Hydrogen Evolution Reaction Research Articles

High-viscoelasticity alginate-based coatings for reversible zinc metal anodes

High-safety aqueous zinc (Zn) ion batteries are troubled by dendrite growth and hydrogen evolution reaction on Zn anode, which can be well solved via the construction of surface protective layer. The recent researches mainly focus on the bulk property of the protective layer, but its separation from Zn anode is ignored. In this work, high-viscoelasticity alginate-based (HVAA) layer was in-situ constructed on Zn anodes by the cross-linking of sodium alginate with formaldehyde and the plastifying of glycerin. HVAA layer can combine with H2O and coordinate with Zn2+ ions in aqueous electrolyte to achieve viscoelasticity on Zn anode, which can accommodate volume change of Zn anode during plating/stripping processes to continuously protect Zn anodes under the real battery system. Physical block effect of HVAA layer impedes hydrogen evolution corrosion reaction by avoiding the immediate contact of Zn anodes with aqueous electrolyte. Ionic conductive ability of HVAA layer by coordinating oxygen-containing groups with Zn2+ can uniform ion flux to induce the homogeneous deposition of Zn2+ on Zn anode. Zn anode with HVAA endows ZnZn symmetric battery with stably cycle of 4000 h and Zn-iodide full batteries with better electrochemical performance of 8000 cycles comparing with bare Zn anode. This work opens a novel route to continuously protect Zn anode through the high-viscoelasticity films to closely fit with Zn surface and implement the high-value application of renewable sources.

Effects of water content on the corrosion behavior of NiCu low alloy steel embedded in compacted GMZ bentonite

Buffer material and metal disposal containers are the key engineering barriers in the geological disposal of high-level radioactive waste. The durability of disposal containers largely depends on the water content in buffer material. This work focused on investigating the corrosion evolution of NiCu low alloy steel in compacted GMZ bentonite with different water contents for 270 d by using weight loss, electrochemical measurements, and various methods for analyzing corrosion products. As the water content increased from 13% to 20%, the water in the bentonite transformed from an unsaturated to a critical saturated state, and the corrosion rate of NiCu steel clearly increased. In these two systems, the oxygen could migrate to the thin liquid film on the steel surface through the air pores in the bentonite in the gas phase and undergo cathodic reduction. Meanwhile, it oxidized the ferrous hydrolysis products into ferric corrosion products and formed a rust layer, which could block the diffusion of oxygen. At that moment, the cathodic process of NiCu steel corrosion changed to rust reduction. When the water content continually increased to 30% and 40%, the compacted bentonite was in a saturation state, and the corrosion rate of NiCu steel was significantly decreased. This was because most pores among the bentonite particles were occupied by a large amount of free water, which hindered the diffusion of oxygen and inhibited its cathodic reduction. Furthermore, it restrained the oxidation of ferrous corrosion products, which greatly weakened the cathodic depolarization of rust, leading to the cathodic process being dominated by the hydrogen evolution reaction.

Enhanced single-atom cobalt layer in MAX phase for biomass electrooxidation integrated with hydrogen evolution

MAX phases have attracted considerable interest due to their structural diversities and potential applications. More than 150 MAX phases have been synthesized, especially expanding the range of A-site atoms from traditional main group elements to subgroup elements with outer layer d electronic structure. However, the functional applications for MAX phases remain somewhat limited. The A-site elements in MAX phases can amplify their inherent properties, transforming primary structural materials into multifunctional materials. As highly catalytic elements, introducing cobalt into the A-site of MAX phases can reveal surprising catalytic activities. Hence, the MAX phase with single-atom-thick cobalt layers was synthesized via an A-site alloying strategy in this work. The obtained V2(Sn2/3Co1/3)C MAX phase demonstrates efficient electrocatalysis in 5-hydroxymethylfurfural (HMF) oxidation reaction along with hydrogen evolution reaction (HER). In-situ electrochemical studies discover that HMF can prevent the self-reconstruction of MAX phase and oxygen evolution reaction (OER). The overall reaction reaches 94.4 % yield to 2,5-furandicarboxylic acid (FDCA) at 1.60 V. Density functional theory calculations suggest that the Co-Sn bimetallic synergy in the A-site promotes the reaction. This groundbreaking investigation into using MAX phases for biomass upgrading highlights their potential in green chemistry and beyond.

