Synthesis and electrocatalytic activity of Ni0.85Se/MoS2 for hydrogen evolution reaction

Recently, the replacement of expensive platinum-based catalytic materials with non-precious metal materials to electrolyze water for hydrogen separation has attracted much attention. In this work, Ni_0.85Se, MoS₂ and their composite Ni_0.85Se/MoS₂ with different mole ratios are prepared successfully, as electrocatalysts to catalyze the hydrogen evolution reaction (HER) in water splitting. The result shows that MoS₂/Ni_0.85Se with a molar ratio of Mo/Ni = 30 (denoted as M30) has the best catalytic performance towards HER, with the lowest overpotential of 118 mV at 10 mA cm⁻², smallest Tafel slope of 49 mV·dec⁻¹ among all the synthesized materials. Long-term electrochemical testing shows that M30 has good stability for HER over at least 30 h. These results maybe due to the large electrochemical active surface area and high conductivity. This work shows that transition metal selenides and sulfides can form effective electrocatalyst for HER.     

A novel efficient dual-functional electrocatalyst for overall water splitting based on Ni0.85Se/RGO/CNTs nanocomposite synthesized via different nickel precursors

Synthesizing efficient and affordable electrocatalysts for the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) remains a crucial problem on the way to practical applications for producing clean H₂ fuel. Herein, high-efficiency and stable transition metal based electrocatalysts Ni_0.85Se-1, Ni_0.85Se-2 and Ni_0.85Se-3 materials with different morphological characteristics were derived via a one-step hydrothermal route using the Ni(OH)₂ and metal-organic framework (Ni-BDC and Ni-BTC) as precursors, respectively. The results showed that Ni_0.85Se-2 exhibited excellent electrocatalytic activity. Subsequently, introducing carbon nanomaterials (RGO and CNTs) to form Ni_0.85Se/RGO/CNTs nanocomposite material further improves the catalytic activity owing to high conductivity. The resulting Ni_0.85Se/RGO/CNTs nanocomposites electrocatalyst showed a low overpotential of 232 mV and 165 mV and a low Tafel slope of 64 mV dec^?1 and 98 mV dec^?1 when the current density was 10 mA cm^?2 for OER and HER, respectively. In addition, the Ni_0.85Se/RGO/CNTs nanocomposites were used as an anode and cathode of the water electrolysis device and the overall water splitting performance was investigated. The results show just a voltage of 1.59 V was required when the current density was 10 mA cm^?2 and good overall water splitting stability for 20 h. The outstanding electrocatalytic performance of Ni_0.85Se/RGO/CNTs is mostly due to its noticeable porous structure, the high conductivity and the large surface area that came from RGO and CNTs.     

Promoted electrocatalytic hydrogen evolution performance by constructing Ni12P5–Ni2P heterointerfaces

Transition metal phosphides (TMPs) have been considered as cheap alternatives of precious metal platinum for electrochemical hydrogen evolution reaction (HER). In the past decades, many reports have indicated that the engineering of heterointerfaces between different components could efficiently enhance the activity of HER catalysts. Here, we report a facile method to construct Ni₁₂P₅–Ni₂P heterostructure by using a low temperature phosphorization strategy. The obtained Ni₁₂P₅–Ni₂P heterostructure shows high activity toward HER with an overpotential value of 166 mV at 10 mA cm^?2 and a Tafel slope of 60 mV dec^?1 in 0.5 M H₂SO₄. Compared with pure Ni₂P and Ni₁₂P₅, the Ni₁₂P₅–Ni₂P heterostructure has more active sites and faster HER kinetics due to the presence of the interfaces between Ni₁₂P₅ and Ni₂P. Furthermore, we used the obtained Ni₁₂P₅–Ni₂P as cathodic catalyst and IrO₂/Ti as anodic material to set up a proton exchange membrane (PEM) electrolyzer which shows good stability after 120 h continuous constant current electrolysis at 200 mA cm^?2. This work demonstrates the positive effect of heterostructure for HER catalysts and provides a feasible strategy for constructing earth-abundant electrocatalysts.     

