High-performance Hydrogen Evolution Reaction Research Articles

Synergistic Configuration of Binary Rhodium Single Atoms in Carbon Nanofibers for High-Performance Alkaline Water Electrolyzer.

Electrochemical alkaline water electrolysis offers significant economic advantages; however, these benefits are hindered by the high kinetic energy barrier of the water dissociation step and the sluggish kinetics of the hydrogen evolution reaction (HER) in alkaline media. Herein, the ensemble effect of binary types of Rh single atoms (Rh-Nx and Rh-Ox) on TiO2-embedded carbon nanofiber (Rh-TiO2/CNF) is reported, which servesas potent active sites for high-performance HER in anion exchange membrane water electrolyzer (AEMWE). Density functional theory (DFT) analyses support the experimental observations, highlighting the critical role of binary types of Rh single atoms facilitated by the TiO2 sites. The Rh-TiO2/CNF demonstrates an impressive areal current density of 1 A cm-2, maintaining extended durability for up to 225 hin a single-cell setup. Furthermore, a 2-cell AEMWE stack utilizing Rh-TiO2/CNF is tested under industrial-scale conditions. This research makes a significant contribution to the commercialization of next-generation high-performance and durable AEMWE stacks for clean hydrogen production.

"Synergistic Hybridization of Mn-MOF@rGO and Ti3C2 for High-Performance Supercapattery Devices and Hydrogen Evolution Reaction"

The burgeoning interest in two-dimensional (2D) materials stems from their heightened storage capacity and superior conductivity. Here, we synthesized a metal-organic framework of manganese (Mn-MOF) and introduced reduced graphene oxide (rGO) doping into this heterostructure using a hydrothermal method. Subsequently, Ti3C2Tx MXene was prepared via a template method. The Mn-MOF@rGO was then combined with Ti3C2Tx MXene in a 50/50 wt% ratio using hydrothermal techniques, and their structural and electrochemical characteristics were evaluated. In 3-electrode measurements, the MnMOF@rGO/Ti3C2Tx composite conductor exhibited a precise capacity of 2645 C/g (5.29 C/cm3) at 1.8 A/g. Furthermore, a hybrid device termed a supercapattery was fabricated employing MnMOF@rGO/Ti3C2Tx along with activated carbon (AC) composite electrodes, demonstrating remarkable energy density of 67 Wh/kg and an impressive power density of 880 W/kg. After 8,000 cycles, the electrode exhibited 84% capacity retention and maintained 92% columbic efficiency. In the hydrogen evolution reaction (HER), the MnMOF@rGO/Ti3C2Tx composite displayed a minimal Tafel slope of 54.65 mV/dec. These two-dimensional composite electrodes offer novel avenues for the advancement of high-performance energy device.

Transition metal-modified armchair graphene network for high-performance hydrogen evolution reaction catalysts

This study explores the structural, electronic, and catalytic properties of armchair hexagonal graphene networks (AHGN) modified with single transition metal (TM) atoms from Period V. Substitutions of Ag, Mo, Nb, Pd, Rh, Ru, Tc, Y, and Zr were investigated, revealing significant changes in bond lengths, bond angles, and dihedral angles. The binding energies indicate that TM substitutions do not drastically destabilize AHGN, suggesting potential applications requiring modified electronic properties. Electronic investigations showed that TM substitutions influence the partial density of states (PDOS) and energy gaps (ΔE), with Tc significantly reducing ΔE, indicating a shift towards metallic behavior. Mulliken charge analysis highlighted the electron density redistribution around TM atoms and edge carbons, enhancing electronic conductivity and chemical reactivity. Based on the results, AHGN-Rh-H, AHGN-Pd-H, and AHGN-Mo-H demonstrate the most efficient catalytic performance for the hydrogen evolution reaction (HER), with ΔG values comparable to platinum, underscoring their potential for practical hydrogen production applications. Conversely, materials like AHGN-Nb-H and AHGN-Zr-H exhibit higher ΔG values, indicating lower efficiency for HER. Global reactivity parameters (GRPs) analysis revealed AHGN-Tc with the most negative chemical potential (−4.010 eV) and highest electronegativity (4.010 eV), indicating strong electron-accepting and electron-attracting abilities. These findings underscore the potential of TM-substituted AHGN for advanced electronic applications and efficient hydrogen production.

