Heterostructure Electrocatalyst Research Articles

Electron modulation strategy of heterogeneous Ni2P/FeP coupled with CeO2 for efficient overall water splitting

Interface engineering presents a promising avenue for elucidating the electronic structure of an electrocatalyst to enhance the ad/desorption process of intermediate substances (H2O*, H*, OH*). This study used a strategy guided by interface engineering optimization to design a heterostructure electrocatalyst (CeO2-Ni2P/FeP/NF). In alkaline media, heterostructure electrocatalyst requires only 103 mV and 189 mV to drive the HER and OER at a current density of 10 mA·cm−2. As a dual-function electrode, CeO2-Ni2P/FeP/NF electrocatalysts require only 1.53, 1.76, and 1.85 V cell voltage to provide 10, 50, and 100 mA·cm−2 current densities. Experiments and DFT calculations reveal that CeO2 can promote electronic reconstruction at heterogeneous interfaces, enhancing the activity of Ni, Fe, and P sites. More importantly, the CeO2-Ni2P/FeP/NF heterojunction exhibits great synergistic effects, optimizing the ad/desorption of H2O* and H*, consequently inducing a substantial increase in the electronic energy at the Fermi level. This work presents a promising electronic structure adjustment strategy to fabricate highly active and durable electrocatalysts for efficient energy conversion.

Constructing Dense CoRu-CoMoO4 Heterointerfaces with Electron Redistribution for Synergistically Boosted Alkaline Electrocatalytic Water Splitting.

Constructing metal alloys/metal oxides heterostructured electrocatalysts with abundant and strongly coupling interfaces is vital yet challenging for practical electrocatalytic water splitting. Herein, CoRu nanoalloys uniformly anchored on CoMoO4 nanosheet heterostructured electrocatalyst (CoRu-CoMoO4/NF) are synthesized via a self-templated strategy by simply annealing of Ru-etched CoMoO4/NF precursor in a reduction atmosphere. The dense and robustly coupled interface not only provides abundant active sites for water splitting but also strengthens the charge transfer efficiency. Furthermore, the theoretical calculations unveil that the strong electronic interaction at CoRu-CoMoO4 interface can induce an interfacial electron redistribution and reduce the energetic barriers for the hydrogen and oxygen intermediates, thereby accelerating the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) kinetics. The resultant catalyst only requires the overpotentials of 49mV for HER and 209mV for OER at 10mAcm-2. Moreover, the constructed CoRu-CoMoO4||CoRu-CoMoO4 two-electrode cell achieves a cell voltage of 1.54V at 10mAcm-2, outperforming the benchmark Pt/C||IrO2. This work explores an avenue for the rational design of heterostructured electrocatalysts with abundant interfaces for practical water-splitting electrocatalysis.

NH4Cl-Assisted Electrosynthesis of P-Doped Co(OH)2 Nanosheet on Cu2S Hollow Nanotube Arrays for Glycerol Electrooxidation.

The glycerol oxidation reaction (GOR) for producing high-value-added organic compounds is of great research interest due to its potential in alleviating the energy crisis. Herein, a facile NH4Cl-assisted electrodeposition strategy is reported to fabricate 3D nano-forest array-like hollow nanostructures. The hierarchical heterojunction by combining phosphorus doping Co(OH)2 nanosheets with Cu2S nanotube arrays (P-Co(OH)2@Cu2S NTs/CF) is developed to realize the optimization on GOR. The optimized P-Co(OH)2@Cu2S NTs/CF catalyst exhibits an exceptional activity with a formate Faradaic efficiency (FE) of 97.40% at a potential of 1.30V (vs RHE). The experimental results indicate that this unique hollow nano-forest structure, grown on a conductive support, can expose more active sites and facilitate electron transfer, thereby demonstrating excellent GOR performance. This work provides new opportunities for the design of electrocatalysts of high-activity and low-cost hollow heterostructure electrocatalysts for glycerol electrooxidation.

