Boron-doped diamond composites for durable oxygen evolution.

The urgent need to develop efficient, durable, and cost-effective oxygen evolution reaction (OER) catalysts for energy conversion and storage has prompted extensive research. Currently available commercial noble metal-based OER catalysts are expensive and exhibit limited long-term stability. In this study, boron-doped diamond composites (BDDCs) consisting of CoFe and CoFe2C nanoparticles supported by boron-doped diamond (BDD) particles have been prepared. The BDDC catalyst, prepared through a straightforward annealing process, exhibits exceptional durability (up to 72 h at 10 mA cm-2), a low overpotential (306 mV at 10 mA cm-2), and modest Tafel slope (58 mV dec-1). The coherent interfaces between CoFe/CoFe2C nanoparticles and the BDD substrate are essential for enhancing the OER performance. The fabrication method and composite structures presented in this study may facilitate the design and production of promising catalysts.

Preparation of cathode catalysts for efficient direct lignin fuel cells by nitrogen doping reduction of oxidized graphene with phthalocyanine iron and Kraft lignin.

Direct lignin fuel cells (DLFC) are one of the important forms of high value-added utilization of lignin. In this study, lignin was studied not only as a fuel but also as a catalyst. Specifically, Kraft lignin was modified with ZnCl2, KOH and THF (Tetrahydrofuran) respectively, and added to the catalyst after activation. The results of scanning electron microscope (SEM), transmission electron microscope (TEM), energy dispersive spectrometer (EDS), Brunauer - Emmett - Teller (BET), X-ray photoelectron spectroscopy (XPS), X-ray diffractometer (XRD), Fourier transform infrared spectroscopy (FT-IR) and Raman spectra shown that AL/FePc-NrGO (activated lignin/iron phthalocyanine/nitrogen-doped reduction of graphene oxide) three-dimensional composite catalyst has been synthesized. The results showed that KOH-activated Kraft lignin had the best performance as an oxygen reduction reaction (ORR) catalyst, with a half-wave potential (E1/2) of 0.73 V and a limiting diffusion current density of 4.3 mA cm-1. The THF-modified catalyst showed similar stability and methanol resistance to 20 % Pt/C at ORR. The ORR catalyst applied to the DLFC has the best electrical performance with an open circuit voltage (OCV) was 0.53 V and the maximum power density it could reach 95.29 mW m-2 when the catalyst was modified with THF. It is encouraging that the AL/FePc-NrGO catalyst has better-generated electricity performance than 20 % Pt/C. This work has provided a new idea for developing non-noble metal catalysts and studying direct biomass liquid fuel cells.

Rational Design of Diatomic Active Sites for Elucidating Oxygen Evolution Reaction Performance Trends.

Diatomic catalysts, especially those with heteronuclear active sites, have recently attracted significant attention for their advantages over single-atom catalysts in reactions with relatively high energy barrier, e.g. oxygen evolution reaction. Rational design and synthesis of heteronuclear diatomic catalysts are of immense significance but have so far been plagued by the lack of a definitive correlation between structure and catalytic properties. Here, we report macrocyclic precursor constrained strategy to fabricate series of transition metal (MT, Ni, Co, Fe, Mn, or Cu)-noble (MN, Ir or Ru) centers in carbon material. One notable performance trend is observed in the order of Cu-MN < Mn-MN < Fe-MN < MN < Co-MN < Ni-MN. However, the pathway has been not altered, still following the traditional adsorption reaction mechanism. The effect of the MT atoms on the performances could possibly originate from the distinct adsorption/desorption behaviors of key intermediates (i.e. *OH, *O and/or *OOH), strongly implying that ΔG*OOH-ΔG*OH could be used as the performance descriptor. We believe that our work provides useful strategy for synthesis of diatomic active sites with sole coordination configuration and varied composition, and in-depth insight to their catalytic mechanism, which could be used for further optimization of diatomic catalysts towards oxygen electrocatalysis.

Surface Optimization of Noble-Metal-Free Conductive [Mn1/4Co1/2Ni1/4]O2 Nanosheets for Boosting Their Efficacy as Hybridization Matrices.

