Electrolytic Hydrogen Production Research Articles

Efficient Hydrogen Production over Molybdenum Tungsten Bimetallic Oxide NF/PMonW12-n Catalyst on Nickel Foam.

Developing inexpensive, efficient, and stable catalysts is crucial for reducing the cost of electrolytic hydrogen production. Recently, polyoxometalates (POMs) have gained attention and widespread use due to their excellent electrocatalytic properties. This study designed and synthesized three composite materials, NF/PMonW12-n, by using phosphomolybdic-tungstic heteropolyacids as precursors to grow in situ on nickel foam via the hydrothermal process and subsequent calcination. Then, their catalytic performances are systematically investigated. This work demonstrates that the NF/PMonW12-n catalysts generate more low valent oxides under the synergistic effect of Mo and W, further enhancing activity for hydrogen evolution reaction (HER). Among these electrocatalysts, NF/PMo6W6 exhibits the perfect HER performance, η10 is only 74 mV. It also shows great stability during long-term electrolysis. The current study introduces a fresh approach for producing electrocatalysts that are both cost-effective and highly efficient.

One-Step Synthesis of High-Efficiency Oxygen Evolution Reaction Catalyst FeSx(Y/MB) with High Temperature Resistance and Strong Alkali

Given the energy crisis and escalating environmental pollution, the imperative for developing clean new energy is evident. Hydrogen has garnered significant attention owing to its clean properties, high energy density, and ease of storage and transportation. This study synthesized four types of catalysts—FeS(DI/MB), FeS(ET/MB), Fe(DI/MB), and Fe(ET/MB)—using two distinct solution systems: DI/MB and ET/MB. The FeS(DI/MB) catalyst, synthesized using the layered solution system (DI/MB), demonstrates a uniformly distributed and dense nanosheet structure, exhibiting excellent resistance to strong bases and superior catalytic properties. The FeS(DI/MB) electrode showed OER overpotentials of 460 mV and 318 mV in 1 M and 6 M, respectively, at current densities of up to 500 mA cm−2. Under industrial electrolysis test conditions, the FeS(DI/MB) electrode required only 262 mV to achieve a current density of 500 mA cm−2, operating in a high-temperature, strong alkaline environment of 6 M at 60 °C. Furthermore, the FeS(DI/MB) electrode exhibited excellent OER catalytic activity and stability, as evidenced by a 60 h stability test These findings provide valuable insights into the preparation of iron nickel sulfide-based catalysts, and further in-depth and comprehensive exploration is anticipated to yield the excellent catalytic performance of these catalysts in the realm of electrolytic water hydrogen production.

Optimizing Renewable Energy Integration for Sustainable Fuel Production: A Techno-Economic Assessment of Dimethyl Ether Synthesis via a Hybrid Microgrid-Hydrogen System

This study offers an in-depth analysis and optimization of a microgrid system powered by renewable sources, designed for the efficient production of hydrogen and dimethyl ether—key elements in the transition toward sustainable fuel alternatives. The system architecture incorporates solar photovoltaic modules, advanced battery storage solutions, and electrolytic hydrogen production units, with a targeted reduction in greenhouse gas emissions and the enhancement of overall energy efficiency. A rigorous economic analysis was conducted utilizing the HYSYS V12 software platform and encompassing capital and operational expenditures alongside profit projections to evaluate the system’s economic viability. Furthermore, thermal optimization was achieved through heat integration strategies, employing a cascade analysis methodology and optimization via the General Algebraic Modeling System (GAMS), yielding an 83% decrease in annual utility expenditures. Comparative analysis revealed that the energy requirement of the optimized system was over 50% lower than that of traditional fossil fuel-based reforming processes. A comprehensive assessment of CO2 emissions demonstrated a significant reduction, with the integration of thermal management solutions facilitating a 99.24% decrease in emissions. The outcomes of this study provide critical insights into the engineering of sustainable, low-carbon energy systems, emphasizing the role of renewable energy technologies in advancing fuel science.

