Mo-/Co-N-C Hybrid Nanosheets Oriented on Hierarchical Nanoporous Cu as Versatile Electrocatalysts for Efficient Water Splitting

Designing robust and cost-effective electrocatalysts based on Earth-abundant elements is crucial for large-scale hydrogen production through electrochemical water splitting. Here, nitrogen-doped carbon engrafted Mo₂N/CoN hybrid nanosheets that are seamlessly oriented on hierarchical nanoporous Cu scaffold (Mo-/Co-N-C/Cu), as highly efficient electrocatalysts for alkaline hydrogen evolution reaction are reported. The constituent heterostructured Mo₂N/CoN nanosheets work as bifunctional electroactive sites for both water dissociation and adsorption/desorption of hydrogen intermediates while the nitrogen-doped carbon bridges electron transfers between electroactive sites and interconnective Cu current collectors by making use of Mo-/Co-N-C bonds and intimate C/Cu contacts at interfaces. As a consequence of unique architecture having electroactive sites to be sufficiently accessible, self-supported nanoporous Mo-/Co-N-C/Cu hybrid electrodes exhibit outstanding electrocatalysis in 1 m KOH, with a negligible onset overpotential and a low Tafel slope of 47 mV dec⁻¹. They only take overpotential of as low as 230 mV to reach current density of 1000 mA cm⁻². When coupled with their electro-oxidized derivatives that mediate efficiently the oxygen evolution reaction, the alkaline water electrolyzer can achieve ≈100 mA cm⁻² at 1.622 V in 1 m KOH electrolyte, ≈0.343 V lower than the device constructed with commercially available Pt/C and Ir/C nanocatalysts immobilized on nanoporous Cu electrodes.     

Bifunctional Heterostructure Assembly of NiFe LDH Nanosheets on NiCoP Nanowires for Highly Efficient and Stable Overall Water Splitting

3D hierarchical heterostructure NiFe LDH@NiCoP/NF electrodes are prepared successfully on nickel foam with special interface engineering and synergistic effects. This research finds that the as‐prepared NiFe LDH@NiCoP/NF electrodes have a more sophisticated inner structure and intensive interface than a simple physical mixture. The NiFe LDH@NiCoP/NF electrodes require an overpotential as low as 120 and 220 mV to deliver 10 mA cm^?2 for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in 1 m KOH, respectively. Tafel and electrochemical impedance spectroscopy further reveal a favorable kinetic during electrolysis. Specifically, the NiFe LDH@NiCoP/NF electrodes are simultaneously used as cathode and anode for overall water splitting, which requires a cell voltage of 1.57 V at 10 mA cm^?2. Furthermore, the synergistic effect of the heterostructure improves the structural stability and promotes the generation of active phases during HER and OER, resulting in excellent stability over 100 h of continuous operation. Moreover, the strategy and interface engineering of the introduced heterostructure can also be used to prepare other bifunctional and cost‐efficient electrocatalysts for various applications.     

Bifunctional Nickel Phosphide Nanocatalysts Supported on Carbon Fiber Paper for Highly Efficient and Stable Overall Water Splitting

Self‐supported electrodes comprising carbon fiber paper (CP) integrated with bifunctional nickel phosphide (Ni‐P) electrocatalysts are fabricated by electrodeposition of Ni on functionalized CP, followed by a convenient one‐step phosphorization treatment in phosphorus vapor at 500 °C. The as‐fabricated CP@Ni‐P electrode exhibits excellent electrocatalytic performance toward hydrogen evolution in both acidic and alkaline solutions, with only small overpotentials of 162 and 250 mV, respectively, attaining a cathodic current density of 100 mA cm^?2. Furthermore, the CP@Ni‐P electrode also exhibits superior catalytic performance toward oxygen evolution reaction (OER). An exceptionally high OER current of 50.4 mA cm^?2 is achieved at an overpotential of 0.3 V in 1.0 m KOH. The electrode can sustain 10 mA cm^?2 for 180 h with only negligible degradation, showing outstanding durability. Detailed microstructural and compositional studies reveal that upon OER in alkaline solution the surface Ni‐P is transformed to NiO covered with a thin Ni(OH)_x layer, forming a Ni‐P/NiO/Ni(OH)_x heterojunction, which presumably enhances the electrocatalytic performance for OER. Given the well‐defined bifunctionality, a full alkaline electrolyzer is constructed using two identical CP@Ni‐P electrodes as cathode and anode, respectively, which can realize overall water splitting with efficiency as high as 91.0% at 10 mA cm^?2 for 100 h.     