Testing and Assessment of Various Catalysts for Uniquely Designed Cathodes for Hydrogen Evolution Reactions

This study reports the electrodeposition of unique catalysts for 3D-printed cathodes for alkaline water electrolysis. This paper explores hydrogen evolution reaction performance for various nickel, nickel-copper, nickel-iron, and nickel-molybdenum 3D-printed electrodes. In particular, this study reports a novel electrodeposition of nickel-iron and nickel-molybdenum on conductive PLA 3D-printed electrode surfaces. The performance of the electrodes is assessed through electrochemical models including cyclic voltammetry (CV), linear sweep voltammetry (LSV), and electrochemical impedance spectroscopy (EIS). The results of the study show considerable differences, at a particular current density of 10 mA/cm2, nickel-iron, and nickel-copper coated 3D-printed electrodes are found to have an overpotential of 270 mV and 275 mV respectively. The nickel-copper and nickel-iron coated electrodes also showed to have a low resistance. The amount of metal deposited also showed to have an important role. At a potential of -2.5V, nickel coated electrode Ni4x with four times the nickel mass deposition (0.178 g/cm2) of another nickel coated electrode Ni1x (0.044 g/cm2) is found to have a current density of -106 mA/cm2 in comparison to -44 mA/cm2 respectively. These findings provide important insights for optimizing additive manufacturing for electrochemical systems.

The effect of different vulcanization reagents on the synthesis of NiFeS and the performance test of seawater electrolysis

Hydrogen energy, as the most promising new energy for sustainable development, has aroused wide concern of researcher in the field of energy chemical industry. Among the many hydrogen generation approaches, electric water splitting for producing H2 is considered to be a simple and environmentally friendly method. Transition metal-based catalysts have become an important field in alkaline seawater electrolysis due to their high abundance and superior catalytic performance. Therefore, NiFeS (Ni3S2@FeS) was in-situ generated on nickel foam through a simple two-step hydrothermal approach in this paper. NiFeS/NF catalysts synthesized by three vulcanization reagents (Na2S·9H2O, CH3CSNH2, CH4N2S) were characterized and compared by a series of electrochemical tests. It is worth noting that for the first time, different vulcanization reagents were used to explore the activity of the same catalyst in seawater splitting and urea splitting. It was found that the NiFeS catalyst synthesized by Na2S·9H2O (Ni3S2@FeS-1/NF) had better oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) performance and good stability in alkaline seawater. The overpotential required for the OER with Ni3S2@FeS-1/NF electrode in alkaline seawater (1 M KOH + seawater electrolyte) is 290 mV at the 10 mA cm-2, and 92 mV for the hydrogen evolution reaction at the 10 mA cm-2. It is found that the NiFeS catalyst obtained by vulcanization of NiFe-LDH not only has high activity and conductivity, but also can effectively inhibit Cl- corrosion. Ni3S2@FeS-1/NF catalyst has a unique cluster rosette nanosheet array structure, which can present more catalytic reaction centres, accelerate the electron transfer rate and promote electrochemistry performance. The work proposes a novel way to explore the effect of different synthesis methods of the same composition on the performance of electrolytic seawater.