Ultrathin-layered MoS2 hollow nanospheres decorating Ni3S2 nanowires as high effective self-supporting electrode for hydrogen evolution reaction

High-activity and cost-effective transition metal sulfides (TMSs) have attracted tremendous attention as promising catalysts for hydrogen evolution reaction (HER). However, a significant challenge is the simultaneous construction of abundant electrochemical active sites and the fast electronic transmission path to boost a high-efficient HER. Herein, we demonstrate a facile one-step hydrothermal preparation of MoS₂ hollow nanospheres decorating Ni₃S₂ nanowires supported on Ni foam (NF), without any other additional template, surfactant or annealing. In this three-dimensional (3D) heterostructure, the ultrathin-layered MoS₂ hollow nanospheres contribute to the promotion of the total surface area and the electrochemical active sites. Meanwhile, the Ni₃S₂ nanowires are beneficial to the high electrical conductivity. Consequently, the optimized MoS₂/Ni₃S₂/NF-200-24 electrocatalyst presents an extremely superior HER activity to that of individual MoS₂/NF and Ni₃S₂/NF. The HER overpotentials are 85 mV at 10 mA cm⁻² and 189 mV at 100 mA cm⁻², which are also comparable with the state-of-the-art 20% Pt/C/NF electrode at both low and high current.     

Self-standing,hybrid three-dimensional-porous MoS2/Ni3S2 foam electrocatalyst for hydrogen evolution reaction in alkaline medium

Self-standing and hybrid MoS₂/Ni₃S₂ foam is fabricated as electrocatalyst for hydrogen evolution reaction (HER) in alkaline medium. The Ni₃S₂ foam with a unique surface morphology results from the sulfurization of Ni foam showing a truncated-hexagonal stacked sheets morphology. A simple dip coating of MoS₂ on the sulfurized Ni foam results in the formation of self-standing and hybrid electrocatalyst. The electrocatalytic HER performance was evaluated using the standard three-electrode setup in the de-aerated 1 M KOH solution. The electrocatalyst shows an overpotential of 190 mV at ?10 mA/cm² with a Tafel slope of 65.6 mV/dec. An increased surface roughness originated from the unique morphology enhances the HER performance of the electrocatalyst. A density functional approach shows that, the hybrid MoS₂/Ni₃S₂ heterostructure synergistically favors the hydrogen adsorption-desorption steps. The hybrid electrocatalyst shows an excellent stability under the HER condition for 12 h without any performance degradation.     

Bimetallic-metal organic framework-derived Ni3S2/MoS2 hollow spheres as bifunctional electrocatalyst for highly efficient and stable overall water splitting

Herein, strongly coupled Ni₃S₂/MoS₂ hollow spheres derived from NiMo-based bimetal-organic frameworks are successfully synthesized for overall water splitting via a one-pot solvothermal method followed by sulfurization. A well-defined hollow spherical structure with a heterointerface between Ni₃S₂ and MoS₂ is constructed using solvothermal and sulfurization processes. Owing to their bimetallic heterostructure, porous hollow carbon structure with large surface area, and numerous exposed active sites, the Ni₃S₂/MoS₂ hollow spheres are found to be efficient electrocatalysts for both the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). The heterostructured Ni₃S₂/MoS₂ hollow spheres show small overpotentials of 303 and 166 mV to reach a current density of 10 mA cm^?2 for the OER and HER in 1.0 M KOH, respectively. Furthermore, an overall water-splitting electrolyzer consisting of the Ni₃S₂/MoS₂ hollow spheres as both the anode and cathode requires a very low cell voltage of 1.62 V to drive a current density of 10 mA cm^?2 with outstanding long-term stability for 100 h. Our findings offer a new pathway for the design and synthesis of electrochemically advanced bifunctional catalysts for various energy storage and conversion applications.     

Ni3S2-MoSx nanorods grown on Ni foam as high-efficient electrocatalysts for overall water splitting

In order to solve the problem of large overpotential in water electrolysis for hydrogen production, transition metal sulfides are promising bifunctional electrocatalysts for hydrogen evolution reaction/oxygen evolution reaction that can significantly reduce overpotential. In this work, Ni₃S₂ and amorphous MoS_x nanorods directly grown on Ni foam (Ni₃S₂-MoS_x/NF) were prepared via one-step solvothermal process, which were used as a high-efficient electrocatalyst for overall water splitting. The Ni₃S₂-MoS_x/NF composite exhibits very low overpotentials of 65 and 312 mV to reach 10 mA cm⁻² and 50 mA cm⁻² in 1.0 M KOH for HER and OER, respectively. Besides, it exhibits a low Tafel slope (81 mV dec⁻¹ for HER, 103 mV dec⁻¹ for OER), high exchange current density (1.51 mA cm⁻² for HER, 0.26 mA cm⁻² for OER), and remarkable long-term cycle stability. This work provides new perspective for further the development of highly effective non-noble-metal materials in the energy field.     