Vertically Aligned WS2 Nanosheets for Water Splitting

Vertically aligned WS₂ (VAWS₂) nanosheet films are prepared using a lithium based anodization electrolyte to fabricate WO₃ films followed by sulfurization. The VAWS₂ synthesized here is self‐organized as a conformal structure to expose active edge sites for water splitting. These vertically aligned nanosheets are composed of exfoliated WS₂ to provide abundant active edges for catalytic reactions. Hydrogen evolution activity of the VAWS₂ is demonstrated to show high catalytic current, low onset overpotential and small Tafel slope. By certain measures, this VAWS₂ nanosheet film outperforms some of the state‐of‐the‐art hydrogen evolution reaction (HER) catalysts, which opens up a new pathway to simply and scalably fabricate high‐performance water electrolysis catalysts.     

Regulating the Electronic Structure of CoP Nanosheets by O Incorporation for High‐Efficiency Electrochemical Overall Water Splitting

The exploration of earth‐abundant and high‐efficiency bifunctional electrocatalysts for overall water splitting is of vital importance for the future of the hydrogen economy. Regulation of electronic structure through heteroatom doping represents one of the most powerful strategies to boost the electrocatalytic performance of hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Herein, a rational design of O‐incorporated CoP (denoted as O‐CoP) nanosheets, which synergistically integrate the favorable thermodynamics through modification of electronic structures with accelerated kinetics through nanostructuring, is reported. Experimental results and density functional theory simulations manifest that the appropriate O incorporation into CoP can dramatically modulate the electronic structure of CoP and alter the adsorption free energies of reaction intermediates, thus promoting the HER and OER activities. Specifically, the optimized O‐CoP nanosheets exhibit efficient bifunctional performance in alkaline electrolyte, requiring overpotentials of 98 and 310 mV to deliver a current density of 10 mA cm^?2 for HER and OER, respectively. When served as bifunctional electrocatalysts for overall water splitting, a low cell voltage of 1.60 V is needed for achieving a current density of 10 mA cm^?2. This proposed anion‐doping strategy will bring new inspiration to boost the electrocatalytic performance of transition metal–based electrocatalysts for energy conversion applications.     

Oriented Growth of ZIF‐67 to Derive 2D Porous CoPO Nanosheets for Electrochemical‐/Photovoltage‐Driven Overall Water Splitting

Hydrogen generation from water splitting driven by electric/solar energy is highly desirable, which requires efficient and robust bifunctional electrocatalysts for both hydrogen and oxygen evolution reactions. 2D porous hybrids with attractive chemical and structural properties are the first‐class candidates for water splitting, while control over efficient and modulable synthesis remains a huge challenge. This work demonstrates a zeolitic imidazolate framework‐67 (ZIF‐67) nanoplate self‐template approach to fabricate 2D porous oxygen‐incorporated cobalt phosphide (CoPO) ultrathin nanosheets. The synthesis starts with the oriented growth of ZIF‐67 nanoplates along [211] crystal plane, followed by oxidation/phosphorization processes for pore generation and O/P coincorporation in the hybrid. The resultant 2D porous CoPO nanosheets afford very small voltages of 1.52 and 1.98 V for overall water splitting at 10 and 200 mA cm^?2, respectively. This excellent bifunctionality further provides the basis for photovoltage‐driven water splitting at a Faradaic efficiency of 97.6%. These findings offer a general strategy for rational design and modulation of 2D porous catalysts for various electrocatalytic and other applications.     

Epitaxial Heterogeneous Interfaces on N‐NiMoO4/NiS2 Nanowires/Nanosheets to Boost Hydrogen and Oxygen Production for Overall Water Splitting

