CoFe-layered Double Hydroxide Research Articles

Reactive layered hydroxide membrane for advanced water treatment: Micropollutant degradation and antifouling potential

The effective removal of micropollutants by water treatment technologies remains a significant challenge. Herein, we develop a CoFe layered double hydroxide (CoFeLDH) catalytic membrane for peroxymonosulfate (PMS) activation to achieve efficient micropollutant removal with improved mass transfer rate and reaction kinetics. This study found that the CoFeLDH membrane/PMS system achieved an impressive above 98% degradation of the probe chemical ranitidine at 0.1 mM of PMS including five more micropollutants (Sulfamethoxazole, Ciprofloxacin, Carbamazepine, Acetaminophen and Bisphenol A) at satisfactory level (above 80%). Moreover, significant improvements in water flux and antifouling properties were observed, marking the membrane as a specific advancement in the removal of membrane fouling in water purification technology. The membrane demonstrated consistent degradation efficiency for several micropollutants and across a range of pH (4–9) as well as different anionic environments, thereby showing it suitability for scale-up application. The key role of reactive species such as SO4•–, and O2• − radicals in the degradation process was elucidated. This is followed by the confirmation of the occurrence of redox cycling between Co and Fe, and the presence of CoOH+ that promotes PMS activation. Over the ten cycles, the membrane could be operated with a flux recovery of up to 99.8% and maintained efficient performance over 24 h continuous operation. Finally, the efficiency in degrading micropollutants, coupled with reduced metal leaching, makes the CoFeLDH membrane as a promising technology for application in water treatment.

Degradation of Tetracycline through peroxymonosulfate activation with Co/Fe-LDH modified magnetic hydrochar: Synergistic effect and low toxicity

In this work, 2LDH-CoFe2O4@BHC catalyst was prepared by modifying magnetic corncob-based hydrochar (CoFe2O4@BHC) with Co/Fe layered double hydroxide (Co/Fe-LDH), which was used to activate peroxymonosulfate (PMS) for tetracycline (TC) degradation. 2LDH-CoFe2O4@BHC demonstrated effective activation of PMS and rapid removal of TC (100 %) within 10 min by leveraging structural modulation and synergistic interactions among multiple components. In contrast, BHC (26.02 %), CoFe2O4 (59.25 %), and CoFe2O4@BHC (61.88 %) presented poor removal efficiency. Furthermore, it was shown that both the free radicals (SO4•-) and non-free radicals (1O2) were essential in the degradation process, and the catalytic mechanism was revealed to be a synergistic process with the characterization results from in-situ Raman, electrochemical characterization, and X-ray photoelectron spectroscopy (XPS). The catalytic performance of 2LDH-CoFe2O4@BHC was also evaluated using a self-developed fixed-bed reactor, demonstrating its strong stability and resistance to interference during long-term operation. The potential degradation pathway of TC in the 2LDH-CoFe2O4@BHC + PMS system was suggested based on the quadrupole time-of-flight mass spectrometry (QTOF/MS) findings. It was found that the toxicity of the intermediates produced by TC degradation significantly reduced. This study presented an insight for the decomposition of organic pollutants by synthetic biochar-loaded catalysts.

Cellulose-based Co[sbnd]Fe LDH composite as a nano-adsorbent for sulfamethoxazole and cefixime residues: Evaluation of performance, green metrics and cytotoxicity