Techno-economic assessment of renewable hydrogen production for mobility: A case study

Renewable hydrogen produced by water electrolysis from intermittent energy sources (i.e. sun and wind) is considered one of the most promising energy carriers for the decarbonisation of the so-called “hard-to-abate” sectors, especially heavy-duty transport and industry. To this reason, several new projects are currently under development and public fundings are widely available to boost the renewable hydrogen market. In this fast-changing scenario, this paper presents the techno-economic analysis of an integrated system where renewable power generation, electrolytic hydrogen production and final hydrogen use are closely integrated within a specific site, allowing higher efficiency as well as a containment of hydrogen production and handling cost. The analysis here presented considers a specific case study that includes a 12.5 MWP photovoltaic plant, a 5 MW electrolyser capable to produce nearly 300 t/yr. of renewable hydrogen, and a compression and storage system, all located in Sardinia (Italy). Differently from previous studies, this work faces the analysis from two opposite perspectives: on the one hand, it allows the assessment of the levelized cost of hydrogen during the whole project’s life, making the results comparable to those from other similar analyses; on the other hand, it presents the calculation of project’s profitability in terms of net present value, internal rate of return and payback time from the perspective of a potential investor. The analysis shows that a whole investment of about 20.3 M€ is required, which allows to achieve a levelised cost of hydrogen of 4.09 €/kg, which can decrease to 2.97 €/kg considering the revenues from selling oxygen and the overproduction of electricity. The potential use of renewable hydrogen in urban public transport (by means of fuel cell electric vehicles) has been considered as well, in comparison with conventional diesel buses. Despite the lower cost for fuel (0.41 €/km for hydrogen buses vs. 0.72 €/km for diesel buses) and maintenance and repair (0.20 €/km vs. 0.27 €/km), as well as the lower CO2 emission (some 76 t/yr. saved per bus), the very high investment cost for hydrogen-fuelled buses (up to 720,000 €) makes hydrogen still not competitive with diesel for urban transport, being hydrogen buses characterised by a whole specific transport cost of 1.45 €/km, to be compared with 1.04 €/km for diesel buses.

Quantitative Evaluation Method of Full‐Cycle Life of Hydrogen Production by Electricity Considering Line Electrothermal Coupler

This study introduces a quantitative evaluation method for the lifecycle of electric hydrogen production in microgrids, considering line electric thermal couplers. By analyzing the operational mechanism and benefits of hydrogen production through residual electricity, we systematically evaluated the cost‐effectiveness of Proton Exchange Membrane electrolytic hydrogen production. A comprehensive lifecycle cost model was constructed, including equipment investment, maintenance, operating costs, and line thermocouple failure costs. By combining hydrogen sales, electricity consumption, new energy subsidies, and delayed construction benefits, a lifecycle benefit model was developed to measure economic performance. Experimental results showed that under a 5% power outage rate, the hydrogen distribution network has a short investment payback period, high production, and significant economic benefits, reaching 23.19 million US dollars by the sixth year. This study provides valuable insights for economic decision‐making in electric hydrogen microgrids.

Effects of emissions caps on the costs and feasibility of low-carbon hydrogen in the European ammonia industry

The European ammonia industry emits 36 million tons of carbon dioxide annually, primarily from steam methane reforming (SMR) hydrogen production. These emissions can be mitigated by producing hydrogen via water electrolysis using dedicated renewables with grid backup. This study investigates the impact of decarbonization targets for hydrogen synthesis on the economic viability and technical feasibility of retrofitting existing European ammonia plants for on-site, semi-islanded electrolytic hydrogen production. Results show that electrolytic hydrogen cuts emissions, on average, by 85% (36%-100% based on grid price and carbon intensity), even without enforcing emission limits. However, an optimal lifespan average well-to-gate emission cap of 1 kg carbon dioxide equivalent (CO2e)/kg H2 leads to a 95% reduction (92%-100%) while maintaining cost-competitiveness with SMR in renewable-rich regions (mean levelized cost of hydrogen (LCOH) of 4.1 euro/kg H2). Conversely, a 100% emissions reduction target dramatically increases costs (mean LCOH: 6.3 euro/kg H2) and land area for renewables installations, likely hindering the transition to electrolytic hydrogen in regions with poor renewables and limited land. Increasing plant flexibility effectively reduces costs, particularly in off-grid plants (mean reduction: 32%). This work guides policymakers in defining cost-effective decarbonization targets and identifying region-based strategies to support an electrolytic hydrogen-fed ammonia industry.

