Hydrogen Evolution Reaction In Alkaline Solution Research Articles

Highly Active W2C-Based Composites for the HER in Alkaline Solution: the Role of Surface Oxide Species.

The hydrogen evolution reaction (HER) is a crucial electrochemical process for the proposed hydrogen economy since it has the potential to provide pure hydrogen for fuel cells. Nowadays, hydrogen electroproduction is considerably expensive, so promoting the development of new non-noble catalysts for the cathode of alkaline electrolyzers appears as a suitable way to reduce the costs of this technology. In this sense, a series of tungsten-based carbide materials have been synthesized by the urea-glass route as candidates to improve the HER in alkaline media. Moreover, two different pyridinium-based ionic liquids were employed to modify the surface of the carbide grains and control the amount and nature of their surface species. The main results indicate that the catalyst surface composition is modified in the hybrid materials, which are then distinguished by the appearance of tungsten suboxide structures. This implies the action of ionic liquids as reducing agents. Consequently, differential electrochemical mass spectrometry (DEMS) is used to precisely determine the onset potentials and rate-determining steps (RDS) for the HER in alkaline media. Remarkably, the modified surfaces show high catalytic performance (overpotentials between 45 and 60 mV) and RDS changes from Heyrovsky-Volmer to Heyrovsky as the surface oxide structures get reduced. H2O molecule reduction is then faster at tungsten suboxide, which allows the formation of the adsorbed hydrogen at the surface, boosting the catalytic activity and the kinetics of the alkaline HER.

Regulating lattice tensile strain of Ru-Co bimetallic nanoparticles on carbonized wood for boosting its hydrogen evolution reaction

The development of high-performance catalysts for hydrogen production originating from water electrolysis at the cathode is very crucial, but still a challenge. Here, trace Ru-doped Co bimetallic nanoparticles (named RuxCoy/CW-z, x/y and z represent the molar ratio and total molar content of metals) were in situ decorated on carbonized wood by the vacuum impregnation and high-temperature annealing method. Ru1Co10/CW-2 demonstrates good hydrogen evolution reaction (HER) intrinsic activity with the overpotential of −42 mV (at −10 mA/cm−2) and Tafel slope of 75 mV dec−1 in a 1.0 M KOH, indicating its favorable HER reaction kinetics, and Ru1Co10/CW-2 exhibits good stability for 100 h (at −50 mA/cm−2). The good performances of Ru1Co10/CW-2 can be ascribed to the adjustable lattice tensile strain and electronic interactions, while the porous carbonized wood promotes electron transfer, electrolyte transport and gas escape. This work combines the advantages of lattice tensile strain with self-supported porous carbonized wood for HER in alkaline solution, which provides a valuable reference for synthesizing carbonized wood electrode materials with very low Ru content.

Tailoring Binding Abilities By Incorporating Oxophilic Transition Metals on 3D Nanostructured Ni Arrays for Accelerated Alkaline Hydrogen Evolution Reaction

Developing efficient and inexpensive electrocatalysts for the hydrogen evolution reaction (HER) in alkaline water electrolysis plays a key role for renewable hydrogen energy technology. The slow reaction kinetics of HER in alkaline solutions, however, has hampered advances in high-performance hydrogen production. Herein, we investigated the trends in HER activity with respect to the binding energies of Ni-based thin film catalysts by incorporating a series of oxophilic transition metal atoms. It was found that the doping of oxophilic atoms enables the modulation of binding abilities of hydrogen and hydroxyl ions on the Ni surfaces, leading to the first establishment of a volcano relation between OH-binding energies and alkaline HER activities. In particular, Cr-incorporated Ni catalyst shows optimized OH-binding as well as H-binding energies for facilitating water dissociation and improving HER activity in alkaline media. Further enhancement of catalytic performance was achieved by introducing an array of three-dimensional (3D) Ni nanohelixes (NHs) that provide abundant surface active sites and effective channels for charge transfer and mass transport. The Cr dopants incorporated into the Ni NHs accelerate the dissociative adsorption process of water, resulting in remarkably enhanced catalytic activities in alkaline medium. Our approach can provide a rational design strategy and experimental methodology toward efficient bimetallic electrocatalysts for alkaline HER using earth-abundant elements.Reference Journal of the American Chemical Society 3, 1399-1408 (2021) [Front Cover]