The increase in antibiotic residues poses a serious threat to ecological and aquatic environments, necessitating the development of cost-effective, convenient, and recyclable adsorbents. In our study, we used cellulose-based layered double hydroxide (LDH) as an efficient adsorbent and nanocarrier for both sulfamethoxazole (SMX) and cefixime (CFX) residues due to their biodegradability and biocompatibility. Chemical processes are measured according to green chemistry metrics to identify which features adhere to the principles. A GREEnness Assessment (ESA), Analytical GREEnness Preparation (AGREEprep), and Analytical Eco-Scale Assessments (ESA) were used to assess the suitability of the proposed analytical method. We extensively analyzed the synthesized CoFe LDH/cellulose before and after the adsorption processes using XRD, FTIR, and SEM. We investigated the factors affecting the adsorption process, such as pH, adsorbent dose, concentrations of SMX and CFX and time. We studied six nonlinear adsorption isotherm models at pH 5 using CoFe LDH, which showed maximum adsorption capacities (qmax) of 272.13 mg/g for SMX and 208.00 mg/g for CFX. Kinetic studies were also conducted. The 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl-2H-tetrazolium bromide (MTT) assay was performed on Vero cells in direct contact with LDH nanocomposites to evaluate the cytotoxicity and side effects of cellulose-based CoFe LDH. The cellulose-based CoFe LDH nanocomposite demonstrated excellent cytocompatibility and less cytotoxic effects on the tested cell line. These results validate the potential use of these unique LDH-based cellulose cytocompatible biomaterials for water treatment applications. The cost of the prepared adsorbents was investigated.

Efficient bimetallic activation of sulfite by CoFe-LDH for bisphenol A removal: Critical role of Co/Fe ratio on ROS generation

The sulfite (S(IV))-based advanced oxidation process is an emerging approach for the treatment of phenolic pollution. In this study, CoFe-layered double hydroxides (CoFe-LDHs), showing superior physicochemical properties as catalysts, were applied to activate S(IV) for bisphenol A (BPA) degradation. The results show that the Co/Fe molar ratios play a crucial role in regulating the physicochemical properties, degradation capacity, and activation mechanism of the catalysts, with Co3Fe1-LDH exhibiting the best performance in BPA degradation. The degradation of BPA is significantly influenced by pH and dissolved oxygen, and proceeds through bimetallic synergism and both radical and non-radical pathways. However, with increasing Co/Fe ratio, SO4•− gradually assumes a more prominent role in degradation by the system, and the contributions from high-valent metals and HO• gradually diminish. Additionally, the system brought about a substantial reduction in toxicity after degradation, and the catalyst demonstrated promise in consecutive recycling experiments, the degradation of other organics, and tests in actual water bodies.

Understanding highly active and durable Fe-decorated Co(OH)2 catalysts in alkaline oxygen evolution reaction by in situ XANES studies

The activation and degradation mechanisms of CoFe layered double hydroxide (CoFe-LDH) and Fe-decorated Co(OH)2 (Fe-Co(OH)2) have been investigated using in situ X-ray absorption spectroscopy coupled with cyclic voltammetry (CV) in 0–0.9 V (vs Hg/HgO). A series of CoFe-LDH samples have been prepared by co-electrodeposition with varying Co/Fe ratios. Fe-decorating on Co(OH)2 has been applied using 10 ppm of Fe in 1.0 M KOH. Electrochemical impedance spectroscopy (EIS) and CV cycles confirm the degradation of Co(OH)2 and CoFe-LDH due to the irreversible redox of Co(OH)2/CoOOH, and Fe extraction. In contrast, Fe-decorated Co(OH)2 shows high activity and stability in the OER. In situ XANES analysis suggests that the Fe-decorating allows the Co(OH)2 to remain as γ-CoOOH even under potential fluctuations.

Application of cobalt-cerium-iron ternary layered double hydroxide for extraction of perfluorooctane sulfonate followed by HPLC-MS/MS analysis