Research on Hybrid Rectifier for High Power Electrolytic Hydrogen Production Based on Modular Multilevel Converter

Aiming at the problem that silicon-controlled rectifiers (SCR) and pulse width modulation (PWM) rectifiers cannot balance high power levels, high hydrogen production efficiency, and high grid connected quality in the current research on rectifier power supplies for electrolytic hydrogen production, a new hybrid rectifier topology based on a modular multilevel converter (MMC) is proposed. The hybrid topology integrates a silicon-controlled rectifier (SCR) with an auxiliary power converter, wherein the SCR is designated as the primary power source for electrolytic hydrogen production. The auxiliary converter employs a cascaded modular multilevel converter (MMC) and an input-series-output-parallel (ISOP) phase-shifted full-bridge (PSFB) arrangement. This configuration allows the auxiliary converter to effectively mitigate AC-side harmonics and minimize DC-side ripple, concurrently transmitting a small amount of power. The effectiveness of the hybrid rectifier in achieving low ripple and harmonic distortion outputs was substantiated through hardware-in-the-loop experiments. Notably, the hybrid topology is characterized by its enhanced electric-to-hydrogen conversion efficiency, elevated power density, cost efficiency, and improved grid compatibility.

First-principles calculation on electronic properties of hydrogen evolution reaction of Ni-based electrode surfaces with different monatomic doping

At present, the hydrogen evolution reaction (HER) of Ni-based electrode has an important influence on water electrolysis hydrogen production technology, involving complex electrochemical process of electrode. In this project, Materials Studio (MS) software was used to design and construct Ni-based electrode surface (NES) models with monatomic Mo, Co, Fe, Cr doping, and the NES models attached 1 H atom and 2H atoms were denoted as the NES-H models and NES-2H model, respectively. Then the first-principles calculation was carried out.The results showed that the doping of different atoms can effectively change the work function of the pure Ni. In the charge transfer process of the four NES-2H models, the distance between the two H atoms is most affected by Mo doping, and they leave the Ni electrode surface as a single H ion, respectively, while the effect on Co, Fe and Cr doping is relatively consistent, and they leave the Ni electrode surface with H2 molecules, respectively. The doping of four single atoms changes the distance of valence band (VB) top and conduction band (CB) bottom from Fermi level in NES, NES-H and NES-2H models, and affects the HER, in which Mo doping has the greatest effect. The TDOS of the above models is mainly derived from the PDOS of the d orbitals of the doped atoms and Ni atoms. The results will provide a theoretical basis for the research and development of Ni-based electrode materials in HER.

Progress in Biomass Electro‐Valorization for Paired Electrosynthesis of Valuable Chemicals and Fuels

Environmental and energy concerns surrounding the use of fossil fuels are driving an increasingly rapid transition to sustainable and eco‐responsible processes. Electrochemical processes can provide the necessary sustainability and economic roadmap for storing intermittent and renewable electricity by synthesizing, in cogeneration electrolyzers, energy carriers and/or synthetic chemicals (hydrogen, ammonia, etc.) via flagship reduction reactions (hydrogen evolution reaction (HER), nitrogen reduction reaction (NRR), etc.). To balance the electrochemical process, these cathodic processes have long been coupled to the oxygen evolution reaction (OER), which ultimately consumes almost 90% of the energy input. Recent years have witnessed an overwhelming development of anode scenarios based on biomass substrates, because OER cannot be driven below a certain potential threshold, while organics are thermodynamically more favorable. Therefore, paired electrolysis, which refers to cases where electrochemical oxidation and reduction are desired, embraces the electrocatalysis community for the electrolytic production of hydrogen, ammonia, etc. (cathode side), in parallel with value‐added chemicals (anode side), all with a modest electricity input. The trade‐off is selectivity at relevant current densities. This review discusses, the progress, challenges, and potential of biomass‐fueled paired electrosynthesis of valuable chemicals and fuels. Fundamental principles, main biomass solubilization methods, and different scenarios for paired electrosynthesis are presented.

Integrated Electrolytic Hydrogen Production for Boosting Energy Utilization

AbstractElectrocatalytic water splitting, powered by clean energy sources, represents a sustainable method for hydrogen (H2) production. Although extensive research has concentrated on performance indicators like current density and faradaic efficiency, the widespread adoption of electrocatalytic water splitting encounters challenges primarily due to high cell voltages and electricity costs. These issues stem from the sluggish kinetics of the anodic oxygen evolution reaction (OER). Various efforts to replace sluggish OER with thermodynamically more favorable anodic reactions have been demonstrated as pathbreaking strategies for energy‐efficient H2 evolution. In this concept, we aim to comprehensively explore alternative electrochemical oxidation reactions combined with H2 evolution and propose insights for the future development of cost‐effective integrated electrolysis for H2 production.