Conductive 2D nanosheets have evoked tremendous scientific efforts because of their high efficiency as hybridization matrices for improving diverse functionalities of nanostructured materials. To address the problems posed by previously reported conductive nanosheets like poorly-interacting graphene and cost-ineffective RuO2 nanosheets, economically feasible noble-metal-free conductive [MnxCo1-2xNix]O2 oxide nanosheets are synthesized with outstanding interfacial interaction capability. The surface-optimized [Mn1/4Co1/2Ni1/4]O2 nanosheets outperformed RuO2/graphene nanosheets as hybridization matrices in exploring high-performance visible-light-active (λ >420 nm) photocatalysts. The most efficient g-C3N4-[Mn1/4Co1/2Ni1/4]O2 nanohybrid exhibited unusually high photocatalytic activity (NH4 + formation rate: 1.2 mmol g-1 h-1), i.e., one of the highest N2 reduction efficiencies. The outstanding hybridization effect of the defective [Mn1/4Co1/2Ni1/4]O2 nanosheets is attributed to the optimization of surface bonding character and electronic structure, allowing for improved interfacial coordination bonding with g-C3N4 at the defect sites. Results from spectroscopic measurements and theoretical calculations reveal that hybridization helps optimize the bandgap energy, and improves charge separation, N2 adsorptivity, and surface reactivity. The universality of the [Mn1/4Co1/2Ni1/4]O2 nanosheet as versatile hybridization matrices is corroborated by the improvement in the electrocatalytic activity of hybridized Co-Fe-LDH as well as the photocatalytic hydrogen production ability of hybridized CdS.

Visualization of Unconventional Rashba Bands and Vortex Zero Mode in the Topological Superconductor Candidate AuSn4.

The noble metal alloy AuSn4 has recently been identified as an intrinsic surface topological superconductor, promisingly hosting the Majorana zero mode (MZM) for topological quantum computing. However, the atomic visualization of its nontrivial surface states and MZM remains elusive. Here, we report the direct observation of unconventional surface states and vortex zero mode in AuSn4 by scanning tunneling microscopy/spectroscopy. Unlike the trivial metallic bulk states of Sn-terminated surfaces, the Au-terminated surfaces exhibit pronounced surface states near the Fermi level, arising from unconventional Rashba bands characterized by shared helical spin textures. In the superconducting state, the Sn-terminated surfaces exhibit conventional Caroli-de Gennes-Matricon bound states, while the Au-terminated surfaces display sharp zero-energy core states resembling MZMs in a nonquantum-limit condition. This distinction may result from the dominant contribution of unconventional Rashba bands on the Au-terminated surface. Our results provide a new platform for studying termination-dependent topological surface states and MZM in noble-metal-based superconductors.

Recent Progress on Covalent Organic Frameworks Supporting Metal Nanoparticles as Promising Materials for Nitrophenol Reduction.

With the utilization of nitrophenols in manufacturing various materials and the expansion of industry, nitrophenols have emerged as water pollutants that pose significant risks to both humans and the environment. Therefore, it is imperative to convert nitrophenols into aminophenols, which are less toxic. This conversion process is achieved through the use of noble metal nanoparticles, such as gold, silver, copper, and palladium. The primary challenge with noble metal nanoparticles lies in their accumulation and deactivation, leading to a decrease in catalyst activity. Covalent organic frameworks (COFs) are materials characterized by a crystalline structure, good stability, and high porosity with active sites. These properties make them ideal substrates for noble metal nanoparticles, enhancing catalytic activity. This overview explores various articles that focus on the synthesis of catalysts containing noble metal nanoparticles attached to COFs as substrates to reduce nitrophenols to aminophenols.

Non-noble metal catalysts for electrooxidation of 5-hydroxymethylfurfural.

2,5-Furandicarboxylic acid (FDCA) is a class of valuable biomass-based platform compounds. The creation of FDCA involves the catalytic oxidation of 5-hydroxymethylfurfural (HMF). As a novel catalytic method, electrocatalysis has been utilized in the 5-hydroxymethylfurfural oxidation reaction (HMFOR). Common noble metal catalysts show catalytic activity, which is limited by price and reaction conditions. Non-noble metal catalyst is known for its environmental friendliness, affordability and high efficiency. The development of energy efficient non-noble metal catalysts plays a crucial role in enhancing the HMFOR process. It can greatly upgrade the demand of industrial production, and has important research significance for electrocatalytic oxidation of HMF. In this paper, the reaction mechanism of HMF undergoes electrocatalytic oxidation to produce FDCA are elaborately summarized. There are two reaction pathways and two oxidation mechanisms of HMFOR discussed deeply. In addition, the speculation on the response of the electrode potential to HMFOR is presented in this paper. The main non-noble metal electrocatalysts currently used are classified and summarized by targeting metal element species. Finally, the paper focus on the mechanistic effects of non-noble metal catalysts in the reaction, and provide the present prospects and challenges in the electrocatalytic oxidation reaction of HMF.