Herein, Ce-doped CoFe layered double hydroxide (LDH), noted as CoCeFe ternary LDH, was prepared using the co-precipitation route. Prosperous synthesis of CoFe LDH and successful partial replacement of iron cations with cerium cations in CoCeFe ternary LDH were confirmed by X-ray diffraction patterns, energy-dispersive X-ray spectroscopy, and elemental dot-mapping images. Nanosheet morphology was recognized for both CoFe LDH and CoCeFe ternary LDH from scanning electron microscopy and transmission electron microscopy micrographs. In the following, a dispersive solid phase extraction (DSPE) method was developed using the synthesized CoCeFe ternary LDH as a sorbent for extracting perfluorooctanesulfonic acid (PFOS) from wastewater samples. For the selective analysis of PFOS, high-performance liquid chromatography-tandem mass spectroscopy (HPLC-MS/MS) in multiple reaction monitoring mode was used. Analytical parameters such as the limit of detection equal to 0.02 μg/L, with a linear range of 0.05–300 μg/L, the limit of quantification equal to 0.05 μg/L, and an enrichment factor equal to 23.3 were achieved for PFOS at the optimized condition (sorbent: 5 mg of CoCeFe ternary LDH, eluent type and volume: 150 μL mobile phase, pH: 3, adsorption time: 3 min, and desorption time: 5 min). The developed strategy for the analysis of PFOS was tested in real wastewater samples, including copper mine and petrochemical wastewater. The amount of analytes in real samples was calculated using the standard addition method, and good relative recovery in the range of 86%–105% was obtained. The main novelty of this research is the application of CoCeFe ternary LDH to extract the PFOS from wastewater using the DSPE method for determination by HPLC-MS/MS.

Cu3P Nanoarrays Fabricated on Copper Foam Substrates Followed by Coating with CoFe Layered Double Hydroxide Nanosheets as Electrocatalysts for Water Splitting

Cu₃P Nanoarrays Fabricated on Copper Foam Substrates Followed by Coating with CoFe Layered Double Hydroxide Nanosheets as Electrocatalysts for Water Splitting

Enhanced photocatalytic performance of MXene-Modified cation-exchanged CoFe-LDH/CoFeCrO4 heterostructure for Antibiotic degradation and hydrogen production through synergistic charge dynamics

Systemizing an effective charge-transfer channel across a junction interface replete with ample active sites for enhancing the photocatalytic activity of semiconducting materials presents a formidable challenge. Here, we present a novel approach based on an in situ hydrothermal method for synthesizing CoFe-Layered Double Hydroxide (LDH)/CoFeCrO4 heterojunction materials that were partially derived from CoFe-LDH. These materials synergistically interact with Ti3C2 MXene nanosheets facilitating multi-interface interactions. Indeed, the highest tetracycline hydrochloride degradation rate of nearly 92% in 2 h was achieved because of the intense synergy between the CoFe-LDH/CoFeCrO4 heterojunction material optimized with 7.5 wt% of MXene nanosheets (CMC-7.5). This degradation performance was 3.1 times greater than that of the original CoFe-LDH. Further, CMC-7.5 produces the highest H2 gas of 458.79 μmol h−1g−1 from a photocatalytic water splitting reaction. The formation of a Schottky energy barrier between the partially derived CoFe-LDH/CoFeCrO4 unit and MXene promoted the fast transfer of photogenerated electrons from CoFe-LDH/CoFeCrO4 to the surface of MXene, thereby providing a plethora of active sites for photocatalytic reactions. Photoelectrochemical assessments using transient and linear sweep voltammetry along with electrochemical impedance spectroscopy confirmed efficient charge carrier transfer. Moreover, the optimized CMC-7.5 photoelectrode has a superior integral area and exhibited excellent stability over 100 cycles. Finally, the study outlines the construction of several advanced materials with multi-interface heterojunctions involving cation-exchanged LDH derivatives with high photogenerated charge carrier separation efficiency and minimal interfacial migration resistance to serve as stability benchmarks for practical applications.

CoFe-Layered Double Hydroxide Needles on MoS2/Ni3S2 Nanoarrays for Applications as Catalysts for Hydrogen Evolution and Oxidation of Organic Chemicals

CoFe-Layered Double Hydroxide Needles on MoS₂/Ni₃S₂ Nanoarrays for Applications as Catalysts for Hydrogen Evolution and Oxidation of Organic Chemicals

In Situ-Generated Hollow CoFe-LDH/Co-MOF Heterostructure Nanorod Arrays for Oxygen Evolution Reaction.

