Enhanced Hydrogen Evolution Reaction Activity Research Articles

Mott-Schottky heterojunction formation between Co and MoSe2 on carbon nanotubes for superior hydrogen evolution

Molybdenum selenide (MoSe2) has been regarded as an advanced electrocatalyst for the hydrogen evolution reaction (HER). However, its electrocatalytic performance is far inferior to platinum (Pt). Combining semiconductors with metals to construct Mott-Schottky heterojunctions has been considered as an effective method to enhance HER activity. In this work, we report a typical Mott-Schottky heterojunction composed of metal Co and semiconductor MoSe2 on carbon nanotubes (Co/MoSe2@CNT), prepared by a sol-gel process followed by thermal reduction. The characterization and theoretical calculations show that a Co/MoSe2 Mott-Schottky heterojunction can cause electron redistribution at the interface and form a built-in electric field, which not only optimizes the free energy of hydrogen atom adsorption, but also improves the charge transfer efficiency during hydrogen evolution. Thus, the Co/MoSe2@CNT has excellent catalytic activity with a low overpotential of 185 mV at 10 mA cm−2 and a small Tafel slope of 69 mV dec−1. This work provides a new strategy for constructing Co/MoSe2 Mott-Schottky heterojunctions and highlights the Mott-Schottky effect, which may inspire the future development of more attractive Mott-Schottky electrocatalysts for H2 production.

Solution combustion synthesis of nanostructured Ni/W-containing electrocatalysts for hydrogen evolution reaction: The effect of fuel-to-oxidant ratio

The effect of varying fuel-to-oxidant ratio (φ) on the physicochemical properties and electrocatalytic performance for the hydrogen evolution reaction (HER) of nanostructured NiW materials produced via solution combustion synthesis (SCS) method was investigated. Agar and nickel nitrate served as the fuel and oxidant, respectively. TGA-MS results revealed that a fuel-to-oxidant ratio of 9 (φ9) provides the optimal conditions for reducing metal oxides to metallic phases due to the highest emission of reducing gas species (H2, CH4, and NH3). N2 adsorption/desorption measurements indicated that under fuel-rich conditions (φ > 1), both the specific surface area and porosity expanded with increasing the fuel quantity. Microscopy characterization was found to be consistent with N2 adsorption/desorption and TGA-MS results, revealing that the increased gas expulsion from higher fuel content led to more pronounced coral-like structures comprising of nano-sized particles and pores. Evaluation of electrocatalytic activity in an acidic medium (0.5 M H2SO4) revealed that the φ9 sample demonstrated the highest electrocatalytic HER performance. XRD and XPS analyses correlated well with this result, attributing the enhanced HER activity to the presence of the Ni0.9W0.1 metallic phase, limited oxide formation, and the highest proportions of metallic Ni and W atomic states, beyond mere surface area effects. Consequently, this study provides valuable insights into the importance of the fuel-to-oxidant ratio in optimizing the SCS method for controlled synthesis of nanostructured NiW materials in terms of morphology and composition, with implications for their potential development as high-performance, cost-effective electrocatalysts.

Self-supported Cr–Cu2S nanoflakes for hydrogen production from seawater

Herein, we report the one-step hydrothermal synthesis of bifunctional Cr–Cu2S Nanoflakes supported on Cu-foam (Cr–Cu2S@CF) for alkaline water electrolyzer for H2 production at an industrial scale. Vertically oriented Cr–Cu2S Nanoflakes, forming a hierarchical network is capable of efficient electrocatalytic activity owing to the high surface area, effective ions channels, and abundant redox sites. Owing to advanced morphological features, Cr–Cu2S@CF demonstrates the binder-free electrocatalytic hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) at an industrial scale high current density of 500 mA/cm2. Exploiting the synergistic features, the optimized chemical composition of Cr–Cu2S delivers the geometric current density of 100 mA/cm2 at overpotential of −407 mV and −350 mV for HER and OER activity, respectively. Alloying Cr in Cu2S networks enhances oxygen desorption at the anode by decreasing the energy of adsorption of *OH intermediates, apart from enhanced HER activity due to enhanced electron density at Cu-sites. Moreover, two a two-electrode electrolyzer assembled using Cr–Cu2S@CF as an electrocatalyst at both electrodes gives current densities of 10 and 100 mA/cm2 at potentials of 1.75 V and 2.07 V, respectively.

