Non-precious Metal Electrocatalysts Research Articles

Cerium-doped Nickel SulfideNanospheres as EfficientCatalysts for Overall Water Splitting.

The development of non-precious metal electrocatalysts with excellent activity and durability for electrochemical water splitting has always been a goal. Transition metal sulfides are attractive electrocatalysts for both hydrogen evolution reaction (HER) and oxygen evolution reaction(OER). In this article, we designed and constructed efficient catalysts with multiple synergistic interactions and synthesized Ce-NiS2@NFnanosphere using a solvothermal method. Ce-NiS2@NF exhibits excellent HER performance, OER performance, and overall water splitting capability in alkaline electrolytes, demonstrating good stability. The addition of Ce influences the activity of the catalysts, attributed to the synergistic interactions creating more active sites and higher intrinsic activity through the introduction of Ce heteroatoms. Additionally, the self-supported conductive substrate promotes electron transfer, enhancing the intrinsic activity and active site density of the catalyst.This study provides an in-depth investigation into structural design and performance enhancement, offering ideas for designing efficient catalysts for overall water electrolysis. This work provides an in-depth study in terms of structural design performance enhancement and provides ideas for designing efficient alkaline bifunctional catalysts. Valuable insights have been provided in elucidating the intrinsic mechanism of the catalytic activity of cerium-doped nickel sulfidenanospheres,thus providing new guidance in the field of energy conversion technology.

Development of Ternary Layered Double Hydroxide Oxygen Evolution Reaction Electrocatalyst for Anion Exchange Membrane Water Electrolysis

To achieve net zero emissions, green hydrogen should be produced via water electrolysis with renewable energy. To develop efficient anion exchange membrane water electrolyzers (AEMWE), the development of efficient and stable non-precious metal electrocatalysts for the oxygen evolution reaction (OER) is essential. In this study, a high-performance ternary NiFeCo-layer double hydroxide (LDH) electrocatalyst for AEMWE was easily developed by the co-precipitation method. The introduction of Co has been shown to have an effect on the electronic structure of Ni and Fe, improving their intrinsic OER properties. In addition, the three-dimensional flower-like nanosheet morphology improved mass transfer and achieved excellent current density at high voltages. The ternary NiFeCo-LDH electrocatalyst requires low overpotentials (253 mV at 10 mA cm<sup>-2</sup>) and Tafel slope (45 mV dec<sup>-1</sup>) in 1 M KOH. AEMWE using the ternary NiFeCo-LDH electrocatalyst showed excellent electrolysis performance with a high current density of 2.27 A cm<sup>-2</sup> at 1.8 V cell. Moreover, an energy conversion efficiency of 86.73 % was achieved during the durability test for 100 hours at a current density of 0.5 A cm<sup>-2</sup>. The performance of the AEMWE electrolyzer utilizing the ternary NiFeCo-LDH electrocatalyst surpassed that of previously reported AEMWE electrolyzers. This work reports a highly active OER electrocatalyst that could open numerous opportunities for the development of ternary LDH electrocatalysts in AEMWE.

Construction of Co-Se-W at Interfaces of Phase-Mixed Cobalt Selenide via Spontaneous Phase Transition for Platinum-Like Hydrogen Evolution Activity and Long-Term Durability in Alkaline and Acidic Media.

Cost-effective transition metal chalcogenides are highly promising electrocatalysts for both alkaline and acidic hydrogen evolution reactions (HER). However, unsatisfactory HER kinetics and stability have severely hindered their applications in industrial water electrolysis. Herein, a nanoflowers-shaped W-doped cubic/orthorhombic phase-mixed CoSe2 catalyst ((c/o)-CoSe2-W) is reported. The W doping induces spontaneous phase transition from stable phase cubic CoSe2 (c-CoSe2) to metastable phase orthorhombic CoSe2, which not only enables precise regulation of the ratio of two phases but also realizes W doping at the interfaces of two phases. The (c/o)-CoSe2-W catalyst exhibits a Pt-like HER activity in both alkaline and acidic media, with record-low HER overpotentials of 29.8mV (alkaline) and 35.9mV (acidic) at 10mAcm-2, respectively, surpassing the vast majority of previously reported non-precious metal electrocatalysts for both alkaline and acidic HER. The Pt-like HER activities originate from the formation of Co-Se-W active species on the c-CoSe2 side at the phase interface, which effectively modulates electron structures of active sites, not only enhancing H2O adsorption and dissociation at Co sites but also optimizing H* adsorption to ΔGH*≈0 at W sites. Benefiting from the abundant phase interfaces, the catalyst also displays outstanding long-term durability in both acidic and alkaline media.