SnO2@PdAg Core-Shell Nanoarchitecture Promotes Active and Stable Alcohol Electrooxidations.

Developing efficient Pd-based electrocatalysts is of vital importance for the application of direct alcohol fuel cells. Designing the core-shell architecture of Pd-based nanomaterials rationally has emerged as an effective strategy to promote the sluggish kinetics of anodic reactions. Herein, the PdAg alloy is reduced on a non-noble metal oxide surface for the formation of a core-shell nanostructure. The optimized SnO2@PdAgh nanospheres deliver the optimal catalytic performance compared with other counterparts and commercial Pd/C. The structural investigation reveals that the introduction of Ag and formation of a PdAg/SnO2 heterointerface effectively regulate the electronic structure of Pd, making SnO2@PdAgh a highly active catalyst for methanol and ethylene glycol oxidation reactions. Impressively, the strong interaction between the PdAg shell and SnO2 core stabilizes the metal-oxide heterointerface, contributing to the improved stability of SnO2@PdAgh in electrocatalytic reactions. This study proposes the use of non-noble metal oxides as the core to suppress the dissolution of the catalysts and highlights the rational design of core@shell nanoarchitectures.

Dual Plasmons with Bioinspired 3D Network Structure Enabling Ultrahigh Efficient Solar Steam Generation.

Plasmonic nanomaterials such as Au, Ag, and Cu are widely recognized for their strong light-matter interactions, making them promising photothermal materials for solar steam generation. However, their practical use in water evaporation is significantly limited by the trade-off between high costs and poor stability. In this regard, we introduce a novel, nonmetallic dual plasmonic TiN/MoO3-x composite. This composite features a three-dimensional, urchin-like biomimetic structure, with plasmonic TiN nanoparticles embedded within a network of plasmonic MoO3-x nanorods. As a solar absorber, the TiN/MoO3-x composite achieves a high evaporation rate of ∼2.05 kg m-2 h-1 with an energy efficiency up to 106.7% under 1 sun illumination, outperforming the state-of-the-art plasmonic systems. The high photothermal stability and unique dual plasmonic nanostructure of the TiN/MoO3-x composite are demonstrated by advanced in situ laser-heating transmission electron microscopy and photon-induced near-field electron microscopy/electron energy-loss spectroscopy, respectively. This work provides new inspiration for the design of plasmonic materials.

Hetero and Homo Metal Exchange of Au25(SR)18 - and Ag25(SR)18 - Clusters with Metal-Thiolate Complexes: Ab Initio Molecular Dynamics Simulation Studies.

The hetero and homo metal exchange of Au25(SR)18 - and Ag25(SR)18 - nanoclusters with metal-thiolate (M-SR) complexes (AuI(SR), AgI(SR), CuI(SR), and CuII(SR)2) are studied using ab initio molecular dynamics (AIMD) simulations. The AIMD simulation results unveil that the M-SR complexes directly displace Au(SR) or Ag(SR) units on the gold or silver core surface through an "anchoring effect". The whole process of metal-exchange reactions can be divided into three steps, including the adsorption of M-SR complexes on clusters, the formation of new staple motif, and the displacement of Au(SR) or Ag(SR) units by M-SR complexes. The key role of sulfur atoms in metal exchange reactions in M-SR complexes is revealed, which facilitates formation of new staple motifs and doping of M-SR complexes into gold and silver cores. This work provides a theoretical basis for further exploring the metal exchange reaction between noble metal nanoclusters and metal-thiolate complexes, as well as the isotope exchange reactions.

Toluene-Poisoning-Resistant High-Entropy Non-Noble Metal Anode for Direct One-Step Hydrogenation of Toluene to Methylcyclohexane.

The direct one-step hydrogenation of toluene to methylcyclohexane facilitated by a proton-exchange membrane water electrolyzer driven by renewable energy has garnered considerable attention for stable hydrogen storage and safe hydrogen transportation. However, a persistent challenge lies in the crossover of toluene from the cathode to the anode chamber, which deteriorates the anode and decreases its energy efficiency and lifetime. To address this challenge, the catalyst-poisoning mechanism is systematically investigated using IrO2 and high-entropic non-noble-metal alloys as anodes in acidic electrolytes saturated with toluene and toluene-oxidized derivatives, such as benzaldehyde, benzyl alcohol, and benzoic acid. Benzoic acid plays an important role in polymer-like carbon-film formation by blocking the catalytically active sites on the anode surface. Moreover, Nb and the highly entropic state on the surface of the multi-element alloy lower the adsorbing ability of toluene and prevent polymer-like carbon film formation. This study contributes to the design of catalyst-poisoning-resistant anodes for organic hydride technology, advanced fuel cells, and batteries.