Developing bifunctional efficient electrocatalysts for both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is in high demand for the development of overall water‐splitting devices. In particular, the electrocatalytic performance can be largely improved by designing positive nanoscale‐heterojunction with well‐tuned interfaces. Herein, a novel top‐down strategy is reported to construct the oxide/sulfide heterostructures (N‐NiMoO₄/NiS₂ nanowires/nanosheets) as a multisite HER/OER catalyst. Starting with the NiMoO₄ nanowires, nitridation in a controlled manner enables activation of Ni sites in NiMoO₄ and then yields oxide/sulfide heterojunction by directly vulcanizing the highly composition‐segregated N‐NiMoO₄ nanowires. The abundant epitaxial heterogeneous interfaces at atomic‐level facilitate the electron transfer from N‐NiMoO₄ to NiS₂, which further cooperate synergistically toward both the hydrogen and oxygen generation in alkali solution. Furthermore, with N‐NiMoO₄/NiS₂ grown carbon fiber cloth as the engineering electrode, the assembled N‐NiMoO₄/NiS₂–N‐NiMoO₄/NiS₂ system can deliver a current density of 10 mA cm^?2 with the cell voltage of 1.60 V in the water‐splitting reaction. This current density is 3.39 times higher than that of the Pt–Ir set (2.95 mA cm^?2). The excellent catalytic performance offered of N‐NiMoO₄/NiS₂ nanowires/nanosheets presents a great example to demonstrate the significance of interface engineering in the field of electrocatalysis.     

Kinetically Controlled Coprecipitation for General Fast Synthesis of Sandwiched Metal Hydroxide Nanosheets/Graphene Composites toward Efficient Water Splitting

The development of cost‐effective and applicable strategies for producing efficient oxygen evolution reaction (OER) electrocatalysts is crucial to advance electrochemical water splitting. Herein, a kinetically controlled room‐temperature coprecipitation is developed as a general strategy to produce a variety of sandwich‐type metal hydroxide/graphene composites. Specifically, well‐defined α‐phase nickel cobalt hydroxide nanosheets are vertically assembled on the entire graphene surface (NiCo‐HS@G) to provide plenty of accessible active sites and enable facile gas escaping. The tight contact between NiCo‐HS and graphene promises effective electron transfer and remarkable durability. It is discovered that Ni doping adjusts the nanosheet morphology to augment active sites and effectively modulates the electronic structure of Co center to favor the adsorption of oxygen species. Consequently, NiCo‐HS@G exhibits superior electrocatalytic activity and durability for OER with a very low overpotential of 259 mV at 10 mA cm^?2. Furthermore, a practical water electrolyzer demonstrates a small cell voltage of 1.51 V to stably achieve the current density of 10 mA cm^?2, and 1.68 V to 50 mA cm^?2. Such superior electrocatalytic performance indicates that this facile and manageable strategy with low energy consumption may open up opportunities for the cost‐effective mass production of various metal hydroxides/graphene nanocomposites with desirable morphology and competing performance for diverse applications.     

Efficient and Stable Bifunctional Electrocatalysts Ni/NixMy (M = P,S) for Overall Water Splitting

Development of easy‐to‐make, highly active, and stable bifunctional electrocatalysts for water splitting is important for future renewable energy systems. Three‐dimension (3D) porous Ni/Ni₈P₃ and Ni/Ni₉S₈ electrodes are prepared by sequential treatment of commercial Ni‐foam with acid activation, followed by phosphorization or sulfurization. The resultant materials can act as self‐supported bifunctional electrocatalytic electrodes for direct water splitting with excellent activity toward oxygen evolution reaction and hydrogen evolution reaction in alkaline media. Stable performance can be maintained for at least 24 h, illustrating their versatile and practical nature for clean energy generation. Furthermore, an advanced water electrolyzer through exploiting Ni/Ni₈P₃ as both anode and cathode is fabricated, which requires a cell voltage of 1.61 V to deliver a 10 mA cm^?2 water splitting current density in 1.0 m KOH solution. This performance is significantly better than that of the noble metal benchmark—integrated Ni/IrO₂ and Ni/Pt–C electrodes. Therefore, these bifunctional electrodes have significant potential for realistic large‐scale production of hydrogen as a replacement clean fuel to polluting and limited fossil‐fuels.     

Density-Controlled Metal Nanocluster with Modulated Surface for pH-Universal and Robust Water Splitting

Reducing the particle sizes of transition metals (TMs) and avoiding their aggregation are crucial for increasing the TMs atom utilization and enhancing their industrial potential. However, it is still challenging to achieve uniform distributed and density-controlled TMs nanoclusters (NCs) under high temperatures due to the strong interatomic metallic bonds and high surface energy of NCs. Herein, a series of TMs NCs with controllable density and nitrogen-modulated surface are prepared with the assistance of a selected covalent organic polymer (COP), which can provide continuous anchoring sites and size-limited skeletons. The prepared Ir NCs show superior hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) activities than commercial Pt/C and Ir/C in both acid and alkaline media. In particular, the as-prepared Ir NCs exhibit remarkable full water splitting performance, reaching a current density of 10 mA cm⁻² at ultralow overpotentials of 1.42 and 1.43 V in alkaline and acidic electrolyte, respectively. The excellent electrocatalytic activities are attributed to the increased surface atom utilization and the improved intrinsic activity of Ir NCs. More importantly, the Ir NCs catalyst shows superior long-term stability due to the strong interaction between Ir NCs and the N-doped carbon layer.     