Assembling a heterostructure is an effective strategy for enhancing the electrocatalytic activity of hybrid materials. Herein, CoFe-layered double hydroxide and Co-metal-organic framework (CoFe-LDH/Co-MOF) hollow heterostructure nanorod arrays are synthesized. First, [Co(DIPL)(H3BTC)(H2O)2]n [named as Co-MOF, DIPL = 2,6-di(pyrid-4-yl)-4-phenylpyridine, H3BTC = 1,3,5-benzenetricarboxylic acid] crystalline materials with a uniform hollow structure were prepared on the nickel foam. The CoFe-LDH/Co-MOF composite perfectly inherits the original hollow nanorod array morphology after the subsequent electrodeposition process. Optimized CoFe-LDH/Co-MOF hollow heterostructure nanorod arrays display excellent performance in oxygen evolution reaction (OER) with ultralow overpotentials of 215 mV to deliver current densities of 10 mA cm-2 and maintain the electrocatalytic activity for a duration as long as 220 h, ranking it one of the non-noble metal-based electrocatalysts for OER. Density functional theory calculations validate the reduction in free energy for the rate-determining step by the synergistic effect of Co-MOF and CoFe-LDH, with the increased charge density and noticeable electron transfer at the Co-O site, which highlights the capability of Co-MOF to finely adjust the electronic structure and facilitate the creation of active sites. This work establishes an experimental and theoretical basis for promoting efficient water splitting through the design of heterostructures in catalysts.

Boosting Efficient Alkaline Hydrogen Evolution Reaction of CoFe-Layered Double Hydroxides Nanosheets via Co-Coordination Mechanism of W-Doping and Oxygen Defect Engineering.

While surface defects and heteroatom doping exhibit promising potential in augmenting the electrocatalytic hydrogen evolution reaction (HER), their performance remains unable to rival that of the costly Pt-based catalysts. Yet, the concurrent modification of catalysts by integrating both approaches stands as a promising strategy to effectively address the aforementioned limitation. In this work, tungsten dopants are introduced into self-supported CoFe-layered double hydroxides (LDH) on nickel foam using a hydrothermal method, and oxygen vacancies (Ov) are further introduced through calcination. The analysis results demonstrated that tungsten doping reduces the Ov formation energy of CoFeW-LDH. The Ov acted as oxophilic sites, facilitating water adsorption and dissociation, and reducing the barrier for cleaving HO─H bonds from 0.64 to 0.14eV. Additionally, Ov regulated the electronic structure of CoFeW-LDH to endow optimized hydrogen binding ability on tungsten atoms, thereby accelerating alkaline Volmer and Heyrovsky reaction kinetics. Specifically, the abundance of Ov induced a transition of tungsten from a six-coordinated to highly active four-coordinated structure, which becomes the active site for HER. Consequently, an ultra-low overpotential of 41mV at 10 mAcm-2 , and a low Tafel slope of 35mVdec-1 are achieved. These findings offer crucial insights for the design of efficient HER electrocatalysts.

An enzyme-free sensor based on La-doped CoFe-layered double hydroxide decorated on reduced graphene oxide for sensitive electrochemical detection of urea.