Non-Noble-Metal-Based Electrocatalysts for Acidic Oxygen Evolution Reaction: Recent Progress, Challenges, and Perspectives.

The oxygen evolution reaction (OER) plays a pivotal role in diverse renewable energy storage and conversion technologies, including water electrolysis, electrochemical CO2 reduction, nitrogen fixation, and metal-air batteries. Among various water electrolysis techniques, proton exchange membrane (PEM)-based water electrolysis devices offer numerous advantages, including high current densities, exceptional chemical stability, excellent proton conductivity, and high-purity H2. Nevertheless, the prohibitive cost associated with Ir/Ru-based OER electrocatalysts poses a significant barrier to the broad-scale application of PEM-based water splitting. Consequently, it is crucial to advance the development of non-noble metal OER catalysis substance with high acid-activity and stability, thereby fostering their widespread integration into PEM water electrolyzers (PEMWEs). In this review, a comprehensive analysis of the acidic OER mechanism, encompassing the adsorbate evolution mechanism (AEM), lattice oxygen mechanism (LOM) and oxide path mechanism (OPM) is offered. Subsequently, a systematic summary of recently reported noble-metal-free catalysts including transition metal-based, carbon-based and other types of catalysts is provided. Additionally, a comprehensive compilation of in situ/operando characterization techniques is provided, serving as invaluable tools for furnishing experimental evidence to comprehend the catalytic mechanism. Finally, the present challenges and future research directions concerning precious-metal-free acidic OER are comprehensively summarized and discussed in this review.

Synergistic SERS enhancement of NiCo-LDHs microurchins and silver nanoparticles for ultra-sensitive and reusable detection of thiabendazole.

Two-dimensional layered semiconductor materials as a distinctive class of materials are comprehensively explored for widespread applications due to narrow bandgap, controllable morphology, and tunable metal cation composition. Herein, we constructed a sensing platform of surface enhanced Raman spectroscopy (SERS) by combination of nickel­cobalt layered double hydroxide (NiCo-LDH) microurchins and plasmonic silver nanoparticles (Ag NPs) for fungicide detection of thiabendazole (TBZ). The NiCo-LDHs/Ag-NPs microcomposites consist of NiCo-LDHs microurchins having a large number of nanoneedles deposited with photoreduced Ag NPs. The SERS platform with NiCo-LDHs/Ag-NPs shows an excellent SERS performance for TBZ detection, including an ultra-low detection limit of 1.49 × 10-11 M, a sublime enhancement factor of 1.71 × 109, high uniformity, good reproducibility, and long-term storage stability. The ultrahigh SERS activity of NiCo-LDH/Ag-NPs can be attributed to strong electromagnetic enhancement in the nanoscale gaps between Ag NPs, massive charge transfer through large-area NiCo-LDH/Ag-NPs interfaces, and the synergistic action of electromagnetic and charge transfer mechanisms. Besides, the unique morphology of NiCo-LDHs/Ag-NPs microcomposite provides a broad surface area for adsorption of TBZ molecules for further Raman signal enhancement. The practicability of the proposed SERS platform is confirmed by detecting TBZ in the real samples of apple juice and river water. The exceptional self-cleaning capability of the NiCo-LDHs/Ag-NPs microcomposite with an retention rate of 81.97 % even after the fifth degradation cycle underscores its impressive sustainable reusability and cost-effectiveness. The findings in this work lay the foundation for the development of high-performance SERS platforms to ensure food safety and environmental protection.

Advances in Noble Metal Electrocatalysts for Acidic Oxygen Evolution Reaction: Construction of Under-Coordinated Active Sites.