N‐, O‐, and S‐Tridoped Carbon‐Encapsulated Co9S8 Nanomaterials: Efficient Bifunctional Electrocatalysts for Overall Water Splitting

The development of highly active and stable earth‐abundant catalysts to reduce or eliminate the reliance on noble‐metal based ones in green and sustainable (electro)chemical processes is nowadays of great interest. Here, N‐, O‐, and S‐tridoped carbon‐encapsulated Co₉S₈ (Co₉S₈@NOSC) nanomaterials are synthesized via simple pyrolysis of S‐ and Co(II)‐containing polypyrrole solid precursors, and the materials are proven to serve as noble metal‐free bifunctional electrocatalysts for water splitting in alkaline medium. The nanomaterials exhibit remarkable catalytic performances for oxygen evolution reaction in basic electrolyte, with small overpotentials, high anodic current densities, low Tafel slopes as well as very high (nearly 100%) Faradic efficiencies. Moreover, the materials are found to efficiently electrocatalyze hydrogen evolution reaction in acidic as well as basic solutions, showing high activity in both cases and maintaining good stability in alkaline medium. A two‐electrode electrolyzer assembled using the material synthesized at 900 °C (Co₉S₈@NOSC‐900) as an electrocatalyst at both electrodes gives current densities of 10 and 20 mA cm^?2 at potentials of 1.60 and 1.74 V, respectively. The excellent electrocatalytic activity exhibited by the materials is proposed to be mainly due to the synergistic effects between the Co₉S₈ nanoparticles cores and the heteroatom‐doped carbon shells in the materials.     

Large‐Size,Porous, Ultrathin NiCoP Nanosheets for Efficient Electro/Photocatalytic Water Splitting

Porous ultrathin 2D catalysts are attracting great attention in the field of electro/photocatalytic hydrogen evolution reaction (HER) and overall water splitting. Herein, a universal pH‐controlled wet‐chemical strategy is reported followed by thermal and phosphorization treatment to prepare large‐size, porous and ultrathin bimetallic phosphide (NiCoP) nanosheets, in which graphene oxide is adopted as a template to determine the size of products. The thickness of the resultant NiCoP nanosheets ranges from 3.5 to 12.8 nm via delicately adjusting pH from 7.8 to 8.5. The thickness‐dependent electrocatalytic performance is evidenced experimentally and explained by computational studies. The prepared large‐size ultrathin NiCoP nanosheets show excellent bifunctional electrocatalytic activity for overall water splitting, with low overpotentials of 34.3 mV for HER and 245.0 mV for oxygen evolution reaction, respectively, at 10 mA cm^?2. Furthermore, the NiCoP nanosheets exhibit superior photocatalytic HER performance, achieving a high HER rate of 238.2 mmol h^?1 g^?1 in combination with commonly used photocatalyst CdS, which is far superior to that of Pt/CdS (81.7 mmol h^?1 g^?1). All these results demonstrate large‐size porous ultrathin NiCoP nanosheets as an efficient and multifunctional electro/photocatalyst for water splitting.     

Single-Atom Co-Decorated MoS2 Nanosheets Assembled on Metal Nitride Nanorod Arrays as an Efficient Bifunctional Electrocatalyst for pH-Universal Water Splitting

The commercialization of electrochemical water splitting technology requires electrocatalysts that are cost-effective, highly efficient, and stable. Herein, an advanced bifunctional electrocatalyst based on single-atom Co-decorated MoS₂ nanosheets grown on 3D titanium nitride (TiN) nanorod arrays (CoSAs-MoS₂/TiN NRs) has been developed for overall water splitting in pH-universal electrolytes. When applied as a self-standing cathodic electrode, the CoSAs-MoS₂/TiN NRs requires overpotentials of 187.5, 131.9, and 203.4 mV to reach a HER current density of 10 mA cm^–2 in acidic, alkaline, and neutral conditions, respectively, which are superior to the most previously reported non-noble metal HER electrocatalysts at the same current density. The CoSAs-MoS₂/TiN NRs anodic electrode also shows low OER overpotentials of 454.9, 340.6, and 508.0 mV, respectively, at a current density of 10 mA cm^–2 in acidic, alkaline, and neutral mediums, markedly outperforming current OER catalysts reported elsewhere. More importantly, an electrolyzer delivered from the cathodic and anodic CoSAs-MoS₂/TiN NRs electrodes exhibits an extraordinary overall water splitting performance with good stability and durability in pH-universal conditions.     