Electrodeposition of Ni–MoS2 as effective hydrogen evolution reaction catalysts in alkaline media

Highly active, long-lasting, and economically feasible nonprecious metal-based electrocatalysts are urgently required for the slow hydrogen evolution reaction (HER) in alkaline conditions. Direct current (DC) electrodeposition was used to develop the highly active Ni–MoS2 composite coatings for efficient hydrogen generation. Scanning electron microscopy (SEM), Energy Dispersive X Ray Spectroscopy (EDS), X-ray diffraction (XRD), and linear sweep voltammetry (LSV) were used to evaluate the coatings. Ni–MoS2 composite coatings behaved almost identically to pure platinum metal. The Ni–MoS2 coating produced 1.0 g/l demonstrated a low overpotential for HER. The HER process's analyzed from Volmer-Tafel mechanistic route has an extremely low slope of 56.5 mV/dec. All the coated samples were subjected to chronopotentiometry (CP). This catalyst's high HER performance shows that it has significant potential for practical applications.

Cerium single atom anchored silver selenide: A high-performance catalyst for hydrogen evolution reaction with ultra-low activation energy and enhanced stability

Single-atom catalysts (SAC) have enabled high electrocatalytic activity production because of the enormous active sites bearing catalysts for hydrogen evolution reaction (HER). Herein, we report cerium single atom (Cesa) anchored silver selenide (Ag2Se) via metal-chalcogenide interaction for high-performance HER evolution. The designed electrocatalyst possesses extraordinary electrochemical and optical properties, thus the Cesa-Ag2Se could be a potential catalyst for the photo-electrochemical HER process. The sluggish diffusion rate of the Ce atom within the Ag2Se facilitates the high stability and the dispersed Cesa displayed ∼2 eV of energy differences with the Ce dimer proving the formation of dispersed Cesa over Ag2Se is potentially favorable. The minimum energy pathway (MEP) suggested the Cesa-Ag2Se system established only 0.003 eV as an ultra-low activation energy barrier in order to produce H2, which is by far the finest performance of Ag2Se-based thermodynamically favourable catalysis. The accumulated electron density due to the presence of Cesa enabled the presence of a large number of potential active sites (Ce and Ag) for hydrogen adsorption, in addition, the supportive zero band gap of the Ag2Se accelerated the kinetics for HER. Ultimately, we employed the Wentzcovitch cell dynamics-based molecular dynamics study for H* adsorbed Cesa-Ag2Se that suggests the stability of the catalyst for 500 fs. The in-depth HER modelling using the Lennard-Jones force field demonstrated the insightful dynamics behaviour of the catalytical system.

Surface Termination (-O, -F or -OH) and Metal Doping on the HER Activity of Mo2CTx MXene.

Two-dimensional MXenes have recently garnered significant attention as electrocatalytic materials for hydrogen evolution reaction (HER). However, previous theoretical studies mainly focused on the effect of pure functional groups while neglecting hybrid functional groups that are commonly observed in experiments. Herein, we investigated the hybrid functionalized Mo2CTx MXene (T=-O, -F or -OH) to probe the HER properties. In binary O/F co-functionalization, the presence of F groups would attenuate the H adsorption and lead to the enhanced HER activity than the fully O-terminated Mo2CO2. However, the surface HER activity of ternary O/F/OH functionalized Mo2CTx is not satisfactory owing to the relatively weak H adsorption capacity. To further enhance the catalytic activity, modification was performed by introducing another metal element into its lattice structure. The doped metal (Fe, Co, Ni, Cu) exhibits reduced charge transfer to O compared to Mo atoms, leading to enhanced H adsorption and improved overall activity. The synergistic effect of hybrid functionalization and TM modification provides useful guidance for achieving feasible Mo2CTx candidates with high HER performance, which can be applied to the electrocatalytic applications of other MXenes.