Active-center-enriched Ni0.85Se/g-C3N4 S-scheme heterojunction for efficient photocatalytic H2 generation

Photocatalysts with abundant active sites are essential for photocatalytic H₂ evolution from water. Herein, Ni_0.85Se-deposited g-C₃N₄ was obtained by a physical solvent evaporation method. The investigation shows that Ni_0.85Se with unsaturated active Se atoms can significantly improve the photocatalytic activity of g-C₃N₄, and the H₂ production rate of Ni_0.85Se/g-C₃N₄ can reach 8780.3 μmol g^?1 h^?1, which is 3.5 and 92.9 times higher than that of Ni_0.85+xSe/g-C₃N₄ (2497.9 μmol g^?1 h^?1) and pure g-C₃N₄ (94.5 μmol g^?1 h^?1), respectively. This improvement can be attributed to the quick charge transfer between Ni_0.85Se and g-C₃N₄ with S-scheme heterojunction feature based on a series of trapping experiments and photoelectrochemical analysis. Moreover, abundant unsaturated Se atoms could provide more H₂ evolution active sites. This work sheds light on the construction of heterojunctions with abundant active sites for H₂ production.     

A nano-spherical structure Ni3S2/Ni(OH)2 electrocatalyst prepared by one-step fast electrodeposition for efficient and durable water splitting

Developing non-noble metal catalysts with excellent electrocatalytic performance and stability is of great significance to hydrogen production by water electrolysis, but there are still problems of low activity, complex preparation and high cost. Herein, we fabricated a novel Ni₃S₂/Ni(OH)₂ dual-functional electrocatalyst by a one-step fast electrodeposition on nickel foam (NF). While maintaining the electrocatalytic performance of Ni₃S₂, the existence of heterostructure and Ni(OH)₂ co-catalyst function greatly improves the overall water splitting performance of Ni₃S₂/Ni(OH)₂–NF. Hence, It shows a low overpotential of 66 mV at 10 mA cm^?2 for HER and 249 mV at 20 mA cm^?2 for OER. The dual-functional electrocatalyst needs only 1.58 V at 20 mA cm^?2 when assembled two-electrode electrolytic cell. Impressively, the electrocatalyst also shows outstanding catalytic stability for about 800 h when 20 and 50 mA cm^?2 constant current was applied, respectively which demonstrates a potential electrocatalyst for overall water splitting.     

3D V–Ni3S2@CoFe-LDH core-shell electrocatalysts for efficient water oxidation

Studying cheap and efficient electrocatalysts is of great significance to promote the sluggish kinetics of oxygen evolution reaction (OER). Here, we adopted a simple two-step method to successfully prepare the 3D V–Ni₃S₂@CoFe-LDH core-shell electrocatalyst. The V–Ni₃S₂@CoFe-LDH/NF shows excellent OER performance with low overpotential (190 mV at 10 mA/cm² and 240 mV at 50 mA/cm²), small Tafel slope (26.8 mV/dec) and good long-term durability. Excitingly, to reach the same current density, V–Ni₃S₂@CoFe-LDH/NF electrode even needs much smaller overpotential than RuO₂. Furthermore, the outstanding OER activity of V–Ni₃S₂@CoFe-LDH/NF is ascribed to the following reasons: (1) V–Ni₃S₂ nanorod cores improve the conductivity and ensure the fast charge transfer; (2) CoFe-LDH nanosheets interconnected with each other provide more exposed active sites; (3) the unique 3D core-shell structures are favorable for electrolyte diffusion and gas releasing. Our work indicates that building 3D core-shell heterostructure will be a useful way to design good electrocatalysts.     

Coaxial Ni3S2@CoMoS4/NiFeOOH nanorods for energy-saving water splitting and urea electrolysis

High efficiency and energy-saving electrochemical hydrogen production has always been a research challenge, mainly due to the limitation of the sluggish kinetics of anodic reactions. Excellent performance depends largely on the clever design of nano-architectures and smart hybridization of active components. It is also very important to establish the relationship between structure and performance of materials. Form perspectives of chemical composition and nanostructure, we developed a novel heterostructure of Ni₃S₂@CoMoS₄/NiFeOOH coaxial nanorods on NF scaffold, in which the two-dimensional CoMoS₄ nanoplates and ultrathin NiFeOOH nanosheets vertically coil around the Ni₃S₂ nanorods by hydrothermal reaction combined with electrodepostion process. Such hierarchical nanorods can provide the heterointerface with highly open surface, ensuring the maximization of synergistic interaction. This heterostructure results in prominent bifunctional activity for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in alkaline water electrolysis systems, and HER coupled with urea oxidation reaction in urea electrolysis devices. It exhibits very low cell voltages for alkaline water splitting (1.732 V) and urea electrolysis (1.660 V) to afford a current density of 100 mA cm^?2 in the two-electrode system as well as excellent long-term stability. Our work provides a new construction for combining various active materials to competitive bifunctional electrocatalysts applied in energy-relative electrochemical devices.     

