsic complexity conceals full understanding of their exact role in HER catalysis, hampering their full potential for water splitting applications. In this report, a unifying approach is adopted accounting for modifications in the inherent electrochemistry (EC), HER mechanism, and surface species to maximize the AE‐MoS_x electroactivity over a broad pH region (0–10). Dramatic enhancements in HER performance by selective electrochemical cycling within reductive (overpotential shift, η_HER ≈ ?350 mV) and electro‐oxidative windows (η_HER ≈ ?290 mV) are accompanied by highly stable performance in mildly acidic electrolytes. Joint analysis of X‐ray photoelectron spectroscopy, Raman, and EC experiments corroborate the key role of bridging and terminal S ligands as active site generators at low pH, and reveal molybdenum oxysulfides (Mo⁵⁺O_xS_y) to be the most active HER moiety in AE‐MoS_x in mildly acidic‐to‐neutral environments. These findings will be extremely beneficial for future tailoring of MoS_x materials and their implementation in commercial electrolyzer technologies.     

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.     

Fine Tuning Electronic Structure of Catalysts through Atomic Engineering for Enhanced Hydrogen Evolution

An efficient, durable, and low‐cost hydrogen evolution reaction (HER) catalyst is an essential requirement for practical hydrogen production. Herein, an effective approach to facilitate the HER kinetics of molybdenum carbide (Mo₂C) electrocatalysts is presented by tuning its electronic structure through atomic engineering of nitrogen implantation. Starting from the organoimido‐derivatized polyoxometalate nanoclusters with inherent Mo? N bonds, the formation of N‐implanted Mo₂C (N@Mo₂C) nanocrystals with perfectly adjustable amounts of N atoms is demonstrated. The optimized N@Mo₂C electrocatalyst exhibits remarkable HER performance and good stability over 20 h in both acid and basic electrolytes. Further density functional theory calculations show that engineering suitable nitrogen atoms into Mo₂C can regulate its electronic structure well and decrease Mo? H strength, leading to a great enhancement of the HER activity. It could be believed that this ligand‐controlled atomic engineering strategy might influence the overall catalyst design strategy for engineering the activation sites of nonprecious metal catalysts for energy conversions.     

A Fully Reversible Water Electrolyzer Cell Made Up from FeCoNi (Oxy)hydroxide Atomic Layers

Renewable electricity powered water electrolysis is a promising solution for the conversion and storage of the intermittent renewable energy resources in the form of hydrogen. Herein, atomically thin FeCoNi ternary (oxy)hydroxide nanosheets (FeCoNi‐ATNs) are developed as efficient and robust bifunctional electrocatalysts for the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) in 1 m KOH solution (pH = 14). The electrocatalyst shows remarkably high apparent catalytic performance (400 mA cm^?2 at 350 mV for OER and 240 mV for HER) and mass activities at modest overpotentials (1931 A g^?1 at 330 mV for OER; 1819 A g^?1 at 200 mV for HER). Moreover, the OER and HER performance of FeCoNi–ATNs are fully reversible and electrochemically switchable, due to the interconversion attribute of two catalytic states for OER and HER. Using the dual functional properties of this catalyst, a fully reversible water electrolyzer cell is fabricated, exhibiting a robust reversibility between two half reactions in water electrolysis under a high current density (100 mA cm^?1), which can effectively overcome the stability issues caused by electrode depolarization during frequent power interruptions, an inevitable phenomenon commonly brought about by the usage of intermittent renewable energy supplies.     

Unsaturated Sulfur Edge Engineering of Strongly Coupled MoS2 Nanosheet–Carbon Macroporous Hybrid Catalyst for Enhanced Hydrogen Generation

The low hydrogen adsorption free energy and strong acid/alkaline resistance of layered MoS₂ render it an excellent pH‐universal electrocatalyst for hydrogen evolution reaction (HER). However, the catalytic activity is dominantly suppressed by its limited active‐edge‐site density. Herein, a new strategy is reported for making a class of strongly coupled MoS₂ nanosheet–carbon macroporous hybrid catalysts with engineered unsaturated sulfur edges for boosting HER catalysis by controlling the precursor decomposition and subsequent sodiation/desodiation. Both surface chemical state analysis and first‐principles calculations verify that the resultant catalysts exhibit a desirable valence‐electron state with high exposure of unsaturated sulfur edges and an optimized hydrogen adsorption free energy, significantly improving the intrinsic HER catalytic activity. Such an electrocatalyst exhibits superior and stable catalytic activity toward HER with small overpotentials of 136 mV in 0.5 m H₂SO₄ and 155 mV in 1 m KOH at 10 mA cm^?2, which is the best report for MoS₂–C hybrid electrocatalysts to date. This work paves a new avenue to improve the intrinsic catalytic activity of 2D materials for hydrogen generation.     