Amorphous quaternary alloy nanoplates for efficient catalysis of hydrogen evolution reaction

Developing a highly efficient non-precious transition metal-based electrocatalyst via a facile approach toward the hydrogen evolution reaction (HER) is critical for large-scale hydrogen production but still remains challenging. Herein, a cost-effective electrochemical deposition strategy is rationally proposed to construct amorphous quaternary FeCoNiCu alloy nanosheets supported on nickel foam (NF) towards this challenge. Benefiting from the synergistic effect of multi-metal atoms interaction and the high exposure of active sites caused by abundant open voids, the as-synthesized FeCoNiCu/NF electrode exhibits high catalytic activity and robustness toward HER in alkaline solution, requiring an overpotential of only 35 mV to reach a current density of 10 mA cm–2. This study may pave a new avenue to design advanced electrocatalyst for energy conversion.

Effect of oxygen vacancy on electrochemical performance of NiCo-layered double oxides as water splitting electrocatalyst

It is of importance for the design of cost-effective bifunctional electrocatalysts with good durability to decrease the energy rampart of total water decomposition. However, few electrocatalysts simultaneously exhibits excellent catalytic property and durability for both oxygen evolution reaction (OER) as well as hydrogen evolution reaction (HER). Herein, we adopt strategies toward defect engineering coupled with metal organic framework (MOF) to synthesize oxygen vacancy abundant NiCo-layered double oxides with hollow nanotube arrays structures supported on Ni foam (Ov-NiCo-LDO HNTAs/NF) via etching of ZnO template, which is considered as an efficient electrocatalyst for water splitting. The optimal Ov-NiCo-LDO HNTAs/NF reveals an ultra-low overpotential of 149 and 30 mV to afford a current density of 10 mA cm−2 for OER and HER in alkaline solution, respectively. Moreover, the catalyst also displays significant stability for 24 h with no significant decrease when a stable current density of 100 mA cm−2 is applied. A full water splitting system coupled with Ov-NiCo-LDO HNTAs/NF as both poles of hydrolysis tank can drive of 20 mA cm−2 current density at a potential of 1.68 V, along with steady operation for over 24 h, indicating that Ov-NiCo-LDO HNTAs/NF is a promising bifunctional electrocatalyst.

A high-performance self-supported multifunctional NF@Pt electrocatalyst for overall water splitting and rechargeable zinc-air battery

Developing multifunctional electrocatalysts has been a lasting challenge. Herein, with dual surface guiding agents NaI and PVP, uniformly dispersive Pt nanoclusters on self-supported nickel foam (NF@Pt-1) has been fabricated with low Pt loading. The obtained NF@Pt-1 performs excellently in hydrogen evolution reaction (HER), oxygen evolution reaction (OER), overall water splitting and rechargeable zinc-air battery. The NF@Pt-1 exhibits low HER overpotentials of 32.8 mV in alkaline solution and 50 mV in acidic solution at 10 mA cm−2. At a high current density of 100 mA cm−2, the overpotential for HER in alkaline solution is only 72.3 mV. The OER overpotential of NF@Pt-1 is 307 mV at 20 mA cm−2. All of these drive a 1.575 V overall water splitting potential. In rechargeable zinc-air battery, the recharging polarization voltage is only 0.869 V, 0.107 V smaller than that of the battery constructed with Pt/C. The excellent performances and the wide range of applications would be ascribed to the highly dispersion of Pt nanoclusters on self-support nickel foam under proper guiding effect of dual surface guiding agents. This work has explored an effective route for fabricating multifunctional electrocatalysts with relatively high performance-cost ratio.

Copper Phosphide Nanowires as High-Performance Catalysts for Urea-Assisted Hydrogen Evolution in Alkaline Medium.

