Regulating Electronic Structure of Iron Nitride by Tungsten Nitride Nanosheets for Accelerated Overall Water Splitting

Two essential characteristics that are required for hybrid electrocatalysts to exhibit higher oxygen and hydrogen evolution reaction (OER and HER, respectively) activity are a favorable electronic configuration and a sufficient density of active sites at the interface between the two materials within the hybrid. In the present study, a hybrid electrocatalyst is introduced with a novel architecture consisting of coral-like iron nitride (Fe₂N) arrays and tungsten nitride (W₂N₃) nanosheets that satisfies these requirements. The resulting W₂N₃/Fe₂N catalyst achieves high OER activity (268.5 mV at 50 mA cm⁻²) and HER activity (85.2 mV at 10 mA cm⁻²) with excellent long-term durability in an alkaline medium. In addition, density functional theory calculations reveal that the individual band centers experience an upshift in the hybrid W₂N₃/Fe₂N structure, thus improving the OER and HER activity. The strategy adopted here thus provides a valuable guide for the fabrication of cost-effective multi-metallic crystalline hybrids for use as multifunctional electrocatalysts.     

Cobalt Phosphides Nanocrystals Encapsulated by P‐Doped Carbon and Married with P‐Doped Graphene for Overall Water Splitting

As one class of important functional materials, transition metal phosphides (TMPs) nanostructures show promising applications in catalysis and energy storage fields. Although great progress has been achieved, phase‐controlled synthesis of cobalt phosphides nanocrystals or related nanohybrids remains a challenge, and their use in overall water splitting (OWS) is not systematically studied. Herein, three kinds of cobalt phosphides nanocrystals encapsulated by P‐doped carbon (PC) and married with P‐doped graphene (PG) nanohybrids, including CoP@PC/PG, CoP‐Co₂P@PC/PG, and Co₂P@PC/PG, are obtained through controllable thermal conversion of presynthesized supramolecular gels that contain cobalt salt, phytic acid, and graphene oxides at proper temperature under Ar/H₂ atmosphere. Among them, the mixed‐phase CoP‐Co₂P@PC/PG nanohybrids manifest high electrocatalytic activity toward both hydrogen and oxygen evolution in alkaline media. Remarkably, using them as bifunctional catalysts, the fabricated CoP‐Co₂P@PC/PG || CoP‐Co₂P@PC/PG electrolyzer only needs a cell voltage of 1.567 V for driving OWS to reach the current density at 10 mA cm^?2, superior to their pure‐phase counterparts and recently reported bifunctional catalysts based devices. Also, such a CoP‐Co₂P@PC/PG || CoP‐Co₂P@PC/PG device exhibits outstanding stability for OWS. This work may shed some light on optimizing TMPs nanostructures based on phase engineering, and promote their applications in OWS or other renewable energy options.     

Cr‐Doped FeNi–P Nanoparticles Encapsulated into N‐Doped Carbon Nanotube as a Robust Bifunctional Catalyst for Efficient Overall Water Splitting

Exploring high‐efficiency, stable, and cost‐effective bifunctional electrocatalysts for overall water splitting is greatly desirable and challenging. Herein, a newly designed hybrid catalyst with Cr‐doped FeNi–P nanoparticles encapsulated into N‐doped carbon nanotubes (Cr‐doped FeNi–P/NCN) with unprecedented electrocatalytic activity is developed by a simple one‐step heating treatment. The as‐synthesized Cr‐doped FeNi–P/NCN with moderate Cr doping exhibits admirable oxygen evolution reaction and hydrogen evolution reaction activities with overpotentials of 240 and 190 mV to reach a current density of 10 mA cm^?2 in 1 m KOH solution. When used in overall water splitting as a bifunctional catalyst, it needs only 1.50 V to give a current density of 10 mA cm^?2, which is superior to its typically integrated Pt/C and RuO₂ counterparts (1.54 V @ 10 mA cm^?2). Density functional theory calculation confirms that Cr doping into a FeNi‐host can effectively alter the relative Gibbs adsorption energy and reduces the theoretical overpotential. Additionally, the synergetic effects between Cr‐doped FeNi–P nanoparticles and NCNs are regarded as significant contributors to accelerate charge transfer and promote electrocatalytic activity in hybrid catalysts.     

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.     

Iron Vacancies Induced Bifunctionality in Ultrathin Feroxyhyte Nanosheets for Overall Water Splitting

Exploring of new catalyst activation principle holds a key to unlock catalytic powers of cheap and earth‐abundant materials for large‐scale applications. In this regard, the vacancy defects have been proven to be effective to initiate catalytic active sites and endow high electrocatalytic activities. However, such electrocatalytically active defects reported to date have been mostly formed by anion vacancies. Herein, it is demonstrated for the first time that iron cation vacancies induce superb water splitting bifunctionality in alkaline media. A simple wet‐chemistry method is developed to grow ultrathin feroxyhyte (δ‐FeOOH) nanosheets with rich Fe vacancies on Ni foam substrate. The theoretical and experimental results confirm that, in contrast to anion vacancies, the formation of rich second neighboring Fe to Fe vacancies in δ‐FeOOH nanosheets can create catalytic active centers for both hydrogen and oxygen evolution reactions. The atomic level insight into the new catalyst activation principle based on metal vacancies is adaptable for developing other transition metal electrocatalysts, including Fe‐based ones.     