Influence of antisite defects on two-dimensional polymeric material for improved hydrogen evolution reaction

Two-dimensional materials (2D) supported by single atom catalysis have emerged as effective catalysts for H2 production at large scale by Hydrogen Evolution Reaction (HER). While there is a research surge on utilizing inexpensive metals as catalysts to replace Platinum (Pt) and other related noble metals, their practical limitations such as oxidation issues remain a concern. In this work, we report electrochemical HER activity of a recently synthesized metal-free 2D Polyaramid (2DPA) using Density Functional Theory (DFT) calculations. Pristine 2DPA exhibits remarkable HER performance in terms of active sites availability for hydrogen adsorption and the lowest Gibb's free energy change (−0.06 eV) close to that of benchmark Pt/C catalyst (−0.09 eV). Furthermore, introduction of antisite defects by substituting carbon for nitrogen (CN) and nitrogen for carbon (NC) in pristine 2DPA depicts enhanced HER activity. CN and NC defects tune the electronic properties by reducing the band gap resulting improved conductivity. Low formation energies calculated for obtaining antisite defects confirm their feasibility of synthesis while ab initio molecular dynamics (AIMD) simulations ensure their thermal stability at room temperature. The change in Gibb's free energy (ΔGH) values for CN-defective and NC-defective 2DPA are computed to be −0.13 eV and −0.11 eV, respectively. Both CN-defective and NC-defective 2DPA favor H2 evolution via Heyrovsky reaction pathways due to their relatively lower activation energy, 0.64 eV and 0.51 eV, respectively. Our findings encourage design and development of a novel 2D metal-free electrocatalyst for enhanced HER.

Ternary Rare Earth Alloy Pt3-xIrxSc Nanoparticles Modulate Negatively Charged Pt via Charge Transfer To Facilitate pH-Universal Hydrogen Evolution.

Rare earth (RE) elements possess electronic configurations that can provide additional pathways for tailoring the electronic structures of active elements through alloying, making it an important area of exploration in electrocatalysis. However, the large negative redox potential between RE and Pt has hindered the development of RE nanoalloys. In this study, a solid-phase synthesis strategy was employed to synthesize ternary Pt3-xIrxSc nanoparticles (NPs). By leveraging the electronegativity difference between Pt (2.28), Ir (2.20), and Sc (1.36), a charge-balance strategy was implemented to stabilize and enhance the catalytic performance of the alloy. The electron transfer from Sc to Pt/Ir results in the latter being negatively charged, and the Ir modifies the electron density of Pt, enabling favorable adsorption of active H species during the hydrogen evolution reaction (HER). Pt2IrSc exhibits enhanced HER activity at all pH values, achieving low overpotentials at 10 mA cm-2 of only 13, 18, and 25 mV in 0.5 M H2SO4, 1 M PBS, and 1 M KOH, respectively. This electrocatalyst also exhibits robust electrocatalytic stability even after 20,000 cycles. This work represents an application of the charge balance strategy to RE nanoalloys, and it is expected to inspire the design and synthesis of highly reactive RE nanoalloys.

Study on effect of vanadium doping in cesium tungsten bronze system and application in HER

Increasing demand for energy and the crisis of fossil fuels have led researchers to search for an alternative energy source. Hydrogen is the cleanest energy source producing water as fuel cells exhaust. However, producing hydrogen could be crucial as only some active catalysts produce pure hydrogen. The expense due to the scarcity of the state-of-the-art catalyst (platinum) for the Hydrogen Evolution Reaction (HER) is the main reason for the higher price of pure hydrogen as a fuel. In our present research, we chose the less expensive cesium tungsten bronzes (CTB) doped with various percentages of vanadium (5 mol% - 20 mol%) to study their HER performance. The materials were prepared hydrothermally at 180 °C at different reaction times. XRD revealed that, upon increasing the vanadium amount, the hexagonal phase of the CTB is transformed to the cubic phase at a higher reaction time. However, the hexagonal phase was retained after vanadium introduction with a lower reaction time. FT-IR, Raman, EDX, SIMS, XPS, and XRF spectroscopy confirmed the incorporation of vanadium into the bronze system. Vanadium-doped samples showed enhanced HER activity compared to the pure CTB. The 20% vanadium-doped hexagonal bronze showed the best HER performance in 0.5 M H2SO4 among all the vanadium-doped materials, which lowered the HER potential of the pure CTB (-0.665 V vs RHE) to -0.288 V vs RHE at -10 mA cm−2. This increase in activity was correlated with a higher surface area, higher electrochemical surface area, faster reaction kinetics with a lower Tafel slope, and a small charge-transfer resistance of the samples after V5+ incorporation compared to the pure CTB.