Design, global energy integration, and sustainability analyses of a process coupling renewable energy water electrolysis for hydrogen production with ammonia synthesis

The conventional ammonia synthesis process typically depends on fossil energy and faces challenges such as low utilization of elements and high CO2 emissions, leading to unsatisfactory economic performance. In order to achieve green synthesis and sustainable development of ammonia, this study constructed a process for renewable energy water electrolysis hydrogen production coupled with ammonia synthesis. The process includes: PEM electrolysis water hydrogen production coupling synthesis ammonia (PEM-GHtA) and SOEC electrolysis water hydrogen production coupling synthesis ammonia (SOEC-GHtA). Compared to traditional ammonia synthesis, the new process eliminates the use of carbon conversion for hydrogen production. Instead, it utilizes green electrolysis to split water into hydrogen and oxygen, leading to enhanced energy efficiency and decreased carbon emissions. By employing modeling, simulation, global energy integration, and conducting technical and economic analysis of the new process, this study elucidates the technical advantages and economic competitiveness of the new process over the traditional ammonia synthesis process. According to the analysis results, the utilization rates of hydrogen element in the PEM-GHtA and SOEC-GHtA processes are 92.64% and 92.59%, and the utilization rate of nitrogen element is 90.56% and 90.50%, respectively, much higher than the traditional ammonia synthesis process. In addition, the SOEC-GHtA demonstrated improved energy efficiency, achieving a range of 72.19–75.08%. The CO2 emissions of the two green ammonia synthesis processes are 0.17–0.81 t CO2/t NH3, much lower than the 1.6–3.6 t CO2/t NH3 of the traditional ammonia synthesis process. Based on the current market price, the production cost of green ammonia is relatively high, which has no economic advantage over the traditional ammonia synthesis process. Considering the future implementation of carbon taxes and the decreasing prices of renewable energy electricity to 0.014 $/kWh, the production costs of PEM-GHtA and SOEC-GHtA will be reduced to 359.7 $/t NH3 and 343.5 $/t NH3 respectively. In comparison to the traditional process (403.1–514.7 $/t NH3), the new process offers substantial economic benefits and shows promising prospects for further development.

Research on Capacity Optimization Configuration of Renewable Energy Off Grid Hydrogen Production System Considering Collaborative Electrolysis

This study proposes a multitype electrolytic collaborative hydrogen production model for optimizing the capacity configuration of renewable energy off grid hydrogen production systems. The electrolytic hydrogen production process utilizes the synergistic electrolysis of an alkaline electrolyzer (AEL) and proton exchange membrane electrolyzer (PEMEL), fully leveraging the advantages of the low cost of the AEL and strong regulation characteristics of the PEMEL. For the convenience of the optimization solution, the article constructs a mixed linear optimization model that considers the constraints during system operation, with the objective function of minimizing total costs while meeting industrial production requirements. Gurobi is used for the optimal solution to obtain the optimal configuration of a renewable energy off grid hydrogen production system. By comparing and analyzing the optimal configuration under conventional load and high-load conditions, it is concluded that collaborative electrolysis has advantages in improving resource consumption and reducing hydrogen production costs. This is of great significance for optimizing the capacity configuration of off grid hydrogen production systems and improving the overall economic benefits of the system.

Bioelectrochemical reactor to manage anthropogenic sulfate pollution for freshwater ecosystems: Mathematical modeling and experimental validation

Anthropogenic sulfate loading into otherwise low-sulfate freshwater systems can cause significant ecological consequences as a biogeochemical stressor. To address this challenge, in situ bioremediation technologies have been developed to leverage naturally occurring microorganisms that transform sulfate into sulfide rather than implementing resource-intensive physio-chemical processes. However, bioremediation technologies often require the supply of electron donors to facilitate biological sulfate reduction. Bioelectrochemical systems (BES) can be an alternative approach for supplying molecular hydrogen as an electron donor for sulfate-reducing bacteria through water electrolysis. Although the fundamental mechanisms behind BESs have been studied, limited research has evaluated the design and operational parameters of treatment systems when developing BESs on a scale relevant to environmental systems. This study aimed to develop an application-based mathematical model to evaluate the performance of BESs across a range of reactor configurations and operational modes. The model was based on sulfate transformation by hydrogenotrophic sulfate-reducing bacteria coupled with the recovery of solid iron sulfide species formed by the oxidative dissolution of dissolved ferrous iron from a stainless steel anode. Sulfate removal closely corresponded to the rate of electrolytic hydrogen production and hydraulic residence time but was less sensitive to specific microbial rate constants. The mathematical model results were compared to experimental data from a pilot-scale BES tested with nonacidic mine drainage as a case study. The close agreement between the mathematical model and the pilot-scale BES experiment highlights the efficacy of using a mathematical model as a tool to develop a conceptual design of a scaled-up treatment system.