Water electrolysis represented a promising avenue for the large-scale production of high-purity hydrogen. However, the high overpotential and sluggish reaction rates associated with the anodic oxygen evolution reaction (OER) posed significant obstacles to efficient water splitting. To tackle these challenges, the urea oxidation reaction (UOR) emerged as a more favorable thermodynamic alternative to OER, offering both the energy-efficient hydrogen evolution reaction (HER) and the potential for the treating of urea-rich wastewater. In this work, a two-step methodology comprising nanowire growth and phosphating treatment was employed to fabricate Cu3P nanowires on Cu foam (Cu3P-NW/CF) catalysts. These novel catalytic architectures exhibited notable efficiencies in facilitating both the UOR and HER in alkaline solutions. Specifically, within urea-containing electrolytes, the UOR manifested desirable operational potentials of 1.43 V and 1.65 V versus the reversible hydrogen electrode (vs. RHE) to reach the current densities of 10 and 100 mA cm-2, respectively. Concurrently, the catalyst displayed a meager overpotential of 60 mV for the HER at a current density of 10 mA cm-2. Remarkably, the two-electrode urea electrolysis system, exploiting the designed catalyst as both the cathode and anode, demonstrated an outstanding performance, attaining a low cell voltage of 1.79 V to achieve a current density of 100 mA cm-2. Importantly, this voltage is preferable to the conventional water electrolysis threshold in the absence of urea molecules. Moreover, our study shed light on the potential of innovative Cu-based materials for the scalable fabrication of electrocatalysts, energy-efficient hydrogen generation, and the treatment of urea-rich wastewater.

Copper-Doped NiCo2S4 Nanosheets Grown on Ni Foam Efficient Hydrogen Evolution Catalyst in Alkaline Solution

The development of economical, efficient and stable electrocatalysts for hydrogen evolution reaction (HER) with non-precious metals remains challenging. In this work, we have prepared Cu-doped NiCo2S4 nanosheets grown on nickel foam that can serve as excellent electrocatalysts for HER in alkaline solutions (Cu-NiCo2S4/NF). The good electrocatalytic properties and excellent stability of the pristine NiCo2S4 were achieved by changing its morphology through a simple Cu doping strategy. The optimum doping ratio for the Cu-NiCo2S4/NF catalyst in the HER requires an overpotential of only 155 mV to achieve a current density of 10 mA cm−2 and can operate stably for at least 12 h. This is mainly due to the fact that the doping of copper optimizes the electronic structure of the NiCo2S4/NF surface, providing more catalytically active sites and thus facilitating the effective release of hydrogen. In addition, the electrocatalytic activity of the Cu-NiCo2S4/NF material exceeds that of most reported noble metal-free catalysts, which also provides a new strategy for the preparation of NiCo2S4-based hydrolysis catalysts.

High-valence metal doped Co2FeAl alloy as efficient noble-metal-free electrocatalyst for alkaline hydrogen evolution reaction

Most efficient electrochemical hydrogen evolution reaction (HER) catalysts in alkaline solutions are based on precious metals, whose rarity and high cost are severely limiting their large-scale applications. In this work, we synthesized Mo-doped and W-doped Co2FeAl alloys by a simple coprecipitation method. The HER in alkaline solution is promoted through the synergistic effect of thermal annealing and doping of high-valence metal atoms. Thermal annealing could optimize the surface morphology and improve the crystallinity. In the meantime, the doping of high-valence metal atoms could further regulate the crystal structure and electronic structure of alloys. Therefore, annealing temperatures and doping concentrations have a marked impact on the catalytic performance. In particular, when the Mo doping concentration is 27 at% and the annealing temperature is 750 ℃, the synthesized Co2FeAlMo1.5 (750 ℃) alloy electrocatalyst exhibits the superior HER performance in alkaline media. It displays a low overpotential of only 71 mV at 10 mA cm−2 and a Tafel slope of 110 mV dec−1. An excellent stability is also demonstrated that the electrocatalyst can work stably for 20 h and the overpotential is only shifted by 2 mV after 1000 cycles. A series of characterization tests indicate that the crystal structure and electronic structure of Co2FeAlMo1.5 (750 ℃) are optimized, which can improve the catalytic activity and promote alkaline HER. This work provides a new strategy for improving the catalytic performance of non-noble metal electrocatalysts for alkaline HER.