Interlaced rosette-like MoS2/Ni3S2/NiFe-LDH grown on nickel foam: A bifunctional electrocatalyst for hydrogen production by urea-assisted electrolysis

In targeting the most important energy and environmental issues in current society, the development of low-cost, bifunctional electrocatalysts for urea-assisted electrocatalytic hydrogen (H₂) production is an urgent and challenging task. In this work, interlaced rosette-like MoS₂/Ni₃S₂/NiFe-layered double hydroxide/nickel foam (LDH/NF) is successfully synthesized by a two-step hydrothermal reaction. Due to its unique interlaced heterostructure, MoS₂/Ni₃S₂/NiFe-LDH/NF exhibits excellent bifunctional catalytic activity towards the urea oxidation reaction (UOR) and the hydrogen evolution reaction (HER) in 1.0 M KOH with 0.5 M urea. In a concurrent two-electrode electrolyser (MoS₂/Ni₃S₂/NiFe-LDH/NF(+,-)), only voltage of 1.343 V is required to reach 50 mA cm⁻², which is 216 mV lower than for pure water splitting. Furthermore, after 16 h of urea electrolysis in 1.0 M KOH with 0.5 M urea, the current density remains at 98% of the original value. Thus, the catalyst is not only favorable for H₂ production, but also has great significance for the problem of urea-rich wastewater treatment.     

Chromium doping and in-grown heterointerface construction for modifying Ni3FeN toward bifunctional electrocatalyst toward alkaline water splitting

Exploring high-performance non-noble metal electrocatalysts is pivotal for eco-friendly hydrogen energy applications. Herein, featuring simultaneous Chromium doping and in-grown heterointerface engineering, the Cr doping Ni₃FeN/Ni heterostructure supported on N-doped graphene tubes (denoted as Cr–Ni₃FeN/Ni@N-GTs) was successfully constructed, which exhibits the superior bifunctional electrocatalytic performances (88 mV and 262 mV at 10 mA cm⁻² for HER and OER, respectively). Furthermore, an alkaline electrolyzer, employing Ni₃FeN/Ni@N-GTs as both the cathode and the anode, requires a low cell voltage of 1.57 V at 10 mA⋅cm⁻². Cr doping not only modulates the electronic structure of host Ni and Fe but also synchronously induces nitrogen vacancies, leading to a higher number of active sites; the in-grown heterointerface Cr–Ni₃FeN/Ni induces the charge redistribution by spontaneous electron transfer across the heterointerface, enhancing the intrinsic catalytic activity; the N-GTs skeleton with excellent electrical conductivity improves the electron transport and mass transfer. The synergy of the above merits endows the designed Cr–Ni₃FeN/Ni@ N-GTs with outstanding electrocatalytic properties for alkaline overall water splitting.     

One-step synthesis of Ni3S2 nanowires at low temperature as efficient electrocatalyst for hydrogen evolution reaction

Ni₃S₂ is an emerging cost-effective catalyst for hydrogen generation. However, a large amount of reported Ni₃S₂ was synthesized via multi-step approaches and few were fabricated based on the one-step strategies. Herein, we report a facile one-step low-temperature synthesis of Ni₃S₂ nanowires (NWs). In this strategy, a resin containing sulfur element is recommended as a sulfur resource to form Ni₃S₂ NWs. It presents a plausible explanation on the vapor–solid–solid (VSS) growth mechanism according to the results of this experiment and reported in literature that has been published. The Ni₃S₂ NW exhibits a potential ∼199 mV at 10 mA cm⁻² and the long-term durability over 30 h at 20 mA cm⁻² HER operation, better than other reported Ni₃S₂. More importantly, according to replace transition metal foam as the initial metal, other transition metal sulfide can be readily synthesized via this original approach.     