Atmosphere-driven metal-support synergy in ZnO/Au catalysts for efficient piezo-catalytic hydrogen evolution

Piezo-catalysis, which leverages mechanical energy to drive chemical reactions, is emerging as a promising method for sustainable energy production. While the enhancement of piezo-catalytic performance through metal-support interactions is well-documented, the critical influence of the synthesis atmosphere during metal-loaded piezo-catalyst preparation has been a notable gap in the field. To this end, we systematically investigate how different atmospheric conditions during the synthesis of catalysts—without gas flow or with Ar, N2 and O2—affect metal dispersion, oxidation states, piezo-carrier dynamics, and electronic structure, and subsequently shape the metal-support interactions and piezo-catalytic activity. ZnO/Au, with Au deposited on ZnO, is selected as the model system, and hydrogen evolution reaction is used as the probe reaction. Our results demonstrate that an oxygen-enriched atmosphere significantly enhances the metal-support interactions, achieving an ultrahigh net hydrogen yield of 16.5 mmol·g–1·h–1 on ZnO/Au, a 3.58-fold increase over pristine ZnO. Specifically, the performance improvements substantially surpass those synthesized under other atmospheric conditions. Conversely, exposure to CO2 transforms the ZnO support into ZnCO3, adversely affecting its catalytic activity. These findings reveal the crucial impact of synthesis conditions on piezo-catalyst performance and thereby open new avenues for optimizing catalyst systems for enhanced sustainability.

Regulating the space charge at interface by negative polar biomolecule enabling ultrastable Zn anode chemistry

The irreversibility of Zn metal anode arising from uncontrollable dendrite growth and hydrogen evolution reaction, especially at high current densities, has challenged the commercialization application of aqueous Zn-ion batteries. Here we report biomolecule additive, named xanthan gum, to solve these issues through making use of dissociated electronegative groups to reduce space charge near the anode-electrolyte interface, tuning solvation structure and form H2O-poor electrical double layer to regulate the Zn deposition behaviors. Meanwhile, the dissolved xanthan gum with multiple polar groups can break the association between H2O and Zn2+ to reconstruct solvated structures of Zn ions to suppress hydrogen evolution reaction (HER). Therefore, the Zn//Zn symmetric cells in ZnSO4 electrolyte with xanthan gum deliver an ultra-long cycle life (>4700 h), and also present excellent cycling performances in other electrolytes (Zn(OAc)2 and Zn(OTf)2). More importantly, a high coulombic efficiency of 99.7 % is achieved using Zn//Cu half cells tested and excellent cycling life for KVO//Zn full cells. This work provides a guidance to design the electrolyte additive for highly reversible Zn metal batteries.

Sulfonate-Functionalized Metal-Organic Framework as a Porous "Proton Reservoir" for Boosting Electrochemical Reduction of Nitrate to Ammonia.

The electrochemical reduction reaction of nitrate (NO3RR) is an attractive route to produce ammonia at ambient conditions, but the conversion from nitrate to ammonia, which requires nine protons, has to compete with both the two-proton process of nitrite formation and the hydrogen evolution reaction. Extensive research efforts have thus been made in recent studies to develop electrocatalysts for the NO3RR facilitating the production of ammonia. Rather than designing another better electrocatalyst, herein, we synthesize an electrochemically inactive, porous, and chemically robust zirconium-based metal-organic framework (MOF) with enriched intraframework sulfonate groups, SO3-MOF-808, as a coating deposited on top of the catalytically active copper-based electrode. Although both the overall reaction rate and electrochemically active surface area of the electrode are barely affected by the MOF coating, with negatively charged sulfonate groups capable of enriching more protons near the electrode surface, the MOF coating significantly promotes the selectivity of the NO3RR toward the production of ammonia. In contrast, the use of MOF coating with positively charged trimethylammonium groups to repulse protons strongly facilitates the conversion of nitrate to nitrite, with selectivity of more than 90% at all potentials. Under the optimal operating conditions, the copper electrocatalyst with SO3-MOF-808 coating can achieve a Faradaic efficiency of 87.5% for ammonia production, a nitrate-to-ammonia selectivity of 95.6%, and an ammonia production rate of 97 μmol/cm2 h, outperforming all of those achieved by both the pristine copper (75.0%; 93.9%; 87 μmol/cm2 h) and copper with optimized Nafion coating (83.3%; 86.9%; 64 μmol/cm2 h). Findings here suggest the function of MOF as an advanced alternative to the commercially available Nafion to enrich protons near the surface of electrocatalyst for NO3RR, and shed light on the potential of utilizing such electrochemically inactive MOF coatings in a range of proton-coupled electrocatalytic reactions.