Unveiling the CoFe LDH generated by partial in situ conversion strategy: Synergistic effect of modified MXene and cationic vacancies for overall water splitting

It remains a challenge to utilize non-precious metal electrocatalysts to increase intrinsic activity and observe more active sites. Herein, we propose a simple partial in situ transformation strategy to form a novel MOF@CoFe LDH heterostructure by Co-MOF template-directed fabrication using modified MXene as substrate, and introduce metal cation vacancy defects on the as-prepared LDH surface to further enhance the performance of the catalysts. Density-functional theory calculations show that the electron transfer rate of a material can be tuned by modulating the electron diffusion phenomenon, thereby lowering the energy barrier of the catalytic reaction. Consistent with the expected results, the catalysts also showed excellent electrochemical performance with HER and OER reaching current densities of 10 mA cm−2 with overpotentials of only 201 mV and 197 mV, and Faraday efficiencies (FE) close to 100 %. Meanwhile, a cell overpotential of only 1.56 V is required to effectively drive a current density of 10 mA cm−2 in the two-electrode system, and the superior long-term stability of the material reveals its potential for cost reduction in large-scale industrial applications.

ZIF-8 derived iron-, sulphur-, and nitrogen-doped catalysts for anion-exchange membrane fuel cell application

This study presents the preparation of tridoped Fe, N, S carbon-based catalysts using ZIF-8 as the main carbon source and iron(II)acetate, 1,10-phenanthroline, ammonia gas and thiourea as precursors for Fe, N and S elements. Thiourea was mixed via planetary ball-milling with a Fe–N–C catalyst prepared by inert gas pyrolysis, and different pyrolysis conditions were applied thereafter. The main goal of the work is to synthesise active non-precious metal electrocatalysts for oxygen reduction reaction (ORR). High electrocatalytic ORR activity in alkaline media was observed for the two materials obtained after thiourea addition and subsequent pyrolysis. Physico-chemical characterisation revealed successful S- and N-doping for all three catalysts with enhanced porosity for the two materials that were subjected to additional pyrolysis after the thiourea addition. The sulphur doping was highest for the FeNSC3 material that was subjected to a second pyrolysis in N2 and a third pyrolysis in NH3, compared to the FeNSC2 material that was subjected to a single pyrolysis in NH3 flow after thiourea addition. The ORR activity of FeNSC2 with half-wave potential of 0.88 V was slightly higher than that of FeNSC3, and the former was selected for evaluation as a cathode catalyst in an anion-exchange membrane fuel cell.

Construction of Heterostructured NiS/NiSe2 and their application in electrocatalytic water splitting

Development of non-precious metal electrocatalyst that can efficiently catalyze the oxygen evolution reaction (OER) and the hydrogen evolution reaction (HER) simultaneously, is a great challenge. Herein, density functional theory (DFT) calculations are first conducted to explore the beneficial effect of NiSe2/NiS heterostructure on OER. Based on this, a series of nickel selenosulfides constructed by different amounts of NiS and NiSe2 are synthesized. Results indicate that Ni4–Se2–S2 with the NiS to NiSe2 ratio of 5.82/2.47 displays outstanding electrocatalytic activity for OER/HER, with overpotentials of 228 mV and 155 mV at 10 mA cm−2, respectively. Moreover, a two-electrode electrolyzer using Ni4–Se2–S2 as the anode and cathode exhibits a lower voltage than RuO2||Pt/C. Moderate ratio of NiS to NiSe2 achieves a balance between conductivity and surface area, which endows Ni4–Se2–S2 the best catalytic performances. Our results pave a way for the optimization of heterostructured catalysts.

Aqueous pH influence on the electrocatalytic hydrogen evolution reaction with carbon nanotube-supported diiron dithiolato compound