Ru–MoS2@PPy hollow nanowire as an ultra-stable catalyst for alkaline hydrogen evolution reaction

Electrocatalytic hydrogen evolution reaction (HER) is one of the green and effective method to produce clean hydrogen energy. However, the development of non-Pt HER catalysts with excellent catalytic activity and long-term stability still remains a great challenge. Herein, a vertically aligned core-shell structure material with hollow polypyrrole (PPy) nanowire as a core and Ru-doped MoS2 (Ru–MoS2) nanosheets as a shell is firstly reported as a highly efficient and ultra-stable catalyst for HER in alkaline solutions. Results indicate that Ru–MoS2@PPy catalyst demands a low overpotential of 37 mV at 10 mA cm−2. In addition, the overpotential at 100 mA cm−2 is 157 mV and it is almost unchanged after 40,000 cyclic voltammetry cycles. The existence of PPy core not only ensures the vertical growth of MoS2 nanosheets to expose more edge sites, but also promotes the rapid transfer of electrons, contributing to the improvement of catalytic activity. More importantly, the strong interface interaction between MoS2 and PPy prevents the collapse of the vertical structure of MoS2 sheets in the electrocatalytic process and greatly enhances the stability of catalysts, which offers an effective strategy to design and synthesize the HER catalysts with superior catalytic stability.

Tailoring Binding Abilities By Incorporating Oxophilic Transition Metals on 3D Nanostructured Ni Arrays for Accelerated Alkaline Hydrogen Evolution Reaction

Developing efficient and inexpensive electrocatalysts for the hydrogen evolution reaction (HER) in alkaline water electrolysis plays a key role for renewable hydrogen energy technology. The slow reaction kinetics of HER in alkaline solutions, however, has hampered advances in high-performance hydrogen production. Herein, we investigated the trends in HER activity with respect to the binding energies of Ni-based thin film catalysts by incorporating a series of oxophilic transition metal atoms. It was found that the doping of oxophilic atoms enables the modulation of binding abilities of hydrogen and hydroxyl ions on the Ni surfaces, leading to the first establishment of a volcano relation between OH-binding energies and alkaline HER activities. In particular, Cr-incorporated Ni catalyst shows optimized OH-binding as well as H-binding energies for facilitating water dissociation and improving HER activity in alkaline media. Further enhancement of catalytic performance was achieved by introducing an array of three-dimensional (3D) Ni nanohelixes (NHs) that provide abundant surface active sites and effective channels for charge transfer and mass transport. The Cr dopants incorporated into the Ni NHs accelerate the dissociative adsorption process of water, resulting in remarkably enhanced catalytic activities in alkaline medium. Our approach can provide a rational design strategy and experimental methodology toward efficient bimetallic electrocatalysts for alkaline HER using earth-abundant elements.

Bimetallic Cobalt–Nickel Electrode Made by a Sputtering Technique for Electrocatalytic Hydrogen Evolution Reaction: Effect of Nickel Ratios

Electrocatalytic hydrogen evolution reaction (HER), a half-reaction of water splitting, is highly important to be developed for green and sustainable hydrogen production. In this work, a bimetallic cobalt–nickel (CoNix) alloy is deposited on nickel foam with a home-made target by using a radio frequency (RF) magnetron sputtering technique at a low deposition temperature. The as-sputtered CoNix was characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and X-ray photoelectron spectroscopy to evaluate its physical and chemical properties. The electrochemical measurement exhibited that the bimetallic CoNix alloy had a promising performance for HER in alkaline solutions. CoNi4, as the optimum ratio, possessed low overpotentials of 53 and 175 mV to achieve current densities of 10 and 100 mA/cm2, respectively. Moreover, among the as-sputtered CoNix, CoNi4 had the largest electrochemical surface-active area (485 cm2) and the lowest electron-transfer resistance (1.14 Ω). CoNi4 was also quite stable under the continuous operation of constant current densities of 10 and 50 mA/cm2 for 20 h. This work is based on the RF magnetron sputtering technique for developing bimetallic CoNix alloy as an efficient HER catalyst for electrochemical energy.

Impact of different metallic forms of nickel on hydrogen evolution reaction

In this work, we show the influence of strain in two different forms (plate and foil) of nickel for hydrogen evolution reaction (HER) in alkaline solution and 3.5% NaCl aqueous solution. The presence of tensile strain in nickel foil lowers the overpotential by about 10 mV to reach a current density of 10 mA cm−2 and improves the reaction kinetics of HER in alkaline solution. The Tafel slope showed a significant change in the strained nickel (i.e., in Ni foil) which gave a value of 111 mV dec−1 compared to unstrained nickel (Ni plate) which was found to be 151 mV dec−1, thus indicating a change in reaction mechanism. Compared to alkaline solution, the effect of strain becomes less pronounced in NaCl solution which can be attributed to Cl− adsorption on the electrode, thereby reducing its catalytic activity.