Influence of platinum content on semiconductor and electrochemical properties of materials based on titanium suboxides

The effect of platinum content on the surface morphology, phase composition and electrochemical properties of materials based on titanium suboxides was investigated. Titanium suboxides are formed at the stage of coating reduction under cathodic polarization, which allows the formation of a porous developed surface for electrodeposition of catalytic platinum layers. The main allotropic modification of TiOx in the studied composite materials is anatase, which contains particles of elemental titanium and platinum. The investigated materials are highly doped semiconductors with a high concentration of charge carriers. With an increase in the platinum content, an extreme dependence of the potential of flat zones is observed, which is associated with the formation of a composite material. The electrocatalytic activity was studied in the reactions of oxygen and hydrogen evolution. The overvoltage of oxygen production on platinum-containing materials is much lower than on the TiOx electrode. The slope of the linear dependence of the potential on the current density decreases with an increase in platinum content. The Tafel slope for the studied materials in the hydrogen evolution reaction was 160 mVdec–1 for coatings containing 0.25 mgcm–2 Pt; whereas it was equal to 42 and 43 mVdec–1 for electrodes with 0.5 and 2 mgcm–2 Pt, respectively.

Unveiling the interaction between corrosion products and oxygen reduction on the corrosion of Mg–4Nd–0.4Zr alloy under thin electrolyte layers

Although hydrogen evolution reaction (HER) is considered to be the main cathodic reaction of Mg corrosion, oxygen reduction reaction (ORR) has been recently confirmed to be a secondary cathodic reaction. The factors affecting ORR of magnesium (Mg) alloys are still unclear, especially in cases under thin electrolyte layers (TEL). In this work, the influence of the corrosion product films on the cathodic reactions of Mg alloys under TEL and in a bulk solution was investigated. ORR does not influence the hydrogen evolution rates in the corrosion of Mg alloys. Therefore, with the existence of oxygen, corrosion rates of Mg alloys measured by hydrogen evolution tests are not accurate under TEL. And weight loss test is a more accurate method to evaluate Mg corrosion rates under TEL. ORR was confirmed to participate in the corrosion of Mg–4Nd–0.4Zr, Mg–4Nd and Mg–0.4Zr alloys under TEL. In 100-μm TEL, the highest contribution of ORR in cathodic reactions for the corrosion of Mg–4Nd–0.4Zr, Mg–4Nd and Mg–0.4Zr alloys are 28.6%, 39.1%, and 35.8%, respectively. The more protective film on Mg–4Nd–0.4Zr alloy provides a stronger inhibition effect against the diffusion of oxygen, leading to decreased ORR contribution in cathodic reactions. In addition, it is suggested that the preparation of Mg alloys with protective corrosion product films can inhibit the corrosion induced by ORR in the atmosphere. This work emphasizes the effects of corrosion product films on ORR in Mg corrosion, especially under TEL.

Unraveling the synergistic mechanisms of dual-atom catalysts on BeN4 substrates for enhanced hydrogen evolution reaction: A machine learning-assisted first-principles study

Synergistic effects have been widely studied in both homogeneous and heterogeneous bimetallic catalysis. However, the exact mechanisms underlying the synergistic effects between bimetallic atoms remain elusive. This study, using density functional theory calculations, systematically explores a dual-atom catalyst (DAC) on a BeN4 substrate, where two beryllium atoms are substituted with transition metals. The results demonstrate that the dual-atom catalysis TMTM’@BeN4 exhibits synergistic effects. Notably, five DAC systems, particularly those co-doped with V and Cr, significantly reduce the Gibbs free energy (ΔGH∗) for the hydrogen evolution reaction (HER). We further utilized machine learning to explore how the dual-atom catalysts exhibit synergistic effects. Machine learning analysis indicates that changes in the average interatomic distance and the Fermi level of the catalyst system are the main factors influencing the Gibbs free energy variation in dual-atom catalysts, jointly determining the hydrogen evolution catalytic activity. This work provides profound insights into understanding the synergistic mechanisms of dual-atom catalysts.