Biomimetic chemistry on structure, function and external environment of [FeFe]-hydrogenases for hydrogen evolution reaction (HER) has shown a promising way to develop non-precious metal electrocatalysts for H2 production in the current Pt-dominated HER system. Herein, three new diiron dithiolato compounds [{(μ-SCH2)2N(C6H4CH2CO2R)}Fe2(CO)6] (R = H (1), C6H4CHO-p (2), and C6H4Me-m (3)) were first prepared and identified as a library of [FeFe]-hydrogenase models in this work. Subsequently, the as-prepared diiron molecule 2 can be covalently attached onto carbon nanotubes (CNTs), resulting in the obtainment of target CNT-supported [FeFe]-hydrogenase model labeling as covalent hybrid 2Fe2S-f-CNT. Notably, the electrocatalytic HER performance and stability of the resulted hybrid 2Fe2S-f-CNT immobilized respectively on a gassy carbon (GC) electrode are systematically studied and compared in 0.1 M KOH (pH = 13), 0.1 M phosphate buffer (pH = 7), and 0.05 M H2SO4 (pH = 1) aqueous solutions by various spectroscopic and electrochemical techniques. The result has shown that the higher electrocatalytic HER activity is observed in alkaline solution (pH = 13) relative to neutral and acidic solutions (pH = 7, 1), being attributed to the different electrochemical HER processes of diiron cluster in wide pH aqueous media as revealed by post operando analysis.

Recent Advancements on Spin Engineering Strategies for Highly Efficient Electrocatalytic Oxygen Evolution Reactions.

Oxygen evolution reaction (OER) is a widely employed half-electrode reaction in oxygen electrochemistry, in applications such as hydrogen evolution, carbon dioxide reduction, ammonia synthesis, and electrocatalytic hydrogenation. Unfortunately, its slow kinetics limits the commercialization of such applications. It is therefore highly imperative to develop highly robust electrocatalysts with high activity, long-term durability, and low noble-metal contents. Previously intensive efforts have been made to introduce the advancements on developing non-precious transition metal electrocatalysts and their OER mechanisms. Electronic structure tuning is one of the most effective and interesting ways to boost OER activity and spin angular momentum is an intrinsic property of the electron. Therefore, modulation on the spin states and the magnetic properties of the electrocatalyst enables the changes on energy associated with interacting electron clouds with radical absorbance, affecting the OER activity and stability. Given that few review efforts have been made on this topic, in this review, the-state-of-the-art research progress on spin-dependent effects in OER will be briefed. Spin engineering strategies, such as strain, crystal surface engineering, crystal doping, etc., will be introduced. The related mechanism for spin manipulation to boost OER activity will also be discussed. Finally, the challenges and prospects for the development of spin catalysis are presented. This review aims to highlight the significance of spin engineering in breaking the bottleneck of electrocatalysis and promoting the practical application of high-efficiency electrocatalysts.

Regulation of electron density redistribution for efficient alkaline hydrogen evolution reaction and overall water splitting

The rational design of morphology and heterogeneous interfaces for non-precious metal electrocatalysts is crucial in electrochemical water decomposition. In this paper, a bifunctional electrocatalyst (Ni/NiFe LDH), which coupling nickel with nickel–iron layer double hydroxide (NiFe LDH), is synthesized on carbon cloth. At current density of 10 mA cm−2, the Ni/NiFe LDH exhibits a low hydrogen evolution reaction (HER) overpotential of only 36 mV due to the accelerated electrolyte penetration, which is caused by superhydrophilic interface. Moreover, an alkaline electrolyzer is formed and provide a current density of 10 mA cm−2 with a voltage of only 1.49 V. It is confirmed by the density functional theory (DFT) that electron from the Ni layer is transferred to NiFe LDH layer, redistributing the local electron density around the heterogeneous phase interface. Thus, the Gibbs free energy for hydrogen adsorption is optimized. This work provides a promising strategy for the rational regulation of electrons at heterogeneous interfaces and the synthesis of flexible electrocatalysts.

Low-temperature plasma-assisted synthesis of iron and nitrogen co-doped CoFeP-N nanowires for high-efficiency electrocatalytic water splitting

Designing efficient, stable, and low-cost non-precious metal electrocatalysts is critical for gainful utilization of renewable resources and effective water splitting. The catalytic efficiency is determined by interactions between the multiple main constituent elements and dopants. However, achieving performance-boosting synergistic interactions between different species in the catalyst is challenging. This work demonstrates such effect using low-temperature plasma-enhanced hydrothermal-phosphorization synthesis of Fe, N co-doped CoFeP-N nanowires. Nickel foam was utilized as the substrate to prepare CoFe-LDH precursor by hydrothermal method and CoFeP nanoparticles were obtained by phosphorization in a tube furnace. The N element was further doped into CoFeP using a low-temperature plasma discharge. The produced CoFeP-N nanowires exhibit far superior hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) activities in an alkaline medium compared to the original CoP due to the incorporation of Fe and N elements, with overpotentials of 64 mV and 219 mV at 10 mA cm−2 respectively, and excellent cycling stability. When CoFeP-N is used as both the cathode and anode of a two-electrode water splitting device, low voltages of only 1.516 V and 1.636 V were needed to achieve current density of 10 mA cm−2 and100 mA cm−2 respectively, which are better than that of Pt/C||RuO2 and most non-precious metal-based electrocatalysts reported to date. These experimental results provide new insights and strategies for developing efficient, stable, and low-cost bifunctional water splitting electrocatalysts.