Bifunctional Porous NiFe/NiCo2O4/Ni Foam Electrodes with Triple Hierarchy and Double Synergies for Efficient Whole Cell Water Splitting

A 3D hierarchical porous catalyst architecture based on earth abundant metals Ni, Fe, and Co has been fabricated through a facile hydrothermal and electrodeposition method for efficient oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). The electrode is comprised of three levels of porous structures including the bottom supermacroporous Ni foam (≈500 μm) substrate, the intermediate layer of vertically aligned macroporous NiCo₂O₄ nanoflakes (≈500 nm), and the topmost NiFe(oxy)hydroxide mesoporous nanosheets (≈5 nm). This hierarchical architecture is binder‐free and beneficial for exposing catalytic active sites, enhancing mass transport and accelerating dissipation of gases generated during water electrolysis. Serving as an anode catalyst, the designed hierarchical electrode displays excellent OER catalytic activity with an overpotential of 340 mV to achieve a high current density of 1200 mA cm^?2. Serving as a cathode catalyst, the catalyst exhibits excellent performance toward HER with a moderate overpotential of 105 mV to deliver a current density of 10 mA cm^?2. Serving as both anode and cathode catalysts in a two‐electrode water electrolysis system, the designed electrode only requires a potential of 1.67 V to deliver a current density of 10 mA cm^?2 and exhibits excellent durability in prolonged bulk alkaline water electrolysis.     

Multicomponent Intermetallic Nanoparticles on Hierarchical Metal Network as Versatile Electrocatalysts for Highly Efficient Water Splitting

Developing high-efficiency and cost-effective alloy catalysts toward hydrogen-evolution reaction (HER) is crucial for large-scale hydrogen production via electrochemical water splitting, but conventional single-principal-element alloy design usually causes insufficient activity and durability of state-of-the-art multimetallic catalysts based on non-precious transition metals. Herein, we report multicomponent intermetallic Mo(NiFeCo)₄ nanoparticles seamlessly integrated on hierarchical nickel network (Mo(NiFeCo)₄/Ni) as robust hydrogen-evolution electrocatalysts with remarkably improved activity and durability by making use of iron and cobalt atoms partially substituting nickel sites to form high-entropy NiFeCo sublattice in intermetallic MoNi₄ matrix, which serve as bifunctional electroactive sites for both water dissociation and adsorption/combination of hydrogen intermediate and improves thermodynamic stability. By virtue of bicontinuous nanoporous nickel skeleton facilitating electron/ion transportation, self-supported nanoporous Mo(NiFeCo)₄/Ni electrode exhibits exceptional HER electrocatalysis, with low Tafel slope (≈35 mV dec⁻¹), high current density (≈2300 mA cm⁻²) at low overpotential (200 mV) and long-term durability in 1 m KOH. When coupled to its electrooxidized and nitrified derivative for oxygen-evolution reaction, their alkaline water electrolyzers operate with a superior overall water-splitting output, outperforming the one constructed with commercially available noble-metal-based catalysts. These electrochemical properties make it an attractive candidate as electrocatalyst in alkaline water electrolysis for large-scale hydrogen generation.     

Corrosion Engineering on Iron Foam toward Efficiently Electrocatalytic Overall Water Splitting Powered by Sustainable Energy

Exploiting highly effective and low-cost electrocatalysts for the hydrogen evolution reaction (HER) is a pressing challenge for the development of sustainable hydrogen energy. In this work, a facile and industrially compatible one-pot corrosion strategy for the rapid synthesis of amorphous RuO₂-decorated FeOOH nanosheets on iron foam (FF Na Ru) within 1 h is reported. Corrosion is a common and inevitable phenomenon that occurs on metal surfaces without electricity input, high temperature, and tedious synthetic procedures. The FF Na Ru electrode is superhydrophilic and aerophobic, which guarantees intimate contact with the electrolyte and accelerates the instantaneous escape of produced gas bubbles during the electrocatalytic process. Moreover, the strong electronic interactions between RuO₂ and FeOOH promote the electrocatalytic process via dramatically improving the electrochemical interfacial properties. Thus, the FF Na Ru electrocatalyst presents excellent catalytic activity towards the HER (30 mV at 10 mA cm^–2) and overall water-splitting (230 mV at 10 mA cm^–2) in 1 M KOH. The overall water-splitting could be simply powered by sustainable and intermittent sunlight, wind, and thermal energies motivated Stirling engine. Density functional theory calculations confirm that coupling effects between RuO₂ and FeOOH are also responsible for promoting the electrocatalytic HER performance.     