Magnetic Co2Si monolayer with high performance hydrogen evolution reaction: a first-principle prediction

Magnetic Co2Si monolayer with high performance hydrogen evolution reaction: a first-principle prediction

An Efficient and Stable MXene-Immobilized, Cobalt-Based Catalyst for Hydrogen Evolution Reaction

Hydrogen (H2) is considered to be the best carbon-free energy carrier that can replace fossil fuels because of its high energy density and the advantages of not producing greenhouse gases and air pollutants. As a green and sustainable method for hydrogen production, the electrochemical hydrogen evolution reaction (HER) has received widespread attention. Currently, it is a great challenge to prepare economically stable electrocatalysts for the HER using non-precious metals. In this study, a Co/Co3O4/Ti3C2Tx catalyst was synthesized by supporting Co/Co3O4 with Ti3C2Tx. The results show that Co/Co3O4/Ti3C2Tx has excellent HER activity and durability in 1 mol L−1 KOH, and the overpotential and Tafel slope at 10 mA·cm−2 were 87 mV and 61.90 mV dec−1, respectively. The excellent HER activity and stability of Co/Co3O4/Ti3C2Tx can be explained as follows: Ti3C2Tx provides a stable skeleton and a large number of attachment sites for Co/Co3O4, thus exposing more active sites; the unique two-dimensional structure of Ti3C2Tx provides an efficient conductive network for rapid electron transfer between the electrolyte and the catalyst during electrocatalysis; Co3O4 makes the Co/Co3O4/Ti3C2Tx catalyst more hydrophilic, which can accelerate the release rate of bubbles; Co/Co3O4 can accelerate the adsorption and deionization of H2O to synthesize H2. This study provides a new approach for the design and preparation of low-cost and high-performance HER catalysts.

High-performance hydrogen evolution reaction in quadratic nodal line semimetal Na2CdSn

Topological nodal line semimetals (TNLSMs), which exhibit one-dimensional (1D) band crossing in their electronic band structure, have been predicted to be potential catalysts in electrocatalytic processes. However, the current studies are limited to the TNLSMs where the dispersion around the nodal line is linear in all directions. Here, the potential application of the quadratic nodal line (QNL) semimetal Na2CdSn in hydrogen evolution reaction is explored. Based on the bulk-boundary correspondence, we find that the topological surface states (TSSs) of the QNL are extended in the entire Brillouin zone. A linear relationship between the density of states of the TSSs and the Gibbs free energy is established in Na2CdSn. Remarkably, the best performance of Na2CdSn can be comparable to that of the noble metal Pt. Therefore, our work not only identifies an innovative type of topological catalyst with a QNL state but also confirms the relationship between TSSs and catalytic performance.

Hybrid Molecular Layer Deposition of Molybdenum-Aminates as Hydrogen Evolution Reaction Electrocatalysts

The development of high-performance hydrogen evolution reaction (HER) electrocatalysts from noble metal-free materials is critical to achieving cost-effective water splitting and ultimately realizing affordable hydrogen based on renewable energy. Compounds based on earth-abundant transition metals have been the subject of great research interest for this purpose, with metal nitrides gaining recent attention due to their high conductivity and corrosion resistance. Molybdenum nitride-based electrocatalysts have shown particular promise, with many of the best reported activities occurring in composite systems wherein crystalline MoNx domains are embedded in an amorphous N-doped carbon matrix. The present work demonstrates the formation of such uniquely active morphologies in films deposited by organic-inorganic hybrid molecular layer deposition (MLD).Hybrid MLD is a hybridization of other well-established layer-by-layer deposition techniques – namely atomic layer deposition (used to deposit inorganic films) and purely organic MLD. This family of techniques involves the cyclical exposure of a growth surface to alternating vapor-phase chemical precursors which react in a self-limiting fashion to saturate available surface sites, offering atomic- and molecular-level control over the resulting films. This presentation will introduce the successful development of hybrid MLD deposition procedures for new Mo-aminate materials using Mo(CO)6 as a Mo precursor and various amine precursors, including ethylenediamine, p-phenylenediamine, and tris(2-aminoethyl)amine.We will describe how the molecular level of control offered by this technique enables tunable variations in film composition and structure, lending unique insights into how the local bonding environment of Mo active sites affects their catalytic properties towards HER. Increased nitrogen loading in the MLD films was shown to decrease the overpotentials required to drive HER in acidic media (0.5 M H2SO4) and improve film stability. Catalysts with N/Mo ratios above 2 demonstrated the best performance, with overpotentials lower than 400 mV at -10 mA/cm2. By incorporating organic components in the MLD films, it was possible to induce desirable morphological changes in the catalytic material – notably including the development of increased active site density – simply through initial exposure to HER testing conditions. The choice of organic precursor affected the rate and extent of these changes through structural effects like crosslinking and crystallinity, which led to more stable catalysts, slowed the rate of morphological changes, and impacted final film structure.