Anion–Cation Double Substitution in Transition Metal Dichalcogenide to Accelerate Water Dissociation Kinetic for Electrocatalysis

Until now, many works have shown that the hydrogen evolution reaction (HER) performance can be improved by anion or cation substitution into the crystal lattice of pyrite‐structure materials. However, the synergistic effects of anion–cation double substitution for overall enhancement of the catalytic activity remains questionable. Here, the simultaneous incorporation of vanadium and phosphorus into the CoS₂ moiety for preparing 3D mesoporous cubic pyrite‐metal Co_1‐xV_xSP is presented. It is demonstrated that the higher catalytic activity of CoS₂ after V incorporation can be primarily attributed to abundance active sites, whereas P substitution is responsible for improving HER kinetics and intrinsic catalyst. Interestingly, due to the synergistic effect of P–V double substitution, the 3D Co_1‐xV_xSP shows superior electrocatalysis toward the HER with a very small overpotential of 55 mV at 10 mA cm^?2, a small Tafel slope of 50 mV dec^?1, and a high turnover frequency of 0.45 H₂ s^?1 at 10 mA cm^?2, which is very close to commercial 20% Pt/C. Density functional theory calculation reveals that the superior catalytic activity of the 3D Co_1‐xV_xSP is contributed by the reduced kinetic energy barrier of rate‐determining HER step as well as the promotion of the desorption H₂ gas process.     

Dual‐Functional N Dopants in Edges and Basal Plane of MoS2 Nanosheets Toward Efficient and Durable Hydrogen Evolution

Herein, the authors explicitly reveal the dual‐functions of N dopants in molybdenum disulfide (MoS₂) catalyst through a combined experimental and first‐principles approach. The authors achieve an economical, ecofriendly, and most efficient MoS₂‐based hydrogen evolution reaction (HER) catalyst of N‐doped MoS₂ nanosheets, exhibiting an onset overpotential of 35 mV, an overpotential of 121 mV at 100 mA cm^?2 and a Tafel slope of 41 mV dec^?1. The dual‐functions of N dopants are (1) activating the HER catalytic activity of MoS₂ S‐edge and (2) enhancing the conductivity of MoS₂ basal plane to promote rapid charge transfer. Comprehensive electrochemical measurements prove that both the amount of active HER sites and the conductivity of N‐doped MoS₂ increase as a result of doping N. Systematic first‐principles calculations identify the active HER sites in N‐doped MoS₂ edges and also illustrate the conducting charges spreading over N‐doped basal plane induced by strong Mo 3d –S 2p –N 2p hybridizations at Fermi level. The experimental and theoretical research on the efficient HER catalysis of N‐doped MoS₂ nanosheets possesses great potential for future sustainable hydrogen production via water electrolysis and will stimulate further development on nonmetal‐doped MoS₂ systems to bring about novel high‐performance HER catalysts.     

Theoretical and Experimental Insight into the Effect of Nitrogen Doping on Hydrogen Evolution Activity of Ni3S2 in Alkaline Medium

Nickel sulfide (Ni₃S₂) is a promising hydrogen evolution reaction (HER) catalyst by virtue of its metallic electrical conductivity and excellent stability in alkaline medium. However, the reported catalytic activities for Ni₃S₂ are still relatively low. Herein, an effective strategy to boost the H adsorption capability and HER performance of Ni₃S₂ through nitrogen (N) doping is demonstrated. N‐doped Ni₃S₂ nanosheets achieve a fairly low overpotential of 155 mV at 10 mA cm^?2 and an excellent exchange current density of 0.42 mA cm^?2 in 1.0 m KOH electrolyte. The mass activity of 16.9 mA mg^?1 and turnover frequency of 2.4 s^?1 obtained at 155 mV are significantly higher than the values reported for other Ni₃S₂‐based HER catalysts, and comparable to the performance of best HER catalysts in alkaline medium. These experimental data together with theoretical analysis suggest that the outstanding catalytic activity of N‐doped Ni₃S₂ is due to the enriched active sites with favorable H adsorption free energy. The activity in the Ni₃S₂ is highly correlated with the coordination number of the surface S atoms and the charge depletion of neighbor Ni atoms. These new findings provide important guidance for future experimental design and synthesis of optimal HER catalysts.     