Recent Progress on Molybdenum Carbide-Based Catalysts for Hydrogen Evolution: A Review

Hydrogen is an ideal alternative energy for fossil fuels to solve aggravating environmental and energy problems. Electrocatalytic hydrogen evolution reaction (HER) driven by renewable electricity (sunlight, wind, tide, etc.) is considered to be one of the most promising approaches for hydrogen production. However, its large-scale applications are greatly limited by the use of noble platinum (Pt) group electrocatalysts. As an earth-abundant/non-noble HER catalyst, molybdenum carbide (MoxC: MoC or Mo2C) has attracted extensive attention in the field of sustainable hydrogen production due to its excellent Pt-like catalytic activity, low cost, high chemical stability, and natural abundance. In this review, the progress on the strategies for optimizing the catalytic activity of MoxC is summarized, including optimization of synthesis methods, composites with carbon material, non-precious metal doping, transition metal doping, construction of the heterogeneous structure, etc. Among them, the importance of sulphur-doping, Ni-doping, and heterophase structure on molybdenum carbide-based catalysts for enhancement of HER activity has been highlighted. In addition, molybdenum carbide-based bi-functional catalysts are presented for the application in full water splitting. Finally, several effective strategies for molybdenum carbide-based catalyst design are concluded, and challenges remained in electrocatalytic water splitting are raised. Future development trends and perspectives for this promising material are also discussed.

Synergistic Promotion of Large-Current Water Splitting through Interfacial Engineering of Hierarchically Structured CoP-FeP Nanosheets with Rich P Vacancies.

The development of hydrogen evolution reaction (HER) catalysts with high performance under large current density is still a challenge. Introducing P vacancies in heterostructure is an appealing strategy to enhance HER kinetics. This study investigates a CoP-FeP heterostructure catalyst with abundant P vacancies (Vp-CoP-FeP/NF) on nickel foam (NF), which was prepared using dipping and phosphating treatment. The optimized Vp-CoP-FeP catalyst exerted prominent HER catalytic capability, requiring an ultra-low overpotential (58 mV @ 10 mA cm-2 ) and displaying robust durability (50 h @ 200 mA cm-2 ) in 1.0 M KOH solution. Furthermore, the catalyst demonstrated superior overall water splitting activity as cathode, demanding only cell voltage of 1.76 V at 200 mA cm-2 , outperforming Pt/C/NF(-) || RuO2 /NF(+) . The catalyst's outstanding performance can be attributed to the hierarchical structure of porous nanosheets, abundant P vacancies, and synergistic effect between CoP and FeP components, which promote water dissociation and H* adsorption and desorption, thereby synergically accelerating HER kinetics and enhancing HER activity. This study demonstrates the potential of HER catalysts with phosphorus-rich vacancies that can work under industrial-scale current density, highlighting the importance of developing durable and efficient catalysts for hydrogen production.

Crystalline/amorphous Ni/NixSy supported on hierarchical porous nickel foam for high-current-density hydrogen evolution

Manufacturing efficient and durable electrodes for alkaline water electrolysis under high-current-density conditions is a great challenge. Herein, Ni/NixSy heterostructure was grown on designed porous nickel foam (PNF) to construct Ni/NixSy-PNF electrode by a facile and scalable method for alkaline hydrogen evolution reaction (HER). The hierarchical porous structure and super-hydrophilic surface of Ni/NixSy-PNF accelerate the mass transfer and bubble detachment at high current densities. Theoretical calculations reveals that the enhanced HER activity of Ni/NixSy heterostructure is attributed to the stronger H2O adsorption. The resulting Ni/NixSy-PNF electrode achieves current densities of 100 and 500 mA cm−2 at low overpotentials of 61 and 121 mV, respectively. When applied for overall water splitting, the Ni/NixSy-PNF||Fe-Ni3S2-PNF electrolyser reaches a current density of 10 mA cm−2 at an extremely low voltage of 1.32 V. This work provides an effective strategy for fabricating high-performance electrodes for practical water electrolysis.