Electrocatalytic activities of iron-supported N-doped porous carbon towards the oxygen/hydrogen evolution reaction

Red mud (RM) disposal has been highly apprehensive due to its environmental impact. The aluminum industry produces large amounts of red mud waste annually, and turning it into a value-added product is a key component of sustainable development. This study combines RM with an N-doped porous carbon (biomass precursor) as an effective electrocatalyst for oxygen evolution and hydrogen evolution reactions (OER and HER). One significant obstacle to anion-exchange membrane (AEM) electrolyzer applications is the development of electrocatalysts that do not require noble metals and are both efficient and effective at HER and OER. The synthesized iron-supported (RM-derived) N-doped porous carbon (RMNPC) exhibits excellent catalytic activities with 276 and 191 mV overpotentials at 10 mA cm−2 for OER and HER, respectively. A two-electrode cell system is designed with an RMNPC/NF electrode as anode and cathode, and it necessitates just 1.82 V to realize 10 mA cm−2 and shows outstanding durability. This study presents a low-cost but effective electrocatalyst for water splitting for renewable hydrogen production, achieving the goal of RM recycling and highlighting the potential of porous carbon electrocatalysts.

Constructing artificial photosynthetic system based on graphdiyne double heterojunction to enhance REDOX capacity and hydrogen evolution efficiency

Although traditional type II heterojunction designs for artificial photosynthesis show promise for photocatalytic hydrogen production, their redox capacity is somewhat limited due to the spatial separation of hydrogen evolution and oxidation reactions at less favorable sites. To overcome this limitation, ohmic junctions based on type II heterojunctions have been designed to enhance hydrogen evolution by transferring electrons to the metal component. In this study, a copper powder graphdiyne (Cu-GDY) composite catalyst with ohmic angle contact was synthesized by coupling copper foil with hexa-hexylbenzene. Incorporating Cu-GDY into CoGdO3 results in an interleaved band structure forming a type II heterojunction at the contact interface. This configuration overcomes the issue of the unfavorable conduction band position of CoGdO3, thereby promoting charge transfer. The internal electric field created by the Fermi level difference between Cu-GDY and CoGdO3, increase in REDOX capacity is the main reason for the increase of carrier separation rate. In addition, the plasmonic properties of copper expand the active reaction sites and promote the hydrogen evolution reaction. The composite catalyst exhibits b a hydrogen production rate that is 10.5 times higher than that of the individual catalysts. This work demonstrates that the formation of two distinct contact interfaces between Cu-GDY and CoGdO3 significantly improves the electron transfer and hydrogen evolution performance.

Enhanced formate production from sulfur modified copper for electrocatalytic CO2 reduction

Producing liquid fuels with high selectivity and low overpotential has long been a goal of electrocatalytic CO2 reduction reaction (CO2RR). Here we present a detailed study on the structural and catalytic properties of sulfur on copper for CO2RR. Cu2S was formed by enabling sulfur to deposit on the copper surface with a simple surface impregnation method. The sulfur modified samples, especially the sulfur modified oxide-derived copper (SM-OD-Cu), have significantly higher selectivity to formate than the pure and oxide-derived copper. At a potential range of -0.51∼-0.75 V vs. RHE, the selectivity of formate for SM-OD-Cu in the liquid phase was nearly 100%. Also, the partial current density of formate reached -4.26 mA/cm2 at -0.75 V vs. RHE. By using density functional theory calculation, we found that Cu2S significantly inhibits the CO pathway and hydrogen evolution reaction, and further improves the selectivity of formate.