Mesoporous MoO3–x Material as an Efficient Electrocatalyst for Hydrogen Evolution Reactions

A unique approach for the synthesis of nonstoichiometric, mesoporous molybdenum oxide (MoO_3–x) with nanosized crystalline walls by using a soft template (PEO‐b‐PS) synthesis method is introduced. The as‐synthesized mesoporous MoO_3–x is very active and stable (durability > 12 h) for the electrochemical hydrogen evolution reaction (HER) under both acidic and alkaline conditions. The intrinsic MoO₃ serves as an HER electrocatalyst without the assistance of carbon materials, noble metals, or MoS₂ materials. The results from transmission electron microscopy and N₂ sorption techniques show that the as‐synthesized mesoporous MoO_3–x has large accessible pores (20–40 nm), which are able to facilitate mass transport and charge transfer during HER. In terms of X‐ray diffraction, X‐ray photoelectron spectroscopy, temperature‐programmed oxidation, and diffusive reflectance UV–vis spectroscopy, the mesoporous MoO_3–x exhibits mixed oxidation states (Mo⁵⁺, Mo⁶⁺) and an oxygen‐deficient structure. The as‐synthesized MoO_3–x only requires a low overpotential (≈0.14 V) to achieve a 10 mA cm^?2 current density in 0.1 m KOH and the Tafel slope is as low as 56 mV dec^?1. Density functional theory calculations demonstrate a change of electronic structure and the possible reaction pathway of HER. Oxygen vacancies and mesoporosity serve as key factors for excellent performance.     

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.     

A Monodisperse Rh2P‐Based Electrocatalyst for Highly Efficient and pH‐Universal Hydrogen Evolution Reaction

The search for Pt‐free electrocatalysts exceeding pH‐universal hydrogen evolution reaction (HER) activities when compared to the state‐of‐the‐art commercial Pt/C is highly desirable for the development of renewable energy conversion systems but still remains a huge challenge. Here a colloidal synthesis of monodisperse Rh₂P nanoparticles with an average size of 2.8 nm and their superior catalytic activities for pH‐universal HER are reported. Significantly, the Rh₂P catalyst displays remarkable HER performance with overpotentials of 14, 30, and 38 mV to achieve 10 mA cm^?2 in 0.5 m H₂SO₄, 1.0 m KOH, and 1.0 m phosphate‐buffered saline, respectively, exceeding almost all the documented electrocatalysts, including the commercial 20 wt% Pt/C. Density functional theory calculations reveal that the introduction of P into Rh can weaken the H adsorption strength of Rh₂P to nearly zero, beneficial for boosting HER performance.     

Mo‐Based Ultrasmall Nanoparticles on Hierarchical Carbon Nanosheets for Superior Lithium Ion Storage and Hydrogen Generation Catalysis

Constructing 3D hierarchical architecture consisting of 2D hybrid nanosheets is very critical to achieve uppermost and stable electrochemical performance for both lithium‐ion batteries (LIBs) and hydrogen evolution reaction (HER). Herein, a simple synthesis of uniform 3D microspheres assembled from carbon nanosheets with the incorporated MoO₂ nanoclusters is demonstrated. The MoO₂ nanoclusters can be readily converted into the molybdenum carbide (Mo₂C) nanocrystals by using high temperature treatment. Such assembling architecture is highly particular for preventing Mo‐based ultrasmall nanoparticles from coalescing or oxidizing and endowing them with rapid electron transfer. Consequently, the MoO₂/C hybrids as LIB anode materials deliver a specific capacity of 625 mA h g^?1 at 1600 mA g^?1 even after 1000 cycles, which is among the best reported values for MoO₂‐based electrode materials. Moreover, the Mo₂C/C hybrids also exhibit excellent electrocatalytic activity for HER with small overpotential and robust durability in both acid and alkaline media. The present work highlights the importance of designing 3D structure and controlling ultrasmall Mo‐based nanoparticles for enhancing electrochemical energy conversion and storage applications.     

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.     

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.     

Wrinkled Rh2P Nanosheets as Superior pH‐Universal Electrocatalysts for Hydrogen Evolution Catalysis

Searching for highly efficient and durable electrocatalysts for the hydrogen evolution reaction (HER) that function effectively at all pHs is of great interest to the scientific community, however it is still a grand challenge, because the HER kinetics of Pt in alkaline solutions are approximately two to three orders of magnitude lower than that in acidic solution. Herein, a new class of wrinkled, ultrathin Rh₂P nanosheets for enhancing HER catalysis at all pHs is reported. They exhibit a small overpotential of 18.3 mV at 10 mA cm^?2, low Tafel slope of 61.5 mV dec^?1, and good durability in alkaline media, much better than the commercial Pt/C catalyst. Density functional theory calculations reveal that the active open‐shell effect from the P‐3p band not only promotes Rh‐4d for increased proton–electron charge exchange but also provides excellent p–p overlapping to locate the O‐related species as distributary center, which can benefit the HER process in alkaline media. It is also demonstrated that the present wrinkled, ultrathin Rh₂P nanosheets are highly efficient and durable electrocatalysts toward HER in both acid and neutral electrolytes. The present work opens a new material design for ultrathin 2D metal phosphide nanostructures for the purpose of boosting HER performance at all pHs.     