Amorphous CoFeB on nickel foam as a high efficient electrocatalyst for hydrogen evolution reaction

The development of high-performance, low cost and earth abundant catalysts for hydrogen evolution reaction (HER) is desired. This work presents amorphous CoFeB supported on nickel foam (NF), prepared by a facial chemical reduction method, as an active catalyst for HER in alkaline solution. Structure characterization indicated that with the incorporation of Fe atom, CoFeB catalysts exhibit similar petal-like granular morphology as CoB. The optimal CoFeB/NF-0.15 catalyst exhibits Brunauer-Emmett-Teller (BET) surface area of 27.4 m2 g−1, nearly two times larger than 13.2 m2 g−1 for CoB, suggesting higher specific surface area. CoFeB/NF-0.15 catalyst shows excellent HER performance and reaches −10 mA cm−2 at overpotential of 35 mV in alkaline solution, and Tafel slope of 84.7 mV dec−1, indicative of Volmer-Heyrovsky reaction mechanism. The synergistic effect among Fe, Co and B atoms and the more exposed active sites as well as faster electron transfer kinetics collectively contributed to the improved intrinsic activity of CoFeB for HER. Moreover, CoFeB/NF-0.15 exhibits good stability for over 16 h.

Synthesis of Co2FeAl alloys as highly efficient electrocatalysts for alkaline hydrogen evolution reaction

The development of cost-effective non-precious metal electrocatalysts is a major challenge for water splitting applications, but it is important for the realization of renewable energy systems. Alloying has proved an effective way to design metal-based electrocatalysts, and by controlling the annealing temperature, the surface morphology and crystallinity of the alloy can be tuned to control the hydrogen evolution reaction (HER) performance. In this work, with a simple coprecipitation method, we have prepared Co 2 FeAl alloys at different annealing temperatures (550 °C–670 °C), which exhibit excellent crystallinity and electrocatalytic performance for HER in alkaline solution. Among all conditions, the Co 2 FeAl alloys prepared at 620 °C shows the better crystallinity and the higher purity, and it could achieve a low overpotential of 149 mV at 10 mA cm −2 in alkaline solution. The overpotential demonstrates persistent stability with only 3 mV change after over 1000 cycles. Both density functional theory (DFT) calculations and experimental results revealed that alloying optimizes the electronic structure near the Fermi surface of the system, improving the electron transport efficiency and enhancing the catalytic activity. These Co 2 FeAl alloys are appealing candidates for high-performance alkaline HER electrocatalytic electrodes in water electrolysis due to their outstanding electrocatalytic properties. We demonstrate that the efficient electrocatalytic activity is due to high temperature annealing, along with the synergistic effect of alloying, lead to the surface structure and electronic structure of the alloy have changed. This strategy enables the Co 2 FeAl alloy electrocatalyst to achieve a low overpotential of 149 mV at 10 mA cm −2 in alkaline solution. • Co 2 FeAl Alloy is prepared by facile coprecipitation method. • High temperature annealing to adjust the crystal plane orientation of alloys. • It could achieve a low overpotential of 149 mV at 10 mA cm −2 in alkaline solution. • It shows highly efficient electrocatalytic activity for HER while remaining stable/durable. • DFT calculations revealed that it optimizes the electronic structure near the Fermi surface.

Designing a smart heterojunction coupling of cobalt-iron layered double hydroxide on nickel selenide nanosheets for highly efficient overall water splitting kinetics

To design heterojunction electrocatalysts for water splitting in industrial plants, replacing RuO2, IrO2, and Pt/C remains challenging. We prepared heterostructures of nickel selenide (NiSe) and cobalt-iron layer double hydroxide (CoFeLDH), CoFeLDH@NiSe, using hydrothermal and electrodeposition processes. The interfacial coupling enhanced the oxygen evolution reaction (OER) and the hydrogen evolution reaction (HER). The CoFeLDH@NiSe required an overpotential of 127 mV and 38 mV for a current density of 10 mA cm−2 with a Tafel slope of 37 mV dec−1 and 33 mV dec−1 for OER and HER in alkaline solutions. Density functional theory calculations showed the enhancement of OER performance. The catalytic activity of CoFeLDH@NiSe increased the electronic conductivity, enhancing the water splitting with 10 mA cm−2 at 1.51 V. The robustness was demonstrated by the long-term stability for 120 h. This study provides a strategy for developing heteronanostructure electrocatalysts for water splitting in fields such as metal-air batteries and energy storage.