The successful synthesis ofLa-doped CoFe LDH@rGO nanocompositeis reported combiningthe advantages of LDH and rGO and shows promising performances in electrochemical sensors. The structure of the obtained nanocomposite was investigated using Fourier transform infrared spectroscopy (FTIR), X-ray diffraction pattern (XRD), and field emission scanning electron microscope images (FE-SEM). Then, it was directly utilized to construct a carbon paste electrode (CPE) for urea detection. The electrochemical performance of the sensor was evaluated by various electrochemical methods. The La-CoFe LDH@rGO electrode exhibited excellent electrocatalytic properties, including a wide linear workingrange of 0.001-23.5 mM, very high sensitivity of 1.07 ± 0.023 µA µM-1 cm-2, a low detection limit of 0.33 ± 0.11 µM, and rapid response time of 5 s towards urea detection at the working potential of 0.4 V. Furthermore, the sensor displayed a high selectivity in different matrices, appropriate reproducibility, and long shelf life without activity loss during 3 months of storage under ambient conditions. Further tests were performed on serum and milk samples to confirm the capability of the proposed sensor for practical applications, demonstrating a reasonable recovery of 94.8 to 102% with an RSD value below 3%. Consequently, the synergistic effect of each component led to the good electrocatalytic activity of the modified electrode towards urea.

Novel Heterostructure-Based CoFe and Cobalt Oxysulfide Nanocubes for Effective Bifunctional Electrocatalytic Water and Urea Oxidation.

The development of effective oxygen evolution reaction (OER) and urea oxidation reaction (UOR) on heterostructure electrocatalysts with specific interfaces and characteristics provides a distinctive character. In this study, heterostructure nanocubes (NCs) comprising inner cobalt oxysulfide (CoOS) NCs and outer CoFe (CF) layered double hydroxide (LDH) are developed using a hydrothermal methodology. During the sulfidation process, the divalent sulfur ions (S2- ) are released from the breakdown of the sulfur source and react with the Co-precursors on the surface leading to the transformation of CoOH nanorods into CoOS nanocubes. Further, X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy (XAS) analyses reveal that the interactions at the interface of the CF@CoOS NCs significantly altered the electronic structure, thus enhancing the electrocatalytic performance. The optimal catalysts exhibited effective OER and UOR activities, the attained potentials are 1.51 and 1.36V. This remarkable performance is attributable to the induction of electron transfer from the CoFe LDH to CoOS, which reduces the energy barrier of the intermediates for the OER and UOR. Furthermore, an alkaline water and urea two-cell electrolyzer assembled using CF@CoOS-2 NCs and Pt/C as the anode and cathode requires a cell voltage of 1.63 and 1.56V along with a durability performance.

Facilitated Visible-Light-Driven Peroxymonosulfate Activation by a Co-Fe Layered Double Hydroxide Derived p-n Heterostructure for Sulfadiazine Degradation: Affecting Parameters, Kinetics, and Mechanistic Insights.

The utilization of multivalence ionic metal species generated through a peroxymonosulfate (PMS)-assisted photocatalytic system is a promising platform for the selective degradation of water contaminants. However, achieving an effective electron transport and enhanced separation efficiency for these metal species is a daunting challenge. Thus, our current study addresses this challenge by using a Co-Fe-based layered-double-hydroxide template to synthesize a Co3O4/FeCo2O4 p-n heterojunction composite via a simple monosynthetic route. The resultant composite is thoroughly validated through advanced characterization techniques that efficiently activate PMS for sulfadiazine (SDZ) degradation under visible light, achieving a remarkable degradation efficiency of up to 90%. This accomplishment is attributed to factors including intimate interfacial contact, excellent light harvesting, mesoporosity, and oxygen vacancies within the composite. The formation of a distinct p-n heterojunction following the S-scheme charge dynamic significantly enhances photogenerated carrier separation and reduces charge recombination. The research delves into comprehensive investigations including degradation studies, active species trapping experiments, parameter exploration, and in-depth liquid chromatography-mass spectrometry for analysis of the degradation byproducts and pathway. Induced oxygen vacancies, strategically placed active surface sites, and mesoporosity in the Co3O4/FeCo2O4 composite synergistically boosted the sluggish PMS activation, leading to enhanced SDZ degradation. This study introduces a new perspective by demonstrating the potential of a single-material, mixed-metal oxide-based p-n heterojunction photocatalytic system following the S-scheme charge-transfer route for SDZ degradation. The findings contribute toward emphasizing the importance of tailored composite materials in tackling persistent contaminants.