Numerical assessment and optimization of photovoltaic-based hydrogen-oxygen Co-production energy system: A machine learning and multi-objective strategy

Green hydrogen production technology based on photovoltaic (PV), battery energy storage system (BESS) and proton exchange membrane (PEM) water electrolysis plays a crucial part in the transition process of energy to zero carbon technology. But few studies have focused on achieving all-day continuous hydrogen production, which is the key to large-scale hydrogen utilization. In this study, we developed an off-grid PV-BESS-PEM system for hydrogen and oxygen production. Firstly, the PV, BESS and PEM water electrolysis components were modeled and model validation was performed. Secondly, an energy management strategy (EMS) is proposed to achieve the goal of continuous and stable hydrogen production. Then, a surrogate model between design variables and optimization objectives is established based on machine learning methods, and a multi-objective optimization algorithm is used to drive the optimization process. Finally, a case study of the PV-BESS-PEM system is presented based on solar irradiation data in Lhasa, where there is sufficient solar resources and oxygen demand. The results demonstrate that the EMS can satisfy the purpose of all-day continuous and stable hydrogen production. The number of cells in the electrolyzer and the water temperature have a significant effect on the hydrogen production and the electrolysis efficiency. And the optimal system has increased the hydrogen production by 16.80 % and the electrolysis efficiency of PEM by 12.08 %, respectively. Herein, the methodological framework is expected to provide theoretical guidance for large-scale water electrolysis hydrogen production applications based on solar energy.

Atomically Precise Mo2Cu17 Bimetallic Nanocluster: Synergistic Mo2O4-Coupled Copper Alkynyl Cluster for the Improved Hydrogen Evolution Reaction Performance.

Electrolytic hydrogen production via water splitting holds significant promise for the future of the energy revolution. The design of efficient and abundant catalysts, coupled with a comprehensive understanding of the hydrogen evolution reaction (HER) mechanism, is of paramount importance. In this study, we propose a strategy to craft an atomically precise cluster catalyst with superior HER performance by cocoupling a Mo2O4 structural unit and a Cu(I) alkynyl cluster into a structured framework. The resulting bimetallic cluster, Mo2Cu17, encapsulates a distinctive structure [Mo2O4Cu17(TC4A)4(PhC≡C)6], comprising a binuclear Mo2O4 subunit and a {Cu17(TC4A)2(PhC≡C)6} cluster, both shielded by thiacalix[4]arene (TC4A) and phenylacetylene (PhC≡CH). Expanding our exploration, we synthesized two homoleptic CuI alkynyl clusters coprotected by the TC4A and PhC≡C- ligands: Cu13 and Cu22. Remarkably, Mo2Cu17 demonstrates superior HER efficiency compared to its counterparts, achieving a current density of 10 mA cm-2 in alkaline solution with an overpotential as low as 120 mV, significantly outperforming Cu13 (178 mV) and Cu22 (214 mV) nanoclusters. DFT calculations illuminate the catalytic mechanism and indicate that the intrinsically higher activity of Mo2Cu17 may be attributed to the synergistic Mo2O4-Cu(I) coupling.

Research Advances of Non-Noble Metal Catalysts for Oxygen Evolution Reaction in Acid.

Water splitting is an important way to obtain hydrogen applied in clean energy, which mainly consists of two half-reactions: hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). However, the kinetics of the OER of water splitting, which occurs at the anode, is slow and inefficient, especially in acid. Currently, the main OER catalysts are still based on noble metals, such as Ir and Ru, which are the main active components. Hence, the exploration of new OER catalysts with low cost, high activity, and stability has become a key issue in the research of electrolytic water hydrogen production technology. In this paper, the reaction mechanism of OER in acid was discussed and summarized, and the main methods to improve the activity and stability of non-noble metal OER catalysts were summarized and categorized. Finally, the future prospects of OER catalysts in acid were made to provide a little reference idea for the development of advanced OER catalysts in acid in the future.