Transforming Nickel Hydroxide into 3D Prussian Blue Analogue Array to Obtain Ni2P/Fe2P for Efficient Hydrogen Evolution Reaction

For the first time, a 3D Prussian blue analogue (PBA) with well‐defined spatial organization is fabricated by using a nickel hydroxide array as a precursor. The nickel hydroxide arrays are synthesized in titanium foil and reacted with K₃[Fe(CN)₆]. The plate‐like morphology of the nickel hydroxide is perfectly preserved and combined with abundant PBA nanocubes. After phosphidation at 350 °C, the obtained sample demonstrated excellent hydrogen evolution reaction (HER) activity in both acid and alkaline solutions to reach a current density of 10 mA cm^?2 with an overpotential of only 70 and 121 mV, respectively. With an overpotential of 266 mV, it can reach a larger current density of 500 mA cm^?2 in acid. The efficient HER activity of the obtained sample is mainly ascribed to its structural advantage with various active metal sites derived from the nickel hydroxide and PBA precursor. In addition, long‐term stability measurements have verified the good performance of the obtained sample in acid and alkaline solutions. An increment of overpotential of only 8 and 9 mV is observed, in the acid and alkaline solutions respectively. Beyond these assets, it is supposed that the strategy to synthesize 3D PBA arrays from nickel hydroxide can be extended to other metal–organic frameworks arrays for more electrochemical applications.     

FeS2 Nanoparticles Embedded in Reduced Graphene Oxide toward Robust,High‐Performance Electrocatalysts

Developing low‐cost, highly efficient, and robust earth‐abundant electrocatalysts for hydrogen evolution reaction (HER) is critical for the scalable production of clean and sustainable hydrogen fuel through electrochemical water splitting. This study presents a facile approach for the synthesis of nanostructured pyrite‐phase transition metal dichalcogenides as highly active, earth‐abundant catalysts in electrochemical hydrogen production. Iron disulfide (FeS₂) nanoparticles are in situ loaded and stabilized on reduced graphene oxide (RGO) through a current‐induced high‐temperature rapid thermal shock (≈12 ms) of crushed iron pyrite powder. FeS₂ nanoparticles embedded in between RGO exhibit remarkably improved electrocatalytic performance for HER, achieving 10 mA cm^?2 current at an overpotential as low as 139 mV versus a reversible hydrogen electrode with outstanding long‐term stability under acidic conditions. The presented strategy for the design and synthesis of highly active earth‐abundant nanomaterial catalysts paves the way for low‐cost and large‐scale electrochemical energy applications.     

Electrochemically Modifying the Electronic Structure of IrO2 Nanoparticles for Overall Electrochemical Water Splitting with Extensive Adaptability

Designing the electrocatalysts that are stable and active for extensively adaptable water splitting is highly desirable for developing hydrogen based energy. IrO₂ is a promising and widely used catalyst for the oxygen evolution reaction in commercial applications, but is rarely used for the hydrogen evolution reaction (HER), due to the high Gibbs free energy for hydrogen adsorption (ΔG_H*). Herein, an approach to modify the electronic structure of IrO₂ via cyclic voltammetry is proposed. In this process, Ir(+4) is partially reduced and trace Pt is simultaneously deposited on IrO₂, which greatly lowers the ΔG_H* and thus accelerates the reaction kinetics. The as‐prepared Pt–IrO₂/CC with low noble metal loading (36.6 µg cm^?2_(Ir+Pt)) exhibits excellent HER activity with overpotentials of 5, 22, and 26 mV at 10 mA cm^?2 in 0.5 m H₂SO₄, 1 m KOH, and 1 m phosphate buffer solution, respectively, making it possible to organize an all‐IrO₂ based water electrolyzer. The Pt–IrO₂/CC||IrO₂/CC couple exhibits a promising activity and stability in pH‐universal conditions as well as natural seawater for H₂ production. Density function theory calculations reveal that the optimized electronic structure of IrO₂ balances the ΔG_H*, resulting in a much enhanced HER performance.