Renewable energy-driven proton exchange membrane water electrolyzer (PEMWE) attracts widespread attention as a zero-emission and sustainable technology. Oxygen evolution reaction (OER) catalysts with sluggish OER kinetics and rapid deactivation are major obstacles to the widespread commercialization of PEMWE. To date, although various advanced electrocatalysts have been reported to enhance acidic OER performance, Ru/Ir-based nanomaterials remain the most promising catalysts for PEMWE applications. Therefore, there is an urgent need to develop efficient, stable, and cost-effective Ru/Ir catalysts. Since the structure-performance relationship is one of the most important tools for studying the reaction mechanism and constructing the optimal catalytic system. In this review, the recent research progress from the construction of unsaturated sites to gain a deeper understanding of the reaction and deactivation mechanism of catalysts is summarized. First, a general understanding of OER reaction mechanism, catalyst dissolution mechanism, and active site structure is provided. Then, advances in the design and synthesis of advanced acidic OER catalysts are reviewed in terms of the classification of unsaturated active site design, i.e., alloy, core-shell, single-atom, and framework structures. Finally, challenges and perspectives are presented for the future development of OER catalysts and renewable energy technologies for hydrogen production.

Study on the Gas-Chromic Character of Pd/TiO2 for Fast Room-Temperature CO Detection.

As a widely used support, TiO2 has often been combined with Pd to form highly sensitive gas-chromic materials. Herein, we prepared a series of Pd/TiO2 catalysts with different Pd content (from 0.1 to 5 wt.%) by the impregnation method for their utilization in fast room-temperature CO detection. The detection was simply based on visible color change when the Pd/TiO2 was exposed to CO. The sample with 1 wt.% Pd/TiO2 presented an excellent CO gasochromic character, associated with a maximum chromatic aberration value of 90 before and after CO exposure. Systematic catalyst characterizations of XPS, FT-IR, CO-TPD, and N2 adsorption-desorption and density functional theory calculations for the CO adsorption and charge transfer over the Pd and PdO surfaces were further carried out. It was found that the interaction between CO and the Pd surface was strong, associated with a large adsorption energy of -1.99 eV and charge transfer of 0.196 e. The color change was caused by a reduction in Pd2+ to metallic Pd0 over the Pd/TiO2 surface after CO exposure.

Determination of the Localized Surface Plasmon Resonance Alteration of AgNPs via Multiwavelength Evanescent Scattering Microscopy for Pb(II) Detection.

We developed multiwavelength evanescent scattering microscopy (MWESM), which can acquire plasmonic nanoparticle images at the particle level using the evanescent field as the incident source and distinguish different LSPR (localized surface plasmon resonance) spectral peaks among four wavelengths. Our microscope could be easily and simply built by modifying a commercial total internal reflection fluorescence microscope (TIRFM) with the substitution of a beamsplitter and the addition of a semicircular stop. The ultrathin depth of illumination and rejection of the reflected incident source together contribute to the high sensitivity and contrast of single nanoparticle imaging. We first validated the capability of our imaging system in distinguishing plasmonic nanoparticles bearing different LSPR spectral peaks, and the results were consistent with the scattering spectra results of hyperspectral imaging. Moreover, we demonstrated high imaging quality from the aspects of the signal/noise ratio and point spread function of the single-particle images. Meaningfully, the system can be utilized in rapidly determining the concentration of toxic lead ions in environmental and biological samples with good linearity and sensitivity, based on single-particle evanescent scattering imaging through the detection of the alteration of the LSPR of silver nanoparticles. This system holds the potential to advance the field of nanoparticle imaging and foster the application of nanomaterials as sensors.

Recent advances of doping strategy for boosting the electrocatalytic performance of two-dimensional noble metal nanosheets.

Benefiting from the ultrahigh specific surface areas, massive exposed surface atoms, and highly tunable microstructures, the two-dimensional (2D) noble metal nanosheets (NSs) have presented promising performance for various electrocatalytic reactions. Nevertheless, the heteroatom doping strategy, and in particular, the electronic structure tuning mechanisms of the 2D noble metal catalysts (NMCs) yet remain ambiguous. Herein, we first review several effective strategies for modulating the electrocatalytic performance of 2D NMCs. Then, the electronic tuning effect of hetero-dopants for boosting the electrocatalytic properties of 2D NMCs is systematically discussed. Finally, we put forward current challenges in the field of 2D NMCs, and propose possible solutions, particularly from the perspective of the evolution of electron microscopy. This review attempts to establish an intrinsic correlation between the electronic structures and the catalytic properties, so as to provide a guideline for designing high-performance electrocatalysts.

Synergistic Active Heterostructure Design for Enhanced Two Electron Oxygen Reduction via Chemical and Electrochemical Reconstruction of Heterosulfides.