Enhanced Adsorption Kinetics and Capacity of a Stable CeF3@Ni3N Heterostructure for Methanol Electro‐Reforming Coupled with Hydrogen Production

Alkaline methanol‐water electrolysis system is regarded as an appealing strategy for electro‐reforming methanol into formate and producing hydrogen with low energy‐consumption compared with alkaline water electrolysis. However, stability and selectivity under high current densities for practical application remain challenging. Herein, a CeF3@Ni3N nanosheets array anchored on carbon cloth (CeF3@Ni3N/CC) was fabricated. The gradual extrusion of F species from Ni(OH)2 lattices can stabilize hierarchical structure and construct abundant heterostructure interfaces. Moreover, CeF3 can modulate electron distribution of Ni3N, thus simultaneously enhancing the surface adsorption kinetics and capability of methanol and OH‐, which is conducive to enhanced methanol oxidation reaction (MOR) activity and selectivity. Therefore, bifunctional CeF3@Ni3N/CC exhibits low potential of 1.43 V at 500 mA cm‐2, along with high stability over 72 h and high faradaic efficiency (FEs) in MOR, as well as an overpotential of 76 mV to achieve 50 mA cm‐2 for hydrogen evolution reaction (HER). Furthermore, membrane‐free CeF3@Ni3N/CC||CeF3@Ni3N/CC cell for MOR||HER delivers high electrocatalytic activity, long‐term stability and FEs at high current density of 300 mA cm‐2. This study highlights the importance of optimizing surface adsorption behavior of active species, as well as rational design of highly efficient heterostructure electrocatalysts for methanol upgrading coupled with hydrogen production.

Enhanced Adsorption Kinetics and Capacity of a Stable CeF3@Ni3N Heterostructure for Methanol Electro-Reforming Coupled with Hydrogen Production.

Alkaline methanol-water electrolysis system is regarded as an appealing strategy for electro-reforming methanol into formate and producing hydrogen with low energy-consumption compared with alkaline water electrolysis. However, stability and selectivity under high current densities for practical application remain challenging. Herein, a CeF3@Ni3N nanosheets array anchored on carbon cloth (CeF3@Ni3N/CC) was fabricated. The gradual extrusion of F species from Ni(OH)2 lattices can stabilize hierarchical structure and construct abundant heterostructure interfaces. Moreover, CeF3 can modulate electron distribution of Ni3N, thus simultaneously enhancing the surface adsorption kinetics and capability of methanol and OH-, which is conducive to enhanced methanol oxidation reaction (MOR) activity and selectivity. Therefore, bifunctional CeF3@Ni3N/CC exhibits low potential of 1.43 V at 500 mA cm-2, along with high stability over 72 h and high faradaic efficiency (FEs) in MOR, as well as an overpotential of 76 mV to achieve 50 mA cm-2 for hydrogen evolution reaction (HER). Furthermore, membrane-free CeF3@Ni3N/CC||CeF3@Ni3N/CC cell for MOR||HER delivers high electrocatalytic activity, long-term stability and FEs at high current density of 300 mA cm-2. This study highlights the importance of optimizing surface adsorption behavior of active species, as well as rational design of highly efficient heterostructure electrocatalysts for methanol upgrading coupled with hydrogen production.

Targeted Topological Routine Regulation of RuNiOx Precursors for Excellent Alkaline Overall Water Splitting

Designing efficient and stable electrocatalysts for the hydrogen and oxygen evolution reactions (HER and OER) is crucial for green hydrogen production via the water‐splitting system. The bifunctional electrocatalyst offers a promising strategy due to the simplified preparation process and reduced expenses. However, the single‐component bifunctional catalysts often struggle to match the redox potential of water and to achieve proper adsorption/desorption of Gibbs free energy for both H and O intermediates simultaneously. Herein, through precisely controlling the topological transformation path of the RuNiOx precursor, we successfully prepared high‐performance RuNi/Ni and Ru/NiO heterostructure electrocatalysts for the HER and OER, respectively. The energy level matching between the fabricated electrocatalyst and water oxidation/reduction potential confirms the feasibility of HER and OER. The synergistic effect between the active sites ensures rapid, intermediate adsorption/desorption kinetics. As a result, the assembled alkaline overall water splitting setup achieves a current density of 1 A cm‐2 at 2 V and maintains stable operation at 100 mA cm‐2 for 100 hours.

NiMo/NiFe-LDH heterostructured electrocatalyst for hydrogen production from water electrolysis

Constructing low-cost and efficient catalysts for electrocatalytic water splitting to produce hydrogen is of great significance. In this study, we successfully prepared NiMo/NiFe-LDH electrocatalysts with abundant coupled interfaces using a hydrothermal method and electrodeposition. The synergistic effect between the NiMo alloy and NiFe-LDH nanosheets induces charge redistribution at the interface and accelerates charge transfer, thus improving reaction kinetics and enhancing electrocatalytic performance. Experimental results show that at a current density of 10 mA cm−2, the HER overpotential of NiMo/NiFe-LDH is 35 mV, demonstrating excellent water-splitting performance. This work provides insights into the development of alloy/transition metal hydroxides for efficient water-splitting hydrogen production.