Dispersive solid phase extraction of perfluorooctanoic acid from wastewater using chromium-doped CoFe layered double hydroxide for determination by LC-MS/MS

Polyfluoroalkyl substances (PFAS) are persistently dangerous substances in the environment, threatening human health even in very low concentrations. This work introduced a dispersive solid phase extraction (DSPE) based on Cr-doped CoFe layered double hydroxide (LDH), which was used as the extraction phase for the effective removal of perfluorooctanoic acid (PFOA) from wastewater samples. Cr-doped CoFe LDH was synthesized using the facile co-precipitation method. Successful partial substitution of Fe3+ by Cr3+ cations in the crystalline lattice of CoFe LDH was affirmed by energy-dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD), and elemental dot-mapping analysis. Layered morphology was observed for both bare and Cr-doped CoFe LDH in scanning and transmission electron microscopy images. The influence of diverse parameters, including sorbent mass, eluent solvent type, volume of eluent, agitation mode, adsorption time, and pH, was assessed on the extraction of PFOA by Cr-doped CoFe LDH. The experimental data from the effective DSPE followed by liquid chromatography–tandem mass spectrometry exhibited a low limit of detection of 0.03 µg/L, broad linear range (0.1–300 µg/L and R2 ≥ 0.997), and good repeatability (6.7 %, n = 5 intraday) for the enrichment and determination of PFOA in wastewater samples.

Interface-engineered urchin-like CoFe-layered double hydroxide for high-efficiency electrocatalytic oxygen evolution

Interface engineering of urchin-like CoFe-layered double hydroxide introduced by ultrafine Ce(OH)3 nanoparticles enhanced the catalytic activity and stability of the oxygen evolution reaction.

Anion-induced vacancy enhances Co3Se4/Fe3Se4 heterostructures for high-efficiency hydrogen production

Modulation of the electronic structure of the active site by defect engineering and heterostructure are effective strategies to improve the electrocatalytic performance of catalysts. Herein, S-doped Co3Se4/Fe3Se4 (S-Co3Se4/Fe3Se4) heterostructures derived from CoFe-layered double hydroxide (CoFe-LDH) with unique nanowire-nanosheet array structures have been constructed using the different solubility product (Ksp) between sulfides and selenides. The intrinsic mechanism of their excellent electrocatalytic performance has been investigated. The unique nanowire-nanosheet array structure increases the number of exposed active sites, and the doping of sulfur not only adjusts the electronic structure of Co but also induces the enhancement of the selenium vacancy and conductivity. S-Co3Se4/Fe3Se4 exhibits excellent oxygen evolution reaction (OER) performance in 1 M KOH, requiring an overpotential of 255 mV to achieve the current density of 100 mA/cm2. With the assistance of the methanol oxidation reaction (MOR), the current density of 10 mA/cm2 is achieved with only 1.48 V while generating high-value formic acid and reducing energy consumption by 10 % relative to conventional electrocatalysts. The main active sites of the OER process have been identified by after OER characterization at the same time, which enriches the OER mechanism study. It provides the feasible strategy for tuning the electronic structure of heterostructures, and the practical reference for the development of OER and MOR bifunctional electrocatalysts.

Boosting Alkaline Seawater Oxidation of CoFe-layered Double Hydroxide Nanosheet Array by Cr Doping.

The pursuit of stable and efficient electrocatalysts toward seawater oxidation is of great interest, yet it poses considerable challenges. Herein, the utilization of Cr-doped CoFe-layered double hydroxide nanosheet array is reported on nickel-foam (Cr-CoFe-LDH/NF) as an efficient electrocatalyst for oxygen evolution reaction in alkaline seawater. The Cr-CoFe-LDH/NF catalyst can achieve current densities of 500 and 1000mAcm-2 with remarkably low overpotentials of only 334 and 369mV, respectively. Furthermore, it maintains at least 100h stability when operated at 500mAcm-2.