A Cost‐Efficient Bifunctional Ultrathin Nanosheets Array for Electrochemical Overall Water Splitting

The design of cost‐efficient earth‐abundant catalysts with superior performance for the electrochemical water splitting is highly desirable. Herein, a general strategy for fabricating superior bifunctional water splitting electrodes is reported, where cost‐efficient earth‐abundant ultrathin Ni‐based nanosheets arrays are directly grown on nickel foam (NF). The newly created Ni‐based nanosheets@NF exhibit unique features of ultrathin building block, 3D hierarchical structure, and alloy effect with the optimized Ni₅Fe layered double hydroxide@NF (Ni₅Fe LDH@NF) exhibiting low overpotentials of 210 and 133 mV toward both oxygen evolution reaction and hydrogen evolution reaction at 10 mA cm^?2 in alkaline condition, respectively. More significantly, when applying as the bifunctional overall water splitting electrocatalyst, the Ni₅Fe LDH@NF shows an appealing potential of 1.59 V at 10 mA cm^?2 and also superior durability at the very high current density of 50 mA cm^?2.     

Boron and Sodium Doping of Polymeric Carbon Nitride Photoanodes for Photoelectrochemical Water Splitting

Polymeric carbon nitride is a promising photoanode material for water-splitting and organic transformation-based photochemical cells. Despite achieving significant progress in performance, these materials still exhibit low photoactivity compared to inorganic photoanodic materials because of a moderate visible light response, poor charge separation, and slow oxidation kinetics. Here, the synthesis of a sodium- and boron-doped carbon nitride layer with excellent activity as a photoanode in a water-splitting photoelectrochemical cell is reported. The new synthesis consists of the direct growth of carbon nitride (CN) monomers from a hot precursor solution, enabling control over the monomer-to-dopant ratio, thus determining the final CN properties. The introduction of Na and B as dopants results in a dense CN layer with a packed morphology, better charge separation thanks to the in situ formation of an electron density gradient, and an extended visible light response up to 550 nm. The optimized photoanode exhibits state-of-the-art performance: photocurrent densities with and without a hole scavenger of about 1.5 and 0.9 mA cm⁻² at 1.23 V versus reversible hydrogen electrode (RHE), and maximal external quantum efficiencies of 56% and 24%, respectively, alongside an onset potential of 0.3 V.     

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.     

Porous Cobalt–Nickel Hydroxide Nanosheets with Active Cobalt Ions for Overall Water Splitting

Low‐cost and high‐performance catalysts are of great significance for electrochemical water splitting. Here, it is reported that a laser‐synthesized catalyst, porous Co_0.75Ni_0.25(OH)₂ nanosheets, is highly active for catalyzing overall water splitting. The porous nanosheets exhibit low overpotentials for hydrogen evolution reaction (95 mV@10 mA cm^?2) and oxygen evolution reaction (235 mV@10 mA cm^?2). As both anode and cathode catalysts, the porous nanosheets achieve a current density of 10 mA cm^?2 at an external voltage of 1.56 V, which is much lower than that of commercial Ir/C‐Pt/C couple (1.62 V). Experimental and theoretical investigations reveal that numerous Co³⁺ ions are generated on the pore wall of nanosheets, and the unique atomic structure around Co³⁺ ions leads to appropriate electronic structure and adsorption energy of intermediates, thus accelerating hydrogen and oxygen evolution.     

Significant Enhancement of Water Splitting Activity of N‐Carbon Electrocatalyst by Trace Level Co Doping

Replacement of precious metal electrocatalysts with highly active and cost efficient alternatives for complete water splitting at low voltage has attracted a growing attention in recent years. Here, this study reports a carbon‐based composite co‐doped with nitrogen and trace amount of metallic cobalt (1 at%) as a bifunctional electrocatalyst for water splitting at low overpotential and high current density. An excellent electrochemical activity of the newly developed electrocatalyst originates from its graphitic nanostructure and highly active Co‐N_x sites. In the case of carefully optimized sample of this electrocatalyst, 10 mA cm^?2 current density can be achieved for two half reactions in alkaline solutions—hydrogen evolution reaction and oxygen evolution reaction—at low overpotentials of 220 and 350 mV, respectively, which are smaller than those previously reported for nonprecious metal and metal‐free counterparts. Based on the spectroscopic and electrochemical investigations, the newly identified Co‐N_x sites in the carbon framework are responsible for high electrocatalytic activity of the Co,N‐doped carbon. This study indicates that a trace level of the introduced Co into N‐doped carbon can significantly enhance its electrocatalytic activity toward water splitting.     