Super-hydrophilic/super-aerophobic Ni2P/Co(PO3)2 heterostructure for high-efficiency and durable hydrogen evolution electrocatalysis at large current density in alkaline fresh water,alkaline seawater and industrial wastewater

Seawater electrolysis has become an efficient method which makes full use of natural resources to produce hydrogen. However, it suffers high energy cost and chloride corrosion. Herein, we first present a Ni₂P/Co(PO₃)₂/NF heterostructure in which Co(PO₃)₂ with the nano-rose morphology in-situ grown on the rough Ni₂P/NF. The unique 3D nano-rose structure and the optimized electronic structure of the heterostructure enable Ni₂P/Co(PO₃)₂/NF super-hydrophilic and super-aerophobic characteristics, and highly facilitate hydrogen evolution reaction (HER) kinetics in alkaline fresh water, alkaline seawater and even industrial wastewater at large current density, which is rarely reported. Significantly, at large current densities, Ni₂P/Co(PO₃)₂/NF only requires overpotentials of 217 and 307 mV for HER to achieve 1000 mA cm⁻² in alkaline fresh water and alkaline seawater, respectively, and requires an overpotential of 469 mV for HER to deliver 500 mA cm⁻² in industrial wastewater. Furthermore, the overall seawater splitting system in the two-electrode electrolyzer only requires voltage of 1.98 V to drive 1000 mA cm⁻², which also demonstrates significant durability to keep 600 mA cm⁻² for at least 60 h. This study opens a new avenue of designing high efficiency electrocatalysts for hydrogen production at large current densities in alkaline seawater and industrial wastewater.     

Fluff spherical Co–Ni3S2/NF for enhanced hydrogen evolution

Ni₃S₂ is a kind of HER catalyst electrode with high efficiency and easy preparation. However, due to the weak electrochemical adsorption capacity of water molecules at the Ni site, it is not conducive to the dissociation of water molecules. At the same time, strong sulfur-hydrogen bond is easily formed at the S site, which greatly hinders the desorption and bonding of hydrogen atom to produce hydrogen. Hydrogen evolution performance of Ni₃S₂ in alkaline media needs to be improved. In this paper, fluff spherical Co–Ni₃S₂ was grown in situ on nickel foam by two-step hydrothermal method successfully. By doping cobalt ions, the strong interaction of S–H bond on Ni₃S₂ surface was weakened, the adsorption and dissociation of water molecules were promoted, and the catalyst was exposed to more reactive centers, so as to improve the hydrogen evolution performance of cathodic reduction reaction. Electrochemical test and Transient Photovoltage (TPV) tests show that Co–Ni₃S₂ has fast reaction kinetics and high electron transfer rate, especially it only needs 148 mV low overpotential to reach 10 mA cm^?2 in 1.0 M KOH alkaline electrolyte, which is better than Ni₃S₂/NF (250 mV). In addition, Co–Ni₃S₂ also has excellent electrochemical stability. Density functional theory (DFT) calculations confirm that the optimized adsorption energy enables the catalyst to exhibit excellent HER activity. This work provides useful guidance to construction of effective nickel related HER catalysts.     

Modular electrochemical production of hydrogen using Mott–Schottky Co9S8/Ni3S2 heterojunction as a redox mediator

Modular electrochemical production (MEP) system could decouple the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), and pairing with a redox mediator (RM), respectively. Herein, Mott–Schottky Co₉S₈/Ni₃S₂ heterojunction was constructed, which was employed as a RM to separate the hydrogen and oxygen production in space and time in MEP system for H₂. The MEP system for H₂ involved a two−step electrochemical−electrochemical (EC−EC) looping process. The reversible redox reaction of Co₉S₈/Ni₃S₂ was paired with HER in step 1 and subsequently paired with OER in step 2. The Mott–Schottky hetero-structures enabled the redistribution of Ni central charge and accelerated the electron transfer from semiconductor Ni₃S₂ to metallic Co₉S₈ on the interface. This made the formation of Lewis acid at the Ni₃S₂ in the heterojunction, which bonded with the OH⁻ Lewis base, facilitating the electrochemical redox kinetics of Co₉S₈/Ni₃S₂. Thus, the Co₉S₈/Ni₃S₂ RM presented a high area capacitance (29.60 F/cm² at 5 mA/cm²), and an excellent stability upon operation over 5000 cycles (15 days). The MEP system can continuously produce H₂ for 1502 s at 10 mA/cm² with a Faradaic efficiency of 100%. The MEP system possessed a high energy efficiency (83%), requiring a lower cell voltage than that of a conventional water electrolysis system. The MEP system for H₂ enabled flexible utilization of renewable solar energy by photovoltaic (PV) panels, thereby facilitating solar-to-hydrogen conversion.     