A strongly coupled 1T'-ReSe2@2H-MoSe2 van der Waals heterostructure for efficient electrocatalytic hydrogen evolution at high current densities.

Developing efficient and durable non-noble metal electrocatalysts for high current-density hydrogen evolution reactions (HER) is a pressing requirement for commercial industrial electrolyzers. In this study, a vertical 1T'-ReSe2@2H-MoSe2 van der Waals heterostructure was developed through interface engineering to enhance the advantages of each component and expose numerous active sites. Experimental investigations and density functional theorycalculations demonstrate significant electronic coupling at the interface between 1T'-ReSe2 and 2H-MoSe2, with suitable Gibbs free energy for hydrogen adsorption. The 1T'-ReSe2@2H-MoSe2 heterostructure catalyst achieves high current density HER with low overpotentials of 191 mV to generate up to 800 mA/cm2 in 0.5 M H2SO4, outperforming commercial 5% Pt/C catalysts. Moreover, this catalyst exhibits rapid reaction kinetics and long-term durability, illustrating a successful approach to designing efficient heterostructure electrocatalysts for hydrogen production through interface engineering.

Constructing 2D PtSe2/PtCo Heterojunctions by Partial Selenization for Enhanced Hydrogen Evolution

AbstractThe rational design and fabrication of 2D heterojuctions are proven a promising strategy for boosting the performance of electrocatalysts. Although 2D platinum diselenide (PtSe2) exhibits catalytic activity for hydrogen evolution reaction (HER), the catalytic performance is still unsatisfactory due to its inert basal plane, wide bandgap, and poor electron transfer ability. Herein, a new strategy is reported to construct PtSe2/PtCo heterojunctions by partial selenization of PtCo alloy for high‐efficiency HER electrocatalyst, which exhibits a low overpotential of 38 mV at the current density of 10 mA cm−2, a small Tafel slope of 22 mV dec−1, and a superior stability over 24 h and 1000 cycles. The outstanding HER activity of the catalyst arises from the strong electronic interactions between PtSe2 and PtCo in the heterojunctions, which induce electron transferring from PtSe2 to PtCo and the d‐band center down shifting, and thus optimize the H* adsorption/desorption. This work provides a novel strategy for constructing highly efficient heterostructure electrocatalysts, which facilitates the applications of hydrogen energy conversion.

Rational design of chromium-doped NiFe phosphide/phosphate heterostructures for inhibiting chloride ion adsorption and achieving alkaline seawater splitting at industrial-level current density

Electrocatalysts with high activity and corrosion resistance, tailored for industrial-grade current densities, played a crucial role in seawater electrolysis. Here, we synthesized a petal-like Cr-doped NiFe phosphate 'semi-coated' phosphide heterostructure electrocatalyst grown on nickel foam (Cr-NiFeP/PO3@NF). This catalyst demonstrated superior catalytic performance in natural seawater, maintaining stability and only a slight increase in cell voltage after operating continuously for 100 h at a current density of 1 A cm−2. The incorporation of Cr introduced a significant number of unpaired electrons, which enhanced the conductivity of the catalyst, facilitated the creation of electron depletion regions around Ni and Fe, and improved the interaction with adsorption intermediates. Furthermore, the high activity and corrosion resistance during the oxygen evolution reaction (OER) were due to the interaction between the in-situ formed high-valent phosphate and NiFeCrOOH during the anodization process.

Upcycling of Spent LiFePO4 Cathodes to Heterostructured Electrocatalysts for Stable Direct Seawater Splitting.

The pursuit of carbon-neutral energy has intensified the interest in green hydrogen production from direct seawater electrolysis, given the scarcity of freshwater resources. While Ni-based catalysts are known for their robust activity in alkaline water oxidation, their catalytic sites are prone to rapid degradation in the chlorine-rich environments of seawater, leading to limited operation time. Herein, we report a Ni(OH)2 catalyst interfaced with laser-ablated LiFePO4 (Ni(OH)2/L-LFP), derived from spent Li-ion batteries (LIBs), as an effective and stable electrocatalyst for direct seawater oxidation. Our comprehensive analyses reveal that the PO4 3- species, formed around L-LFP, effectively repels Cl- ions during seawater oxidation, mitigating corrosion. Simultaneously, the interface between in situ generated NiOOH and Fe3(PO4)2 enhances OH- adsorption and electron transfer during the oxygen evolution reaction. This synergistic effect leads to a low overpotential of 237 mV to attain a current density of 10 mA cm-2 and remarkable durability, with only a 3.3 % activity loss after 600 h at 100 mA cm-2 in alkaline seawater. Our findings present a viable strategy for repurposing spent LIBs into high-performance catalysts for sustainable seawater electrolysis, contributing to the advancement of green hydrogen production technologies.