Layered double hydroxides derived prussian blue analogue nanocage confining NiCoP nanoparticles as efficient bifunctional electrocatalyst

Designing novel electrocatalysts with excellent catalytic activity for efficient water splitting is necessary to achieve the large-scale H2/O2 production from renewable resources. In this study, a facile hydrothermal method followed by low-temperature phosphorylation treatment was employed to fabricate a nanocage of prussian blue analogue encapsulating NiCoP nanoparticles (NiCoP@PBA), which was derived from the layered double hydroxide precursor. As a bifunctional non-precious metal electrocatalyst, NiCoP@PBA demonstrates superior performance in KOH electrolyte water splitting, with overpotentials of 59 mV for electrocatalytic hydrogen evolution reaction (HER) and 263 mV for oxygen evolution reaction (OER) at 10 mA cm−2. The catalyst also exhibits low Tafel slopes of 54 mV dec−1 for HER and 120 mV dec−1 for OER, reflecting efficient charge transfer kinetics. DFT simulations show that the Co–N moieties at the heterogeneous interface of NiCoP@PBA can optimize the surface electron distribution and energy states, thus facilitating efficient electron-hole pair separation, significantly enhancing catalytic activity for both HER and OER process, and significantly extending the electrocatalyst's service life. Our approach can be extended to more non-precious metal electrocatalysts, which is significant for the design of efficient bifunctional water splitting electrocatalysts.

Nanosheets-assembled hollow N-doped carbon nanospheres encapsulated with ultrasmall NiSe nanoparticles for electrocatalytic hydrogen evolution

Developing highly active and stably non-precious metal electrocatalysts for hydrogen production in alkaline conditions is of paramount importance to hydrogen economy. Herein, nanosheet-assembled hollow nitrogen-doped carbon nanospheres confined with ultrasmall NiSe nanoparticles (NiSe@NC) are synthesized by employing a SiO2 template-assisted approach. As expected, the as-prepared NiSe@NC electrocatalyst delivers an overpotential of 169 mV at the current density of 10 mA/cm2 without iR-correction, and sustains at least 80 h for continuous operation, far outperforming the NiSe-p catalyst in 1 M KOH medium toward hydrogen evolution reaction (HER). The appealing HER performance is mainly ascribed to the synergy effect between hollow nitrogen-doped carbon and highly active NiSe nanoparticles, which improves catalytically active sites, expedites electron transfer rate and optimizes the electronic structure of NiSe@NC nanomaterial. More strikingly, this study presents the feasible insights for constructing robust cost-effective electrocatalysts towards efficient HER in harsh alkaline media.

Enzymolytic lignin derived Fe–N codoped porous carbon materials as catalysts for oxygen reduction reactions

Numerous active sites and hierarchical pore structures are important for improving catalytic performance for the oxygen reduction reaction (ORR). In this work, a series of iron-nitrogen-doped porous carbon materials (Fe–N–C) with ORR catalytic activity were prepared by a one-step pyrolysis method using enzymolytic lignin as the raw material, soy protein isolate and iron chloride as dopants. The results showed that the samples with the best performance have abundant Fe-Nx active sites and mesoporous structures. At the same time, the electrocatalytic results indicate that the half-wave potential of catalyst was 0.84 V, which reached 96.55% of commercial Pt/C catalysts (E1/2 = 0.86 V), it still preserves an initial current density of 92%, after 10,000 s of circulation, which is much better than Pt/C (86%). Due to the low cost, high activity and stable ORR property, the prepared non-precious metal electrocatalyst will play an important role in the applications of fuel cells.

Highly active and durable NiCoP electrocatalyst through Ga ion intercalation strategy for long-lasting water electrolysis

Developing non-precious catalysts with optimal catalytic performance is very crucial for sustainable energy-related systems. However, the sluggish kinetics and low efficiency limits their practical applications. Herein, we report several Ga intercalated NiCoP nanoneedle (Ga-NiCoP) catalysts. It indicates that the introduction of Ga ions increases the exposed active sites and accelerates the species reconstruction. The prepared catalyst drives HER with an overpotential of 348 mV at 500 mA cm−2 and 270 mV at 100 mA cm−2 for OER. Meanwhile, it achieves a cell voltage of 1.47 V at current density 10 mA cm−2 in a two-electrode system and maintains stability for 150 h. This work provides a general approach to fabricate some other non-precious metal electrocatalysts to produce hydrogen.