Synergistic electrochemical performance of NdFeO3/rGO composite for enhanced oxygen and hydrogen evolution reactions

Synergistic electrochemical performance of NdFeO3/rGO composite for enhanced oxygen and hydrogen evolution reactions

Malic acid additive with a dual regulating mechanism for high-performances aqueous zinc-ion batteries

Aqueous zinc-ion batteries (AZIBs) are widely used in energy storage devices due to their high safety and low cost. However, the practical application of AZIBs is constrained by the formation of dendrites and the occurrence of severe side reactions. Herein, these problems are addressed by introducing malic acid (MA) as a multifunctional additive into electrolyte. Theoretical calculations, finite element simulations and experimental tests show that MA can adsorb on the surface of the Zn anode and change the solvated structure of Zn2+ and promote the desolvation of [Zn (H2O)6]2+, thus inhibiting the hydrogen evolution reaction (HER) and the generation of by-products, and promoting the uniform deposition of Zn. Additionally, benefiting from this dual effect of solvent structure and interface adsorption regulation, a high Coulombic efficiency of 99.83 % can be achieved for the Zn//Cu half cell in an electrolyte containing a small amount of MA, and an excellent lifetime of beyond 4000 h can be achieved in a Zn//Zn symmetric cell at 5 mA cm−2 and 1 mAh cm−2. Even under deep plating/stripping conditions (5 mA cm−2 and 5 mAh cm−2), it is still capable of stabling operation for 600 h. In addition, the Zn//V2O5 full cell with MA also exhibited higher capacity and better rate performance. The incorporation of MA improves the electrochemical performance of zinc ion batteries to a great extent relative to the pure ZnSO4 electrolyte.

N-doped porous graphite with multilevel pore defects and ultra-high conductivity anchoring Pt nanoparticles for proton exchange membrane water electrolyzers

Water electrolysis for hydrogen production offers a promising solution to future energy crises and environmental challenges. Although platinum is an efficient catalyst for hydrogen evolution reactions (HERs), its high cost and stability challenges limit its widespread use. A novel platinum-based catalyst, comprising platinum nanoparticles on nitrogen-doped porous graphite (Pt-N-porous graphite), addresses these limitations. This catalyst prevents nanoparticle aggregation, provides a high specific surface area of 1308 m2 g−1, and enhances mass transfer and active site exposure. Additionally, it exhibits superior electrical conductivity compared to commercial Pt-C, enhancing charge transfer efficiency. The Pt-N-porous graphite catalyst achieves an overpotential of 99 mV at 100 mA cm−2 and maintains stable performance after 10000 cycles. Applied as a catalyst-coated membrane (CCM) in a proton exchange membrane (PEM) electrolyzer, it demonstrates excellent performance. Thus, the industrially synthesizable Pt-N-porous graphite catalyst holds great potential for large-scale energy applications.

Theoretical insights into the essential role of weak interactions in the electrocatalytic reduction of nitrobenzene: Ag-anchored graphene electrode

We used identical transition metal dimer with six coordinated nitrogen atoms to dope a monolayer graphene to construct homonuclear double-atom catalysts (DACs) and probed their catalytic efficiency for nitrobenzene reduction reaction (Ph-NO2RR) using density functional theory. The findings predict that Ag2N6@G possesses significant activity and selectivity, whose potential determining step (PDS) and competitive hydrogen evolution reaction (HER) process have the Gibbs free energy changes of 0.31 and −1.49 eV, respectively. An analysis of IRI (interaction region indicator) and IGMH (independent gradient model (IGM) based on Hirshfeld partition of molecular density) indicates a pronounced van der Waals interactions between Ph-NO2 and Ag2N6@G due to the benzene ring. When silver atom is introduced, the Gibbs free energy change of its PDS is reduced by 0.09 eV compared to the pure graphene as a catalyst. Through IRI, IGMH, and charge transfer analysis, it is confirmed that the van der Waals interactions between the catalyst and nitrobenzene crucially influences the activation of Ph-NO2.