Upcycling of Spent LiFePO4 Cathodes to Heterostructured Electrocatalysts for Stable Direct Seawater Splitting

AbstractThe pursuit of carbon‐neutral energy has intensified the interest in green hydrogen production from direct seawater electrolysis, given the scarcity of freshwater resources. While Ni‐based catalysts are known for their robust activity in alkaline water oxidation, their catalytic sites are prone to rapid degradation in the chlorine‐rich environments of seawater, leading to limited operation time. Herein, we report a Ni(OH)2 catalyst interfaced with laser‐ablated LiFePO4 (Ni(OH)2/L‐LFP), derived from spent Li‐ion batteries (LIBs), as an effective and stable electrocatalyst for direct seawater oxidation. Our comprehensive analyses reveal that the PO43− species, formed around L‐LFP, effectively repels Cl− ions during seawater oxidation, mitigating corrosion. Simultaneously, the interface between in situ generated NiOOH and Fe3(PO4)2 enhances OH− adsorption and electron transfer during the oxygen evolution reaction. This synergistic effect leads to a low overpotential of 237 mV to attain a current density of 10 mA cm−2 and remarkable durability, with only a 3.3 % activity loss after 600 h at 100 mA cm−2 in alkaline seawater. Our findings present a viable strategy for repurposing spent LIBs into high‐performance catalysts for sustainable seawater electrolysis, contributing to the advancement of green hydrogen production technologies.

Engineering of MnTe/MnO Heterostructures with Interfacial Electric Field Modulation for Efficient and Durable Li–O2 Batteries

AbstractDesign and synthesis of highly active and robust bifunctional cathode catalysts for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are of vital significance for practical applications of lithium–oxygen (Li–O2) batteries. Herein, a built‐in electric field (BIEF) strategy is reported to fabricate MnTe/MnO heterostructures with a large work function difference (ΔΦ) as a bifunctional cathode catalyst in Li–O2 batteries. The MnTe/MnO heterostructures with nanosheets and microporous structures result in an abundance of exposed active sites and facilitate mass transfer. More importantly, the heterogeneous MnTe/MnO nano‐interface region provides a BIEF that can trigger interfacial charge redistribution, fine‐tune the adsorption energy of oxygen intermediates, and alter the morphology of discharge products to accelerate ORR/OER kinetics. Impressively, the fabricated Li–O2 batteries with MnTe/MnO cathode showcases exhibit excellent electrochemical performances, including low charging overpotential, a high specific capacity of 11930 mA h g−1, and good cycle stability over 350 cycles even with a fixed specific capacity of 500 mA h g−1 at a current density of 500 mA g−1. This work provides an avenue for the rational design of high performance heterostructure electrocatalysts toward practical applications for rechargeable Li–O2 batteries.

Deliberate Amorphization of Co-MOF for Constructing Crystalline-Amorphous Heterostructures Toward High-Performance Water Electrolysis.

The endowment of metal organic frameworks (MOF) with superior electrocatalytic performance without compromising their structural/compositional superiorities is of great significance for the development of renewable energy devices, yet remains a grand challenge. Herein, a deliberate partial amorphization strategy is developed to construct a heterostructured electrocatalyst consisting of crystalline Co-MOF and amorphous Co-S nanoflake arrays aligned on the carbon cloth (CC) substrate (abbreviated as Co-MOF/Co-S@CC hereafter) through a rapid sulfuration method. The simultaneous implement of crystalline-amorphous (c-a) heterostructure and nanoflake arrayed architecture on CC substrate renders the Co-MOF/Co-S@CC with abundant and tight active sites, accelerated charge transfer rate, regulated electronic structures, and reinforced structural stability. As such, the obtained Co-MOF/Co-S@CC electrode demonstrates outstanding electrochemical hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) performances with the overpotentials of 64 and 217mV at 10mA cm-2, respectively. Moreover, a two-electrode electrolyzer assembled by Co-MOF/Co-S@CC electrodes exhibits the lower cell voltages and larger current densities than those of Pt/C and RuO2 counterparts, excellent reversibility and prominent long-term stability, representing a great prospect for feasible H2 production. This adopted concept of c-a heterostructure for electronic regulation may bring about insightful inspiration for designing high-performance electrocatalysts for sustainable energy systems.