Facile hydrothermal synthesis of ZnIn2S4/TiO2 nanosheets for promoted hydrogen evolution reaction

The current study was conducted by introducing a narrow bandgap semiconductor, ZnIn2S4, with the goal of addressing the inefficiency of hydrolysis dissociation and the limited visible light absorption capacity faced by TiO2 as a hydrogen evolution reaction (HER) catalyst due to its low conduction band position and wide bandgap. Using a one-step hydrothermal process, ZnIn2S4 nanosheet/TiO2 nanorod heterostructures were built on nickel foam substrates. The nanosheet structure of ZnIn2S4 is shaped like a flower, which greatly increased the roughness of the TiO2 surface and revealed additional active sites. The ZnIn2S4/TiO2 heterostructure demonstrates quick reaction kinetics and effective electron transport capability, as demonstrated by the electrochemical test results. An overpotential of just 195 mV is required to obtain a current density of 10 mA cm−2. In addition, the overpotential is further decreased to 160 mV under simulated solar radiation. Furthermore, ZnIn2S4 addition minimizes the free energy of hydrogen adsorption on the TiO2 surface and optimizes the position of its Fermi energy level, improving the usage of photogenerated carriers, according to density functional theory (DFT) calculations. This work validates the prospective use of ZnIn2S4/TiO2 heterostructures in photoelectrocatalysis and offers a fresh viewpoint for developing high-performance HER catalysts.

Engineering interfacial sulfur migration in transition-metal sulfide enables low overpotential for durable hydrogen evolution in seawater

Hydrogen production from seawater remains challenging due to the deactivation of the hydrogen evolution reaction (HER) electrode under high current density. To overcome the activity-stability trade-offs in transition-metal sulfides, we propose a strategy to engineer sulfur migration by constructing a nickel-cobalt sulfides heterostructure with nitrogen-doped carbon shell encapsulation (CN@NiCoS) electrocatalyst. State-of-the-art ex situ/in situ characterizations and density functional theory calculations reveal the restructuring of the CN@NiCoS interface, clearly identifying dynamic sulfur migration. The NiCoS heterostructure stimulates sulfur migration by creating sulfur vacancies at the Ni3S2-Co9S8 heterointerface, while the migrated sulfur atoms are subsequently captured by the CN shell via strong C-S bond, preventing sulfide dissolution into alkaline electrolyte. Remarkably, the dynamically formed sulfur-doped CN shell and sulfur vacancies pairing sites significantly enhances HER activity by altering the d-band center near Fermi level, resulting in a low overpotential of 4.6 and 8 mV at 10 mA cm−2 in alkaline freshwater and seawater media, and long-term stability up to 1000 h. This work thus provides a guidance for the design of high-performance HER electrocatalyst by engineering interfacial atomic migration.

Pt cluster incorporated NiO nanoflower boosts hydrogen evolution reaction via enhanced metal support interaction

Hydrogen serves as a potent and environment friendly energy source, and developing high performance hydrogen evolution reaction (HER) electrocatalysts is crucial for water splitting. In this work, Pt nanoparticles incorporated NiO nanoflower (Pt-NiO) is synthesized using an ethylene glycol reduction method. The incorporation of Pt not only introduces extra high active sites, but also induces strong interaction between NiO and Pt. Meanwhile, the NiO nanoflower support enables the dispersion of Pt and ensure high electrochemically surface area as well as fast mass transport, which greatly improves catalytic activity of Pt-NiO. Pt-NiO-3 only requires a small overpotential of 26 mV to reach 10 mA cm−2 and the Tafel slope is only 19.49 mV dec−1. In addition, the mass activity can achieve 2000 mA mgPt−1 at an overpotential of 63 mV. Moreover, obvious bubbles can be observed in the assembled H-type for overall water splitting, and the Faraday efficiency is close to 100 %, highlighting the superiority of Pt-NiO-3. This work provides insights for designing high effective electrocatalysts for HER.