Self-standing Ni–Cu–Ti/NCNTs electrocatalyst with porous structure for hydrogen evolution reaction

The development of water electrolysis hydrogen production technology is of great significance for accelerating the global carbon neutrality goals. Nickel-based electrode materials are considered the most promising catalysts for alkaline water electrolysis. However, the slow kinetics of the hydrogen evolution reaction remains a key challenge to be solved. To address this, a porous Ni–Cu–Ti/NCNTs cathode electrode was prepared using the powder metallurgy method. The microstructure characterizations and electrochemical measurements revealed that adjusting the content of NCNTs, while maintaining the Ni–Cu–Ti ratio of 5.5:3.5:1, can improve the catalytic activity of hydrogen evolution to a certain extent. Among the electrodes tested at room temperature, the one with 0.7% NCNT content exhibited the best performance in terms of hydrogen evolution. The analysis suggests that the porous structure of the electrode provides ample channels for object transmission. The addition of NCNTs further enhances the surface roughness of the electrode, exposing more active sites. Additionally, NCNTs promote electron transfer, synergize with Ni, Cu, and Ti, and improve the catalytic activity of hydrogen evolution.

Using electrolytic hydrogen production and energy storage for balancing a low carbon electricity grid: Scenario assessments for India

Nuclear reactors and variable renewables will play a significant role in the global energy transition as providers of low carbon electricity to various end use sectors. Real time balancing of power demand and supply without modulation or curtailment is possible using electrolytic hydrogen plants and energy storage systems. The generation mix adopted and load profiles are unique to a country and this study considers the specific case of India. This work analyses the use of grid connected water electrolysers, grid scale battery storage, hydrogen storage and fuel cells as flexible loads and dispatch schemes for grid balancing. Based on postulated long term power generation scenarios for India, the minimum required system sizes for grid balancing are estimated and techno-economic uncertainties are assessed. The use of water electrolysers is prioritized to make use of excess power, while minimizing battery storage requirement. This scheme can potentially produce a substantial share of low carbon hydrogen in India for use in industrial decarbonization, thus reducing the need for additional generation infrastructure.

Hydrogen production via electrolysis: State-of-the-art and research needs in risk and reliability analysis

Water electrolysis is the primary production technology for clean hydrogen, and thus ensuring safe and reliable deployment and operation of electrolyzers is essential to global sustainability efforts. In this paper, electrolytic hydrogen production pathways and upcoming deployment capacities are briefly discussed. Then we examine the main risk and reliability challenges and analyze the state of the art in quantitative risk assessment (QRA) of electrolysis technologies. We identify gaps in electrolysis QRA studies and present recommendations to enable more robust risk and reliability analysis for these technologies. Recommendations and opportunities for research to fill these gaps include: developing and adopting a system reliability approach in electrolysis risk analysis, developing and disseminating detailed electrolysis system design documentation, developing reliability data collection and analysis methods and tools, conducting importance measures analysis, conducting uncertainty analysis and propagation, developing electrolysis QRA standards, and creating programs to develop and educate the hydrogen risk and reliability workforce.

Synthesis and HER properties of honeycomb Mo2WS6/NF nanorod array solid solution alloys

The electrolytic water-based hydrogen production demonstrates exceptional selectivity, minimal environmental impact, and superior purity of the generated hydrogen, thereby presenting promising prospects for a wide range of applications. The scarcity and high cost of Pt-based catalysts for industrial applications necessitate the development of low-cost, stable, and efficient transition metal electrocatalysts for hydrogen electrochemical precipitation (HER). In this paper, Mo2WS6 nanorod array with honeycomb structure was successfully synthesized via one-step hydrothermal vulcanisation of transition metals W and Mo on nickel foam (NF) substrate. The honeycomb nanorod array structure exhibits enhanced specific surface area and abundant active sites, and the well-defined pore structure facilitates the transport of electrolyte and reactive substances. The intrinsic activity of the active sites is significantly enhanced by the synergistic effect of MoS2 and WS2, facilitated by the formation of solid solution alloys. Excellent HER performance (η10=63 mV, η100=183 mV) was demonstrated in alkaline electrolyte (1.0 M KOH) with a corresponding Tafel slope of 93 mV dec−1. Furthermore, Mo2WS6 exhibited excellent stability after undergoing 5000 cycles of charge/discharge and a constant voltage test lasting for 96 hours. This study provides a novel approach for facile synthesis of high-efficiency HER catalysts by a one-step hydrothermal method.