In-situ fabrication of defect rich Cu2+1O on electrodeposited Cu cone arrays for promoting electrocatalytic anode hydrogen production

The low-potential formaldehyde oxidation reaction (FOR) is a significant replacement for oxygen evolution reaction, as FOR can couple with the cathode hydrogen evolution reaction (HER) to obtain a bipolar H2 production system with an extra low cell voltage. Cu-based electrocatalysts offer cost advantages in FOR but suffer from poor intrinsic activity and stability. Herein, a novel defect rich CF-Cu@Cu2+1O/Cu pinecone-shaped array electrocatalyst is fabricated by in-situ solution immersion of electrodeposited Cu cone arrays on foam for efficient and stable formaldehyde selective oxidation reaction to co-produce hydrogen and valuable formate. Benefitting from the partially mixed Cu2+1O in metallic copper and concomitant production of defect rich oxygen vacancies, only 0.04 VRHE is required for electrocatalytic FOR at 100 mA·cm−2 under alkaline conditions. FOR current density of CF-Cu@Cu2+1O/Cu electrode exhibits 2.35 times than that of CF-Cu (144 mA·cm−2) and 77 times than that of copper foam (4.4 mA·cm−2) at 0.5 VRHE. Moreover, the special pinecone-shaped structure is constructed to modify Cu-based catalysts with substantially enhanced stability. A FOR-HER co-electrolysis device of CF-Cu@Cu2+1O/Cu(+)||Pt/C(−) can achieve bipolar H2 production with an approaching 200 % Faradaic efficiency, requiring an extremely low electrical energy consumption of only ∼ 0.35 kWh per m3 of H2 and potential of 0.291 V at 100 mA·cm−2 at room temperature.

Cr-doped NiFe sulfides nanoplate array: Highly efficient and robust bifunctional electrocatalyst for the overall water splitting and seawater electrolysis

To replace precious metals and reduce production costs for large-scale hydrogen production, developing stable, high-performance transition metal electrocatalysts that can be used in a wide range of environments is desirable yet challenging. Herein, a self-supported hybrid catalyst (NiFeCrSx/NF) with high electrocatalytic activity was designed and constructed using conductive nickel foam as a substrate via manipulation of the cation doping ratio of transition metal compounds. Due to the strong coupling synergy between the metal sulfides NiS2, Fe9S11, and Cr2S3, as well as their interaction with the conductive nickel foam (NF), the energy barrier for catalytic reactions is reduced, and the charge transfer rate is enhanced. This significantly improves the hydrogen evolution reaction (HER) performance of NiFeCrSx/NF, achieving a current density of 10 mA cm−2 with an overpotential of just 66 mV. Furthermore, doping with chromium generates different valence states of Cr during the catalytic process, which can synergize with the high-valent Fe and Ni, promoting the formation of oxygen vacancies and enriching the active sites for the oxygen evolution reaction (OER). Consequently, at a current density of 10 mA cm−2 in 1.0 M KOH, the overpotential for OER is only 223 mV for NiFeCrSx/NF. Additionally, the in situ grown of self-supporting nanoflower structure on NiFe-LDH not only provides a large catalytic surface area but also facilitates electrolyte penetration during the catalytic process, endowing NiFeCrSx/NF with high long-term stability. When used as a bifunctional catalyst for overall water splitting, the NiFeCrSx/NF||NiFeCrSx/NF electrolyzer requires only 1.29 V to deliver a current density of 10 mA cm−2. Simultaneously, Cr doping protects the Fe sites by maintaining stable valence states, ensuring high performance and stability of NiFeCrSx/NF, even when it is utilized for seawater splitting. This strategy offers novel concepts for creating catalysts based on non-precious metals that can be utilized in various application scenarios.