Transition metal sulfides, particularly heterostructures, represent a promising class of electrocatalysts for two electron oxygen reduction (2e- ORR), however, understanding the dynamic structural evolution of these catalysts during alkaline ORR remains relatively unexplored. Herein, NiS2/In2.77S4 heterostructure was synthesized as a precatalyst and through a series of comprehensive ex-situ and in-situ characterizations, including X-ray absorption spectroscopy, Raman spectroscopy, transient photo-induced voltage measurements, electron energy loss spectroscopy, and spherical aberration-corrected electron microscopy, it was revealed that nickel/indium (oxy)hydroxides (NiOOH/In(OH)3) could be evolved from the initial NiS2/In2.77S4 via both electrochemical and chemical-driven methods. The electrochemical-driven phase featured abundant bridging oxygen-deficient [NiO6]-[InO6] units at the interfaces of NiOOH/In(OH)3, facilitating a synergistic effect between active Ni and In sites, thus enabling an enhanced alkaline 2e- ORR capability than that of chemical-driven process. Remarkably, electrochemically induced NiOOH/In(OH)3 exhibited exceptional performance, achieving H2O2 selectivity of >90% across the wide potential window (up to 0.4 V) with a peak selectivity of >99%. Notably, within the flow cell, a current density exceeding 200 mA cm-2 was sustained for over 20 h, together with an impressive Faradaic efficiency of approximately 90% and a hydrogen peroxide production rate surpassing 4 mol g-1 h-1.

A Straightforward Solvent-Pair-Enabled Multicomponent Coassembly Approach toward Noble-Metal-Nanoparticle-Decorated Mesoporous Tungsten Oxide for Trace Ammonia Sensing.

The straightforward synthesis of noble-metal-nanoparticle-decorated ordered mesoporous transition metal oxides remains a great challenge due to the difficulty of balancing the interactions between precursors and templates. Herein, a solvent-pair-enabled multicomponent coassembly (SPEMC) strategy is developed for straightforward synthesis of noble-metal-nanoparticle-decorated nitrogen-doped ordered mesoporous tungsten oxide (abbreviated as NM/N-mWO3, NM = Pt, Rh, Pd). The amphiphilic poly(ethylene oxide)-block-polystyrene (PEO-b-PS) copolymers coassemble with ammonium metatungstate (AMT) clusters and different kinds of hydrophilic noble metal precursors without phase separation. SPEMC synthesis requires no direct interaction between PEO-b-PS and AMT, thus the assembly equilibriums between noble metal precursors and PEO-b-PS can be readily controlled. The obtained NM/N-mWO3 nanocomposites possess ordered mesopores, abundant oxygen vacancies, and metal-metal oxide interfaces. As a result, the Pt/N-mWO3 sensors exhibit superior ammonia sensing performances with high sensitivity, an ultralow limit of detection (51.2 ppb), good selectivity, and long-term stability. Spectroscopic analysis reveals that ammonia is oxidized stepwise to NO, NO2 -, and NO3 - during the sensing process. Moreover, a portable wireless module based on Pt/N-mWO3 sensor can recognize ppm-level concentration of ammonia, which lays a solid foundation for its application in various fields.

The cobalt-based metal organic frameworks array derived CoFeNi-layered double hydroxides anode and CoP/FeNi2P heterojunction cathode for ampere-level seawater overall splitting.

The seawater electrolysis technology powered by renewable energy is recognized as the promising "green hydrogen" production method to solve serious energy and environmental problems. The lack of low-cost and ampere-level current OER (oxygen evolution reaction) and HER (hydrogen evolution reaction) catalysis limits their industrial application. In this work, a unique tri-metal (Co/Fe/Ni) layered double hydroxide hollow array anode catalyst (CFN-LDH/NF) and the CoP/FeNi2P heterojunction hollow array cathode are successfully prepared via one in-situ growth of Co-MOF on nickel foam (Co-MOF/NF) precursor, which exhibits excellent catalytic performance. The η1000 values of 352 and 392 mV are achieved for CFN-LDH/NF (OER catalyst) in 1.0 M KOH and alkaline seawater solution, respectively. The CFNP/NF with a low overpotential of 281 mV is required to reach 1000 mA cm-2 current density for HER in 1.0 M KOH solution, while the η1000 in alkaline seawater solution is 312 mV. The CFN-LDH/NF||CFNP/NF electrolyzer exhibits excellent long-term durability over 100 h, achieving current density of 500 mA cm-2 at 1.825 V in 1.0 M KOH solution. The construction of hollow tri-metal LDH and phosphides heterostructures may open a new and relatively unexplored path for fabricating high performance seawater splitting catalysis.