Enhanced HER activity of transition metal cluster decorated ReS2 monolayer

Two-dimensional material rhenium disulfide (ReS2) has attracted much attention recently as a potential electrochemical catalyst for the Hydrogen Evolution Reaction (HER). The ReS2 monolayer is found to be catalytically inert. The challenge lies in activating the ReS2 monolayer to increase HER output. One of the approaches to this lies in depositing small metal clusters on the monolayer. This paper examines the formation and stability of small metal clusters on 1T distorted ReS2 monolayer using dispersion-corrected Density Functional Theory. Four different kinds of transition metal clusters, viz. Au, Pt, Mo, and Cr are investigated for geometry and binding on the ReS2 monolayer. HER activity of each type of ReS2-supported metal cluster is investigated based on computed free energy. The HER mechanism was investigated for clusters with optimal activity, and it was found that while the ReS2 monolayer follows the Volmer-Heyrovsky route, for the transition metal cluster decorated ReS2, the Volmer-Tafel route is more probable.

Modulating the crystallinity of 1D MoO3 and its conversion to 2D MoS2 nanosheets for efficient hydrogen evolution reaction catalysts

Molybdenum sulfide (MoS2) has been identified as a promising and ample electrocatalyst for hydrogen evolution reaction (HER). Herein, we have synthesized 2D MoS2 from 1D Molybdenum oxide (MoO3) prepared via hydrothermal method and subsequent annealing. The HER of the prepared MoO3 and MoO3 annealed at temperature varying from 100 to 700 °C is evaluated by utilizing linear sweep voltammetry (LSV) in acidic electrolyte medium with MoO3@300 °C displaying the best overpotential at 229 mV vs RHE, respectively. The enhanced HER activity of MoO3 annealed at 300°C is attributed to its higher crystallinity. Further, the MoO3 annealed at 300 °C is converted to MoS2 exhibiting excellent HER performance with overpotential of 197 mV. The Tafel slope, electrochemical active surface area (ECSA) and turn over frequency (TOF) values of MoS2, MoO3, at different annealed temperatures have also been analysed in this work.

Efficient Electrocatalytic Hydrogen Evolution Reaction on CuO Immobilized Stainless‐Steel Electrode Prepared by the SILAR Method

AbstractThe development of cost‐effective and efficient catalysts for the hydrogen evolution reaction (HER) has been a subject of intense research for sustainable and clean energy in recent decades. For this purpose, CuO‐modified stainless steel (CuO‐SS) electrode was fabricated to attain HER in acidic media. Here in, CuO film was fabricated on a stainless steel (SS) surface following successive ionic layer adsorption and reaction (SILAR) method. A 60‐cycle CuO modification resulted in enhanced HER activity compared to the bare SS or CuO electrode with an average 99 % Faradic efficiency. Based on the Electrochemical Impedance Spectroscopy (EIS), at an HER potential, the bare SS electrode exhibited charge transfer resistance of 24.7 Ω whereas CuO‐SS electrode exhibited 6.47 Ω only. The overpotential was calculated to be 154 mV at the CuO‐SS electrode regarding HER. The results have significant implications for the development of cost‐effective and efficient electrocatalysts for hydrogen production.

Trace Ru-tuned NiO/CNT electrocatalysts outperform benchmark Pt for alkaline hydrogen evolution with superior mass activity

The exploitation of highly active and durable electrocatalysts that can replace high-cost Pt/C for hydrogen evolution reaction (HER) is urgently required. The challenge lies in diminishing the usage of noble metals without sacrificing HER activity. In this work, trace Ru-doped transition metal oxides (TMOs) nanoparticles (∼7 nm) with high dispersion loaded by the carbon nanotubes (CNTs) were developed. Specifically, Ru-NiO/CNTs with a low Ru content of 0.94 wt% exhibits excellent alkaline HER activity with the low overpotential of 19 mV and 98 mV to achieve the current density of 10 mA·cm−2 and 100 mA·cm−2, respectively, outperforming Ru/CNTs counterpart and most previously Ru-based nanocatalysts. Notably, the mass activity (1.83 A·mgRu-1) and price activity (301.51 A·dollar-1) of Ru-NiO/CNTs are separately more than 7 times and 18 times higher than that of the commercial 20% Pt/C benchmark. Moreover, the catalyst can operate without activity decay after 100 h long-term stability test. DFT calculation reveals that the synergy effects are originated from (i) the accelerated adsorption and dissociation of H2O by Ru, and (ii) the optimized electronic structure of Ni that tunes the H* adsorption/desorption. Furthermore, we discover that Ru-promoted HER activity shows a metal-dependent relationship (Ni ≈ Cu > Mn > Co > Fe), which can use binding energy shift (ΔE) as a highly correlated descriptor. This work may provide an insightful understanding of Ru dopant for enhanced HER activity.