Interfacial Coupling Engineering Boosting Electrocatalytic Performance of CoFe Layered Double Hydroxide Assembled on N-Doped Porous Carbon Nanosheets for Water Splitting and Flexible Zinc-Air Batteries.

The disadvantages of layered double hydroxides (LDHs) such as easy stacking, poor inherent conductivity, and limited versatility hinder their application in splitting water and zinc-air batteries (ZABs). Interface engineering to regulate the electron distribution of LDHs by introducing another component is a way to compensate for the poor electron transport capacity of LDHs during catalysis. Herein, a hierarchical structure is synthesized by assembling CoFe-LDH nanosheets onto the surface of layered N-doped porous carbon (NPC), CoFe-LDH@NPC, by using an interface engineering strategy. CoFe-LDH@NPC has high catalytic activity for the oxygen/hydrogen evolution reaction (OER/HER) with overpotentials of 280/100 mV, respectively. The two-electrode water splitting catalyzed by CoFe-LDH@NPC only needs 1.61 V to drive a current density of 10 mA cm-2 for 60 h. The theoretical results show that there is an electron-deficient/electron-rich interface between the NPC substrate and the CoFe-LDH in CoFe-LDH@NPC. The electrons on the coupling interface are easily transferred, which results in a change of the adsorption behavior of the reaction intermediates and improves the catalytic activity for the OER and HER. In addition, CoFe-LDH@NPC-catalyzed rechargeable flexible ZABs have excellent performance with low charge-discharge polarization (0.87 V) and a long-term stability of 65 h.

In-situ fabrication of bimetallic FeCo2O4-FeCo2S4 heterostructure for high-efficient alkaline freshwater/seawater electrolysis

Rational construction of bifunctional electrocatalysts with long-term stability and high electrocatalytic activity is of great importance, but it is challenging to obtain highly efficient non-precious metal-based catalysts for overall seawater electrolysis. Herein, a nickel foam (NF) self-supporting CoFe-layered double hydroxide (CoFe-LDH/NF) was directly converted into FeCo2O4-FeCo2S4 heterostructure via hydrothermal method in 50 mM Na2S solution, instead of FeCo2O4@FeCo2S4 core-shell structure. The FeCo2O4-FeCo2S4 heterojunction shows nanosheets structure with rough surface (the thickness of ∼ 198.9 nm), which provides rich oxide/sulfide interfaces, high electrochemical active area, a large number of active sites, as well as fast charge and mass transfer. In 1.0 M KOH solution, 1.0 M KOH + 0.5 M NaCl, and alkaline natural seawater, the FeCo2O4-FeCo2S4 heterojunction exhibits eminently electrocatalytic performance, with overpotentials of η-100 = 225 mV, η-100 = 233 mV, and η-100 = 238 mV for OER, as well as η-100 = 271 mV, η-100 = 273 mV, and η-100 = 277 mV for HER, respectively. Furthermore, self-supporting FeCo2O4-FeCo2S4 electrode (FeCo2O4-FeCo2S4/NF) as the cathode and anode of an electrolyzer exhibits a lower cell voltage of E-100 = 1.75 V in alkaline seawater than those of FeCo2S4/NF (1.77 V), CoFe-LDH/NF (1.87 V), and FeCo2O4/NF (1.91 V). Specifically, FeCo2O4-FeCo2S4 electrolyzer can stably produce hydrogen for over 48 h in alkaline freshwater/seawater electrolyte. These outstanding electrocatalytic performances and corrosion resistance to salty-water can be attributed to the surface reconstruction behavior of the FeCo2O4-FeCo2S4/NF catalyst during OER, which leads to the in-situ formation of metal oxyhydroxides. In particular, the FeCo2O4-FeCo2S4 heterojunction is also very competitive among most state-of-the-art non-noble metal-based catalysts, whether in KOH or alkaline salty-water electrolytes.