Single-Layer Graphene Coated-Metal Nanoparticles for Water Splitting

Graphene-coated metal nanoparticles (NPs) have attracted great attention owing to their unique structural, photochemical and electrochemical properties based on electron communication between graphene and metal NPs. The development of highly efficient and non-precious metal-based electrocatalysts for water splitting comprising hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is still a big challenge. The hybridization of nitrogen (N)-doped carbon and cost-effective transition metals is a promising approach to produce highly active catalysts for HER and OER. Herein, a highly controllable chemical vapor deposition method is designed for large-scale synthesis of nickel nanoparticle wrapped by single-layer N-doped graphene (Ni@SNG), where silica work as molecule sieve to tactfully assist single-layer graphene growth by depressing diffusion of carbon radicals. The Ni@SNG sample synthesized at 800 oC shows excellent activity for HER in alkaline solution with a low overpotential of 100 mV at 10 mA cm-2, which is close to state-of-the-art Pt/C catalyst. Furthermore, the Ni@SNG catalyst supported on nickel foil is developed as a magnetic adsorption binder-free electrode, which exhibits much improved performance on catalytic activity and stability than common Nafion binder-based electrode. Therefore, magnetism adsorption technique, taking full advantages of magnetic catalysts, will be a greatly promising approach to overcome high electron resistance and poor adhesive stability of polymer binder-based electrodes in actual applications.

Hole‐Storage Enhanced a‐Si Photocathodes for Efficient Hydrogen Production

AbstractFerrihydrite (Fh) has been demonstrated as an effective interfacial layer for photoanodes to achieve outstanding photoelectrochemical (PEC) performance for water oxidation reaction owing to its unique hole‐storage function. However, it is unknown whether such a hole‐storage layer can be used to construct highly efficient photocathodes for hydrogen evolution reaction (HER). In this work, we report Fh interfacial engineering of amorphous silicon photocathode (with nickel as HER cocatalyst) achieving a photocurrent density of 15.6 mA cm−2 at 0 V vs. the reversible hydrogen electrode and a half‐cell energy conversion efficiency of 4.08 % in alkaline solution, outperforming most of reported a‐Si based photocathodes including multi‐junction configurations integrated with noble metal cocatalysts in acid solution. Besides, the photocurrent density is maintained above 14 mA cm−2 for 175 min with 100 % Faradaic efficiency for HER in alkaline solution. Our results demonstrate a feasible approach to construct efficient photocathodes via the application of a hole‐storage layer.

FeMn bimetallic MOF directly applicable as an efficient electrocatalyst for overall water splitting

The preparation of high-efficiency, stable and low-cost oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) electrocatalysts is always a challenge for new energy systems. In this work, a simple hydrothermal synthesis method was used to obtain FeMn bimetallic organic materials (FeMn-MOF/NF) grown on foamed nickel (NF) in one step. Moreover, FeMn-MOF/NF(1:1) had larger electrochemical specific surface area and unique nano-flower-like structure. The overpotentials of OER and HER in alkaline solution at a current density of 50 mA·cm−2 were 290 mV and 260 mV, respectively, and the total water splitting potential at this current density is only 1.7 V. The excellent activity and stability were attributed to the synergistic effect of FeMn. The bimetal and abundant active sites could promote the release of oxygen during the catalytic process.

Engineering heterostructure and crystallinity of Ru/RuS2 nanoparticle composited with N-doped graphene as electrocatalysts for alkaline hydrogen evolution

Crystalline engineering and heterostructure have attracted much attention as effective strategies to improve the electrocatalytic activity for hydrogen evolution reaction (HER). In this study, a new heterostructure catalyst (Ru/RuS2@N-rGO) with low crystallinity was fabricated by a simple and low-temperature method for HER in alkaline solution, applying the Na2SO4 as S source and polypyrrole as N source. Optimizing through the controllable crystalline engineering and composition ratio of Ru and RuS2, the Ru/RuS2@N-rGO heterocatalyst at the calcining 500 °C revealed highly efficient HER activity with overpotential 18 mV at a current density 10 mA/cm2 and remarkable stability for 24 h in 1.0 mol/L KOH. This work provides a facile and effective method in designing advanced electrocatalysts for HER in the alkaline electrolytes by synergistically structural and component modulations.