Microstructures and hydrogen evolution reaction performance of Ru-M(M=Cu, Ni and Nb) system by magnetron sputtering: The mixing enthalpy effect

Nanostructured hydrogen evolution reaction (HER) electrocatalysts were prepared by magnetron sputtering. With increasing sputtering power of the Ru target, the catalytic performance of Cu-Ru system improved. Pure Ru sample shows the best performance, due to the larger electrochemical surface area, better hydrophily and smaller electron transfer impedance. No Cu-Ru interaction to improve the catalytic property was observed. This can be attributed to the formation of Cu and Ru nanograins rather than CuRu alloys, due to the repulsive force between Ru and Cu resulted by the positive mixing enthalpy. For Ni-Ru system with a mixing enthalpy close to 0, nanocrystalline NiRu alloys formed. Ru1Ni3 showed a high HER performance close to pure Ru due to the synergistic effect. Nb-Ru also shows synergistic interaction to improve the HER performance. Though the active area is smaller than pure Ru, Nb1Ru1 sample achieves an overpotential of 39 mV at a current density of 10 mA/cm2, lower than that of pure Ru. The main reason can be attributed to the formation of amorphous/crystalline heterojunction due to the negative mixing enthalpy. This promotes the charge transfer at the interface, leading to a smaller electrochemical impedance. The Nb1Ru1 sample also shows better stability for 100 h test with an increasing of only 6 mV of the overpotential at 10 mA/cm2.

A highly efficient and self-supporting nanoporous FeMoC catalyst for enhanced hydrogen evolution reaction

Optimizing structure and surface morphologies in electrocatalyst design are important to enhance the intrinsic activity of the hydrogen evolution reaction (HER). Mo-based phosphides and carbides have been confirmed as the widely-reported catalysts for HER. However, the origin of their enhanced catalytic activity is not fully clarified. Herein, the np-FeMoC and np-FeMoP with a self-supporting nanoporous structure were prepared using the melt-spinning and dealloying methods. Benefiting from the self-supporting electrode, nanoporous structure, abundant active species, low charge-transfer resistance and electron synergy, the np-FeMoC exhibits good catalytic performance. The np-FeMoC performs a low overpotential of 50.8 mV at 10 mA cm−2 current density for HER in 1 M KOH. This value is 2.7 times lower than that of the np-FeMoP sample, indicating a synergistic effect between Mo2C and Fe. From XPS and in-situ Raman results, it was observed that the dissolution of Mo2C occurs accompanied by dynamic evolution during the HER process on the np-FeMoC surface. This work unveils the intrinsic activity of Mo-based carbide and phosphide, providing valuable guidance for reasonable exploit of high-performance HER catalysts.

Capillary-Driven Separate Gas-Liquid Transport: Alleviating Mass Transport Losses for Efficient Hydrogen Evolution.

Developing earth-abundant transition metal electrodes with high activity and durability is crucial for efficient and cost-effective hydrogen production. However, numerous studies in the hydrogen evolution reaction (HER) primarily focus on improving the inherent activity of catalysts, and the critical influence of gas-liquid countercurrent transport behavior is often overlooked. In this study, we introduce the concept of separate-path gas-liquid transport to alleviate mass transport losses for the HER by developing a novel hierarchical porous Ni-doped cobalt phosphide electrode (CoNix-P@Ni). The CoNix-P@Ni electrodes with abundant microvalleys and crack structures facilitate the gas-liquid cotransport by separating the bubble release and water supply paths. Visualization and numerical simulation results demonstrate that cracks primarily serve as water supply paths, with capillary pressure facilitating the transport of water from the cracks to the microvalleys. This process ensures the continuous wetting of electrolytes in the electrode, reduces hydrogen supersaturation near the active site, and increases hydrogen transport flux to the microvalleys for accelerating bubble growth. Additionally, the microvalleys act as preferential sites for bubble evolution, preventing bubble coverage on other active sites. By regulating the amount of nickel, the CoNi1-P@Ni electrode exhibited the smallest and densest microvalleys and cracks, achieving superior HER performance with an overpotential of 51 mV at 10 mA cm-2. The results offer a promising direction for constructing high-performance HER electrodes.

Co/CoO nanoparticles loaded on multi-walled carbon Nanotubes@Covalent organic frameworks for electrocatalytic hydrogen evolution