Cation‐Modulated HER and OER Activities of Hierarchical VOOH Hollow Architectures for High‐Efficiency and Stable Overall Water Splitting

Atom‐scale modulation of electronic regulation in nonprecious‐based electrocatalysts is promising for efficient catalytic activities. Here, hierarchically hollow VOOH nanostructures are rationally constructed by partial iron substitution and systematically investigated for electrocatalytic water splitting. Benefiting from the hierarchically stable scaffold configuration, highly electrochemically active surface area, the synergistic effect of the active metal atoms, and optimal adsorption energies, the 3% Fe (mole ratio) substituted electrocatalyst (VOOH‐3Fe) exhibits a low overpotential of 90 and 195 mV at 10 mA cm^?2 for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in alkaline media, respectively, superior than the other samples with a different substituted ratio. To the best of current knowledge, 195 mV overpotential at 10 mA cm^?2 is the best value reported for V or Fe (oxy)hydroxide‐based OER catalysts. Moreover, the electrolytic cell employing the VOOH‐3Fe electrode as both the cathode and anode exhibits a cell voltage of 0.30 V at 10 mA cm^?2 with a remarkable stability over 60 h. This work heralds a new pathway to design efficient bifunctional catalysts toward overall water splitting.     

Nitrogen‐Doped Carbon Encapsulated Mesoporous Vanadium Nitride Nanowires as Self‐Supported Electrodes for Flexible All‐Solid‐State Supercapacitors

Flexible 3D nanoarchitectures have received tremendous interest recently because of their potential applications in flexible/wearable energy storage devices. Herein, 3D intertwined nitrogen‐doped carbon encapsulated mesoporous vanadium nitride nanowires (MVN@NC NWs) are investigated as thin, lightweight, and self‐supported electrodes for flexible supercapacitors (SCs). The MVN NWs have abundant active sites accessible to charge storage, and the N‐doped carbon shell suppresses electrochemical dissolution of the inner MVN NWs in an alkaline electrolyte, leading to excellent capacitive properties. The flexible MVN@NC NWs film electrode delivers a high areal capacitance of 282 mF cm⁻² and exhibits excellent long‐term stability with 91.8% capacitance retention after 12 000 cycles in a KOH electrolyte. All‐solid‐state flexible SCs assembled by sandwiching two flexible MVN@NC NWs film electrodes with alkaline poly(vinyl alcohol) (PVA), sodium polyacrylate, and KOH gel electrolyte boast a high volumetric capacitance of 10.9 F cm⁻³, an energy density of 0.97 mWh cm⁻³, and a power density of 2.72 W cm⁻³ at a current density of 0.051 A cm⁻³ based on the entire cell. By virtue of the excellent mechanical flexibility, high capacitance, and large energy/power density, the self‐supported MVN@NC NWs paper‐like electrodes have large potential applications in portable and wearable flexible electronics.     

Construction of Defect‐Rich Ni‐Fe‐Doped K0.23MnO2 Cubic Nanoflowers via Etching Prussian Blue Analogue for Efficient Overall Water Splitting

Designing elaborate nanostructures and engineering defects have been promising approaches to fabricate cost‐efficient electrocatalysts toward overall water splitting. In this work, a controllable Prussian‐blue‐analogue‐sacrificed strategy followed by an annealing process to harvest defect‐rich Ni‐Fe‐doped K_0.23MnO₂ cubic nanoflowers (Ni‐Fe‐K_0.23MnO₂ CNFs‐300) as highly active bifunctional catalysts for oxygen and hydrogen evolution reactions (OER and HER) is reported. Benefiting from many merits, including unique morphology, abundant defects, and doping effect, Ni‐Fe‐K_0.23MnO₂ CNFs‐300 shows the best electrocatalytic performances among currently reported Mn oxide‐based electrocatalysts. This catalyst affords low overpotentials of 270 (320) mV at 10 (100) mA cm^?2 for OER with a small Tafel slope of 42.3 mV dec^?1, while requiring overpotentials of 116 and 243 mV to attain 10 and 100 mA cm^?2 for HER respectively. Moreover, Ni‐Fe‐K_0.23MnO₂ CNFs‐300 applied to overall water splitting exhibits a low cell voltage of 1.62 V at 10 mA cm^?2 and excellent durability, even superior to the Pt/C||IrO₂ cell at large current density. Density functional theory calculations further confirm that doping Ni and Fe into the crystal lattice of δ‐MnO₂ can not only reinforce the conductivity but also reduces the adsorption free‐energy barriers on the active sites during OER and HER.