Vermicular Ni3S2–Ni(OH)2 heterostructure supported on nickel foam as efficient electrocatalyst for hydrogen evolution reaction in alkaline solution

Alkaline solution is considered to be more suitable for industrial application of hydrogen production by water electrolysis. However, most of the low-cost electrocatalyts such as Ni₃S₂ has poor ability to dissociate HO–H, resulting in unsatisfied hydrogen evolution performance in alkaline media. In this paper, a novel vermicular structure of Ni₃S₂–Ni(OH)₂ hybrid have been successfully prepared on nickel foam substrate (v-Ni₃S₂–Ni(OH)₂/NF) through a facile two-step containing hydrothermal and electrodeposition processes. The heterostructure consists of rod-like Ni₃S₂ and Ni(OH)₂ nanosheets, in which Ni(OH)₂ is coated on the surface of Ni₃S₂. This structure not only constructs a fast electron transfer channel but also possesses rich heterointerface, thus accelerating the Volmer step and allowing more active sites of Ni₃S₂ to functioning well. As a result, v-Ni₃S₂–Ni(OH)₂/NF exhibited excellent electrocatalytic activity toward HER in 1.0 M KOH solution. It only needs 78 mV and 137 mV to drive current density of 10 mA cm⁻² and 100 mA cm⁻². Moreover, the catalytic stability of this electrocatalyst in alkaline solution is also satisfactory.     

Fabrication of robust CoP/Ni2P/CC composite for efficient hydrogen evolution reaction and the reduction of graphene oxide

Developing the novel catalysts with an excellent performance of hydrogen generation is essential to facilitate the application of hydrogen evolution reaction (HER). Herein, a heterostructured cobalt phosphide/nickel phosphide/carbon cloth (CoP/Ni₂P/CC) composite was fabricated via an interfacial engineering strategy to achieve the modification of CoP nanoleaf on Ni₂P nanosheet skeleton supported by carbon cloth. By virtue of the unique heterostructure, abundant exposing active sites and the synergistic coupling effect of CoP and Ni₂P nanoparticles, the elaborated CoP/Ni₂P/CC composite exhibits a robust catalytic property. Among fabricated composites, the optimal CoP/Ni₂P/CC-4 catalyst behaves an excellent HER performance at a wide pH range (overpotentials of 67, 71 and 95 mV to afford 10 mA cm^?2 in 0.5 M H₂SO₄, 1 M KOH and 1 M PBS, respectively). The HER current density of this composite shows a negligible degradation after continuous test for 24 h. Charmingly, the HER process of this catalyst was innovatively applied to reduce graphene oxide, and thus exploiting the fabrication route of reduced graphene oxide (rGO). We are sure that this work will provide a firm guideline for the exploitation of pH-universal HER catalysts and the exploration of HER application.     

Superhydrophilic 3D peony flower-like Mo-doped Ni2S3@NiFe LDH heterostructure electrocatalyst for accelerating water splitting

Constructing highly efficient nonprecious electrocatalysts for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) is essential to improve the efficiency of overall water splitting, but still remains lots of obstacles. Herein, a novel 3D peony flower-like electrocatalyst was synthesized by employing Mo–Ni₂S₃/NF nanorod arrays as scaffolds to in situ growth ultrathin NiFe LDH nanosheets (Mo-Ni₂S₃@NiFe LDH). As expected, the novel peony flower-like Mo–Ni₂S₃@NiFe LDH displays superior electrocatalytic activity and stability for both OER and HER in alkaline media. Low overpotentials of only 228 mV and 109 mV are required to achieve the current densities of 50 mA cm^?2 and 10 mA cm^?2 for OER and HER, respectively. Additionally, the material remarkably accelerates water splitting with a low voltage of 1.54 V at 10 mA cm^?2, which outperforms most transition metal electrodes. The outstanding electrocatalytic activity benefits from the following these features: 3D peony flower-like structure with rough surface provides more accessible active sites; superhydrophilic surfaces lead to the tight affinity between electrode with electrolyte; metallic Ni substrate and highly conductive Mo–Ni₂S₃ nanorods scaffold together with offer fast electron transfer; the nanorod arrays and porous Ni foam accelerate gas bubble release and ions transmission; the strong interfacial effect between Mo-doped Ni₃S₂ and NiFe LDH shortens transport pathway, which are benefit for electrocatalytic performance enhancement. This work paves a new avenue for construction and fabrication the 3D porous structure to boost the intrinsic catalytic activities for energy conversion and storage applications.