Facile synthesis of spherical-shaped CeC2–TiO2 nanocomposite electrocatalyst with boosted alkaline OER

Developing noble metal-free multifunctional electrocatalysts to catalyze water oxidation is vital for future renewable energy systems. Herein, through several defect modifications, the CeC2–TiO2 nanocomposite on the strength of enriched oxygen vacancies was successfully fabricated by facile hydrothermal method on SS (stainless steel) substrate, attributed to the conductive ability for fast electron transportation. A well-defined phase growth, vibrational bonding of metal atoms, morphological determination, and elemental composition for synthesized heterostructured electrocatalysts were revealed by XRD, FTIR, TEM, and EDX, respectively. XPS has complied to understand the moderate binding energies of CeC2–TiO2 for OER intermediates, which signifies the strong interactions between electronic states of Ce, C, Ti, and O atoms. With the plentiful catalytic active sites, the resultant CeC2–TiO2 entails low overpotentials of only 169 mV and 108.8 mV/dec Tafel slope to afford 10 mA cm−2 for OER in 1.0 M KOH are tested through cyclic and linear sweep voltammogram measurements, thereby exhibit promising activity in alkaline water electrolysis. EIS measurements revealed a decreased polarization resistance for the composite dominated by the small semicircle diameter, corresponding to the adsorption of intermediates. Finally, observed results strongly recommended that the CeC2–TiO2 catalyst exhibited superior OER performance due to excellent electrical chemical coupling between CeC2 and TiO2.

Nickel-Iron Layered Double Hydroxides/Nickel Sulfide Heterostructured Electrocatalysts on Surface-Modified Ti Foam for the Oxygen Evolution Reaction.

Electrochemical approaches for generating hydrogen from water splitting can be more promising if the challenges in the anodic oxygen evolution reaction (OER) can be harnessed. The interface heterostructure materials offer strong electronic coupling and appropriate charge transport at the interface regions, promoting accessible active sites to prompt kinetics and optimize the adsorption-desorption of active species. Herein, we have designed an efficient multi-interface-engineered Ni3Fe1 LDH/Ni3S2/TW heterostructure on in situ generated titanate web layers from the titanium foam. The synergistic effects of the multi-interface heterostructure caused the exposure of rich interfacial electronic coupling, fast reaction kinetics, and enhanced accessible site activity and site populations. The as-prepared electrocatalyst demonstrates outstanding OER activity, demanding a low overpotential of 220 mV at a high current density of 100 mA cm-2. Similarly, the designed Ni3Fe1 LDH/Ni3S2/TW electrocatalyst exhibits a low Tafel slope of 43.2 mV dec-1 and excellent stability for 100 h of operation, suggesting rapid kinetics and good structural stability. Also, the electrocatalyst shows a low overpotential of 260 mV at 100 mA cm-2 for HER activity. Moreover, the integrated electrocatalyst exhibits an incredible OER activity in simulated seawater with an overpotential of 370 mV at 100 mA cm-2 and stability for 100 h of operation, indicating good OER selectivity. This work might benefit further fabricating effective and stable self-sustained electrocatalysts for water splitting in large-scale applications.

Surface Reconstruction Regulation of Co3N Through Heterostructure Engineering Toward Efficient Oxygen Evolution Reaction.

Oxygen evolution reaction (OER) electrocatalysts generally experience structural and electronic modifications during electrocatalysis. This phenomenon, referred to as surface reconstruction, results in the formation of catalytically active species that act as real OER sites. Controlling surface reconstruction therefore is vital for enhancing the OER performance of electrocatalysts. In this study, a new approach is introduced of heterostructure engineering to facilitate the surface reconstruction of target catalysts. Using MnCo carbonate hydroxide (MnCo─CH)@Co3N as a demonstration, it is discovered that the surface reconstruction occurs more readily and rapidly on MnCo─CH@Co3N than on Co3N. More interestingly, during the reconstruction process, Mn species migrate to the surface, enabling the in situ formation of highly active Mn-doped CoOOH. Consequently, the MnCo─CH@Co3N catalyst after reconstruction exhibits a low overpotential of 257mV at 10mAcm-2, compared to 379mV of individual Co3N. This work offers fresh perspectives on understanding the enhanced OER performance of heterostructure electrocatalysts and the role of heterostructure in promoting surface reconstruction.