Producing hydrogen by electrolyzing water has received increased attention. Nevertheless, a major challenge remains in the search for high performance hydrogen evolution reaction (HER) electrocatalysts. In this work, multi-walled carbon nanotubes (MWCNTs) capped by TpPa covalent organic framework (TpPa-COF) react with cobalt nitrate hexahydrate (Co(NO3)2·6H2O) to form a novel ternary one-body complex (MWCNTs@TpPa-COF@Co/CoO). Wherein, TpPa-COF is constructed from 2,4,6-Triformylphloroglucinol (Tp) and p-phenylenediamine (Pa) as structural units. This COF is relatively inexpensive, provides more coordination sites for metal loading, and is particularly stable in acidic and basic media. The results show that the composite material has high electrocatalytic HER activity in a potassium hydroxide (KOH) condition with an overpotential value of 28.8 mV and a Tafel slope of 69.07 mV dec−1 at a current density of 10 mA cm−2. Meanwhile, the MWCNTs@TpPa-COF@Co/CoO showed excellent stability after 2000 cycles in alkaline media. The characterization demonstrated that the material provided low resistance during the charge transfer process, which resulted in improved electrochemical performance. In addition, the COF loaded with cobalt nanoparticles provided more active sites for the reaction. Thus, the synthesized MWCNTs@TpPa-COF@Co/CoO emerges turns out to be a Pt-free, stable and efficient HER electrocatalyst, holding significant promise for practical applications.

Synergistic Effect of P and Co Dual Doping Endows CuNi with High-Performance Hydrogen Evolution Reaction.

The rational design of highly active and durable non-noble electrocatalysts for hydrogen evolution reaction (HER) is significantly important but technically challenging. Herein, a phosphor and cobalt dual doped copper-nickel alloy (P, Co-CuNi) electrocatalyst with high-efficient HER performance is prepared by one-step electrodeposition method and reported for the first time. As a result, P, Co-CuNi only requires an ultralow overpotential of 56mV to drive the current density of 10mA cm-2, with remarkable stability for over 360h, surpassing most previously reported transition metal-based materials. It is discovered that the P doping can simultaneously increase the electrical conductivity and enhance the corrosion resistance, while the introduction of Co can precisely modulate the sub-nanosheets morphology to expose more accessible active sites. Moreover, XPS, UPS, and DFT calculations reveal that the synergistic effect of different dopants can achieve the most optimal electronic structure around Cu and Ni, causing a down-shifted d-band center, which reduces the hydrogen desorption free energy of the rate-determining step (H2O + e- + H* → H2 + OH-) and consequently enhances the intrinsic activity. This work provides a new cognition toward the development of excellent activity and stability HER electrocatalysts and spurs future study for other NiCu-based alloy materials.

Confining ruthenium nanoparticles in MOF pores for high-performance hydrogen evolution reaction

The exploration of low-cost catalysts for hydrogen evolution reaction holds great significance in application. Ruthenium nanoparticles (Ru NPs)-based composites have emerged as a type of promising candidates. This study focuses on the impact of metal–organic framework (MOF) pore structure on the growth of Ru NPs, as well as the resulting effects on their electrocatalytic properties using two Ru@MOFs electrodes (Ru@Ni-BPM/NF and Ru@Ni-BPDC/NF). 3D Ni-BPM can effectively load Ru NPs with uniform and controlled size, while 2D Ni-BPDC leads to uncontrolled growth of Ru NPs. Consequently, Ru@Ni-BPM/NF shows superior catalytic performance with a smaller overpotential of 12 mV at 10 mA cm−2 and a lower Tafel slope of 40.3 mV dec-1, outperforming Ru@Ni-BPDC/NF and commercial Pt/C in alkaline media. Meanwhile, the pore confinement effect of Ni-BPM significantly reduces the aggregation of Ru NPs during extended stability testing, guaranteeing the structural integrity of the electrode and sustained exposure of the active sites.

Interface engineering of MoS2–CoS2 heteronanosheets for enhanced electrochemical hydrogen evolution reaction

The heterostructured electrocatalysts with tunable electronic interaction and distinct synergetic effects have been confirmed as an efficient strategy for realizing high-performance hydrogen evolution reaction (HER). Herein, a simple synthetic strategy is reported for the growth of MoS2–CoS2 nanosheets on highly conductive reduced graphene oxide (MoS2–CoS2/RGO) to innovatively construct an electron-reconfiguration heterointerface. The strong electronic interactions between MoS2 and CoS2 interfaces lead to the redistribution of charge, which optimizes the adsorption-desorption of intermediates. Thus, the MoS2–CoS2/RGO exhibits superior catalytic activity toward HER with small overpotentials of 67 mV (1.0 M KOH) and 95 mV (0.5 M H2SO4), and remarkable stability. In addition, theoretical calculations reveal the redistribution of charge at the heterointerfaces, which decreases the energy barrier of adsorption for H intermediates and simultaneously enhances the kinetic of water dissociation. This work provides a simple strategy for designing heterostructured bimetallic electrocatalysts with a highly active interface.