Synthesis of NbC@C(Nx) nanoparticles using DC arc discharge plasma for highly efficient oxygen reduction reaction

Development of the low-cost, high-efficiency, and durable non-precious metal electrocatalysts for cathodic oxygen reduction reaction (ORR) is of vital importance for fuel cells and metal-air batteries. Herein, the carbon-coated NbC nanoparticles (NbC@C NPs) were prepared using DC arc discharge plasma under a methane atmosphere. Then, the nitrogen-doping was conducted by heat treatment, resulting in nitrogen-doped carbon-coated NbC nanoparticles (NbC@C(Nx) NPs). Benefiting from the merit of unique core-shell structure and best synergy between the nitrogen-doped carbon shell and the NbC core, the obtained highest nitrogen-doped NbC@C(N1.36) NPs showed an onset potential (Eonset) of 0.89 V (vs. RHE) and a half-wave potential (E1/2) of 0.79 V, which are comparable to those of commercial Pt/C (20 wt%) (Eonset = 0.90 V, E1/2 = 0.80 V), and its diffusion-limited current density (JL) of 5.99 mA·cm−2 is even higher than that of commercial Pt/C (5.43 mA·cm−2). Moreover, it exhibited a remarkable long-term durability and impressive methanol resistance than Pt/C catalyst. In addition, the real-time optical emission spectrum (OES) analysis of arc plasma shows that the electron temperature (Te) is 7562.9 K in local thermal equilibrium (LTE) plasma. Therefore, the use of the DC arc discharge plasma method opens a fast and simple way to develop cost-effective and highly efficient non-precious metal catalysts for ORR.

Controlled synthesis of self-supportive hydrangea shaped Ni based hydroxide/phosphide for efficient overall water splitting and full pH hydrogen evolution

The exploration of efficient, robust and nonprecious transition metal electrocatalysts for electrochemical hydrolysis is urgently needed. Herein, we developed Ni(OH)2 with 3D nanoflower structure on the titanium mesh by a simple electrodeposition method. The Ni(OH)2/Ti exhibited excellent oxygen evolution reaction performance and achieved 10 mA cm−2 at 190 mV with fast kinetics in alkaline conditions. Ni2P, NiS2 and NiSe2 were prepared by solid-phase reaction, and the 3D nanoflower increased the open structure and greatly enhanced catalytic activity. The Ni2P/Ti electrode required an overpotential of 52, 88 and 109 mV to reach 10 mA cm−2 for hydrogen evolution reaction in acidic, alkaline and neutral media, respectively. The results of electrochemical measurements and mechanistic studies showed that the catalytic activity of HER: Ni2P > NiS2 > NiSe2 > Ni(OH)2. The Ni2P/Ti and Ni(OH)2/Ti electrodes were assembled into an integrated water splitting electrolytic cell. The water electrolysis device assembled with the Ni2P/Ti and Ni(OH)2/Ti electrodes only needed a low potential of 1.608 V to achieve 50 mA cm−2 in alkaline environment and was operated stably for 50 h.

FeNi3 nanosheets with multiple defects induced by H+-ion irradiation show enhanced electrocatalytic action during the oxygen evolution reaction

The oxygen evolution reaction (OER) is vital in electrocatalytic water-splitting. However, efficient non-precious metal electrocatalysts are required to improve the reaction efficiency. Therefore, this study aims to increase the OER activity of FeNi3 nanosheets using high-energy H+-ion irradiation to create multiple defects. The optimized sample (FeNi3-16) achieves a lower overpotential of 260 mV at a current density of 10 mA cm−2 than its pristine counterpart (FeNi3, 320 mV). Density functional theory (DFT) calculations show that the multiple defects in Fe and Ni can synergistically reduce the d-band centres of the Fe and Ni sites, which improves the electron transfer efficiency during the OER. This ion-irradiation technique may be applied to other electrocatalysts for various energy device.