Fabrication of Polyoxometalate Anchored Zinc Cobalt Sulfide Nanowires as a Remarkable Bifunctional Electrocatalyst for Overall Water Splitting

The advancement of a naturally rich and effective bifunctional substance for hydrogen and oxygen evolution reaction is crucial to enhance hydrogen fuel production efficiency via the electrolysis process. Herein, facile and scalable hydrothermal synthesis of bifunctional electrocatalyst of polyoxometalate anchored zinc cobalt sulfide nanowire on Ni-foam (NF) for overall water splitting is reported for the first time. The electrochemical analysis of POM@ZnCoS/NF displays significantly low HER and OER overpotentials of 170/337 and 200/300 mV to attain a current density of 10/40 and 20/50 mA cm⁻², respectively, demonstrating the notable performance of POM@ZnCoS/NF toward H₂ and O₂ evolution reaction in alkaline medium. Additionally, the electrolyzer consisting of the POM@ZnCoS/NF anode and cathode shows an appealing potential of 1.56 V to deliver 10 mA cm⁻² current density for overall water splitting. The high electrocatalytic activity of the POM@ZnCoS/NF is attributed to modulation of the electronic and chemical properties, increment of the electroactive sites and electrochemically active surface area of the zinc cobalt sulfide nanowires due to the anchorage of polyoxometalate nanoparticles. These results demonstrate the advantage of the polyoxometalate incorporation strategy for the design of cost-effective and highly competent bifunctional catalysts for complete water splitting.     

Novel Iron/Cobalt‐Containing Polypyrrole Hydrogel‐Derived Trifunctional Electrocatalyst for Self‐Powered Overall Water Splitting

Development of efficient, low‐cost, and durable electrocatalysts for the oxygen reduction reaction (ORR), oxygen evolution reaction (OER), and hydrogen evolution reaction (HER) is of significant importance for many electrochemical devices, such as rechargeable metal–air batteries, fuel cells, and water electrolyzers. Here, a novel approach for the synthesis of a trifunctional electrocatalyst derived from iron/cobalt‐containing polypyrrole (PPy) hydrogel is reported. This strategy relies on the formation of a supramolecularly cross‐linked PPy hydrogel that allows for efficient and homogeneous incorporation of highly active Fe/Co–N–C species. Meanwhile, Co nanoparticles are also formed and embedded into the carbon scaffold during the pyrolysis process, further promoting electrochemical activities. The resultant electrocatalyst exhibits prominent catalytic activities for ORR, OER, and HER, surpassing previously reported trifunctional electrocatalysts. Finally, it is demonstrated that the as‐obtained trifunctional electrocatalyst can be used for electrocatalytic overall water splitting in a self‐powered manner under ambient conditions. This work offers new prospects in developing highly active, nonprecious‐metal‐based electrocatalysts in electrochemical energy devices.     

Ar/H2/O2-Controlled Growth Thermodynamics and Kinetics to Create Zero-, One-, and Two-Dimensional Ruthenium Nanocrystals towards Acidic Overall Water Splitting

A gas controlled formation strategy is developed to synthesize free-standing 0D Ru nanoparticles, 1D Ru nanowires, and 2D Ru nanosheets through in-situ regulated growth thermodynamics and kinetics with typical inert, reductive, and oxidative gases (Ar/H₂/O₂). The growth process of these Ru nanoparticles, nanowires, and nanosheets follow non-directional growth, shape-directed nanoparticle attachment, and directional growth mechanisms, respectively. Kinetics studies approve that H₂ accelerates the reduction rate of the Ru precursor, while O₂ depresses the reduction. The calculation results of the Gibbs surface free energy under different gas coverage further show that small molecules’ gas can effectively regulate the surface state and growth rate. These Ru nanocrystals exhibit excellent acidic water splitting performance. This work has systematically studied the influence of the small molecule gas on the formation process of the Ru nanocrystals, and provides an effective idea for the development and research of high-performance nanomaterials in the future.