Modulation of interface electric field over CoMoP-CoMoP2 heterostructure for high-efficiency oxygen evolution reaction

The construction of a heterostructure can significantly enhance the intrinsic activity of the electrocatalysts. In this study, a simple electrospinning combined with post-treatment strategy is successively employed to fabricate novel CoMoP-CoMoP2 heterostructure nanofibers. Experimental results and density functional theory (DFT) calculations demonstrate that the formation of CoMoP-CoMoP2 heterointerface can optimize the kinetics of the oxygen evolution reaction (OER) and enhance the intrinsic catalytic activity. As anticipated, the resulting CoMoP-CoMoP2 electrocatalyst displays outstanding OER performance (184 mV @ 10 mA cm−2, and 302 mV @100 mA cm−2) as well as excellent stability in 1 M KOH. Moreover, the OER test results of CoMoP-CoMoP2 with varying CoMoP and CoMoP2 contents indicate that CoMoP-CoMoP2-1 (with a mass ratio of approximately 1.01/10.1) exhibits the highest OER activity. Utilized as the overall water splitting electrocatalyst, CoMoP-CoMoP2-1 demonstrates exceptional durability and outperforms Pt/C||RuO2 electrolyzer, achieving a current density of 10 mA cm−2 and a battery voltage of only 1.53 V during continuous operation for 260 h. These findings suggest the practical application potential of this material, confirming the promising nature of bimetallic phosphide-bimetallic phosphide heterostructure electrocatalysts.

Paired array electrocatalyst coupling NiFe-MOF and NiFe-LDH for boosting oxygen evolution reaction

Developing affordable and highly efficient electrocatalytic materials is of utmost importance and indispensable for the process of water splitting, specifically for the oxygen evolution reaction (OER). To improve the OER process, a remarkable pair sites OER catalyst was successfully synthesized by coupling array NiFe-LDH and NiFe-MOF, which grew close together and support each other, some evidences prove that NiFe-LDH and NiFe-MOF heterostructure could enhance the electrocatalytic activities. The array NiFe-LDH/NiFe-MOF/NF-20 exhibits exceptional performance in the OER as evidenced by remarkably low overpotentials of 244 mV and 261 mV at the current densities of 50 and 100 mA/cm2, respectively. These significantly reduced overpotentials demonstrate the ability of the catalyst to facilitate the OER with minimal energy input, highlighting its remarkable efficiency. Furthermore, the OER overpotential was merely increased 23 mV after a rigorous 100 hours durability test. The results reveal that the heterostructures of NiFe-MOF and NiFe-LDH of the catalyst are the key factors for maintaining its excellent OER performance of over extended periods of operation. All the evidences show an excellent OER catalyst is fabricated resoundingly. This work could offer a feasibility reference of a simple way to construct a heterostructure electrocatalyst.

Highly efficient NiCo/VN electrocatalyst co-facilitated by interfacial engineering and support effect for large-current-density alkaline water/seawater hydrogen evolution reaction

Developing efficient and continuously stable water electrolysis catalysts to cope with harsh industrial conditions remains a huge challenge in the alkaline seawater electrolysis hydrogen production process. Transition metal nitrides are potential catalysts for seawater electrolysis, but they are still being modified to further improve catalytic performance. Here, a nanosheet-like NiCo/VN heterostructure electrocatalyst was prepared. The heterogeneous interface formed between and VN and NiCo alloy and the strong metal-support interaction regulate the electronic structure and optimizes the adsorption and desorption of intermediates. Moreover, the introduction of the NiCo alloy greatly facilitates the water dissociation step. Therefore, the prepared NiCo/VN catalyst exhibits excellent alkaline HER performance, with a low overpotential of 38 mV and 318 mV at a current density of 10 mA cm−2 and 1000 mA cm−2, shows high durability in 50 h of constant current tests at current densities of 10, 100, and 1000 mA cm−2 in alkaline seawater. This work proposes an effective strategy for preparing multiphase electrocatalysts, and the mechanism research fully confirms that it can promote the dissociation of water and the adsorption and desorption of intermediates.