Simple synthesis of peanut shell-like MoCoFe-HO@CoMo-LDH for efficient alkaline oxygen evolution reaction

Due to the depletion of fossil energy on earth, it is crucial to develop resource rich and efficient non-precious metal electrocatalysts for oxygen evolution reaction (OER). Herein, we synthesized an efficient and economical electrocatalyst using a simple self-assembly strategy. Firstly, rod-shaped MIL-88A was synthesized by hydrothermal method. Then, the surface of MIL-88A was functionalized and encapsulated in zeolitic imidazolate framework-67 (ZIF-67) by hydrothermal method. The combination of MIL-88A and ZIF-67 resulted in a slight ion-exchange reaction between Co2+ and the surface of MIL-88A to generate CoFe-LDH@ZIF-67 core–shell structure. Afterwards, in the presence of Mo6+, ZIF-67 was converted into CoMo-nanocages through ion-exchange reactions, forming a core–shell structure of MoCoFe hydr (oxy) oxide@CoMo-LDH (MoCoFe-HO@CoMo-LDH). Due to the advantages of core–shell structure and composition, this material exhibits excellent OER characteristics, with a small Tafel slope (45.11 mV dec-1) and low overpotential (324 mV) at 10 mA cm−2. It exhibits good stability in alkaline media. This research work provides a novel approach for the development of efficient and economical non-precious metal electrocatalysts.

Porphyrin-based frameworks and derivatives for the oxygen reduction reaction

The global energy crisis and environmental pollution issues caused by the continuous consumption of fossil fuels are increasingly becoming severe. Developing clean and sustainable hydrogen (H2) energy and corresponding storage and conversion devices have attracted increasing attention. The utilization of H2 energy highly depends on the fuel cell (FC). However, the slow kinetics of oxygen reduction reaction (ORR) on the cathode of FC cannot be improved without efficient catalysts. Currently, precious metal platinum (Pt) and its alloys are commonly used catalysts for ORR process. However, the scarcity and high cost of Pt hinder their large-scale practical application. To replace typical Pt-based catalysts, non-precious metal electrocatalysts have been investigated for ORR. Inspired by the catalytic ORR active center Fe porphyrin of cytochrome c oxidase in nature, metalloporphyrin-based frameworks and their derivatives have become promising electrocatalysts due to their abundant conjugated electronic structure, tunable functional groups, and large specific surface area. First, this review briefly introduces porphyrins and catalytic ORR mechanisms. Second, recent progress on porphyrin-based ORR catalysts including porphyrin-based frameworks, framework@substrate composites, and framework-based derivatives was summarized. Porphyrin-based frameworks mainly include metal-organic frameworks (MOFs), covalent organic frameworks (COFs), hydrogen-bonded organic frameworks (HOFs), and polymers constructed with porphyrin building blocks. Porphyrin-based framework@substrate composites were usually assembled and constructed to improve the electron transfer rate of frameworks. To further improve the conductivity, framework-based derivatives, usually named metal, nitrogen-doped carbon (M-N-C) materials, were synthesized through pyrolyzing frameworks at high temperatures. Finally, research challenges and directions of porphyrin-based electrocatalysts for ORR were discussed. This review is meaningful and enlightening for designing and developing other porphyrin-based electrocatalysts for ORR.

Strongly Coupled Heterostructured CoP/MoO2 as an Advanced Electrocatalyst for Urea-Assisted Water Electrolysis.

Developing low-cost electrocatalysts with excellent activity and durability in urea-assisted water splitting is urgently needed in order to achieve sustainable hydrogen production. Herein, we in situ synthesized a robust coupled heterostructured electrocatalyst (CoP/MoO2) on a nickel foam (NF) substrate and explored its electrocatalytic performances in the hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and urea oxidation reaction (UOR). The overpotential of CoP/MoO2/NF is found to be only 11 mV at 10 mA cm-2 during the HER process, which is significantly lower than that of commercial Pt/C. Meanwhile, the UOR catalytic performance of CoP/MoO2/NF indicates fast reaction kinetics, along with a considerable low driving potential (1.26 V) compared to that of the OER (1.51 V). In situ and ex situ techniques demonstrate that these excellent electrocatalytic properties are mainly ascribed to the effective synergistic coupled effect and strong electronic interactions between single-component CoP and MoO2, which can tune electronic states of Co and Mo, expose more active sites, enhance intrinsic catalytic activity, and accelerate charge transfer. Moreover, when used in electrochemical overall water splitting and urea-assisted water electrolysis, CoP/MoO2/NF can reach a current density of 10 mA cm-2 at only 1.46 and 1.32 V. This outperforms Pt/C||RuO2 and numerous nonprecious metal electrocatalysts and maintains a stable long-term electrolytic operation for 84 h. This work provides a promising pathway for the development of efficient catalysts during urea-assisted water electrolysis for hydrogen production.