Enhanced activity and durability of FeCoCrMoCBY nanoglass in acidic hydrogen evolution reaction

In the present work, a multi-element nanoglass (m-NG) of FeCoCrMoCBY is obtained first time by the laser ablation combined with inert gas condensation (laser-IGC) technique. Compared with the conventional rapid-quenched metallic glass (MG) with identical composition, the Fe-based m-NG demonstrates a superior performance as a self-supported electrocatalyst for hydrogen evolution reaction (HER) in acidic solution. The enhanced HER activity of m-NG is proposed to be closely related to its high energy states, which is originated from the unique inhomogeneous nanostructures with a high density of low-coordinated atoms. Additionally, the Fe-based m-NG exhibits an outstanding comprehensive catalytic performance even beyond the commercial Pt/C catalyst in long-term test due to its self-optimization ability. This work not only opens the way to the preparation of m-NGs by the novel laser-IGC technique, but also makes a great contribution to developing low-cost, high-efficient, and super-durable HER electrocatalysts in acidic environment.

“One stone three birds” plasma engraving strategy to boost the hydrogen evolution reaction activity of layered double hydroxides

Possessing large specific surface areas and rich metal redox sites, layered double hydroxides (LDHs) are potentially suitable oxygen evolution reaction catalysts. It is a pity that they usually show poor hydrogen evolution reaction (HER) activity on account of the limited conductivity and deficient active sites. Taking NiFe LDH nanosheets as an example, we develop a “one stone three birds” plasma engraving strategy to enhance the HER activity of NiFe LDH. The “three birds,” including the reduction of Ni2+ to Ni nanoparticles (Ni NPs), generation of more oxygen vacancies (Ov), and exfoliation of nanosheets into much thinner ones, can obviously improve the conductivity and active sites of NiFe LDH. The plasma processing can also enhance water adsorption and accelerate the Volmer step during HER. As expected, the plasma-engraved NiFe LDH (PEH) exhibits enhanced HER activity with a low overpotential of 22 mV at 10 mA cm−2 and a small Tafel slope of 38 mV dec−1 in 1 M KOH, much better than NiFe LDH (202 mV, 145 mV dec−1). By combining optical emission spectroscopy diagnosis and structural/electrochemical characterizations, the relationship among the electron excitation temperature (Texc) in plasma, the amount of Ni NPs and Ov in PEH, and the HER activity of PEH is established. Excitingly, the PEH also displays splendid HER activity in both alkaline real seawater and overall water splitting.

Boosting the alkaline hydrogen evolution reaction of Ni/Co9S8@FP heterostructures via interfacial synergistic effects

Hydrogen from electrolysis cell driven by sustainable electricity is one of the most clean and renewable energy sources. The design and synthesis of efficient and robust noble-metal-free electrocatalyst for hydrogen evolution reaction (HER) are of paramount importance in modern society. Herein, we developed a simple two-step strategy to construct a new Ni/Co9S8 heterostructure using carbonised (900 °C) filter paper (FP) as a precious metal-free electrocatalyst for hydrogen evolution reaction (HER) in alkaline media. The optimized electrocatalyst can achieve an ultralow overpotentials of 76 mV for HER at 10 mA cm−2 in 1.0 M KOH. Moreover, it can be maintained a current density of 100 mA cm−2 at 380 mV (vs. RHE) for 37 h. More importantly, experimental and theoretical calculations reveal that the remarkable enhancement of HER activity could be attributed to the synergistic effect of Ni and Co9S8 that lead to the moderate hydrogen adsorption on Ni surface and improve the water dissociation at the interface of Ni/Co9S8. Our work paves a new pathway to design high-efficient electrocatalysts for massive hydrogen production.

Hydrogen production via water electrolysis on an active electrocatalyst rGONi nanocomposite

The development of inexpensive and effective electrocatalyses are all-important for hydrogen production from water electrolysis. In this study, a facile design of a reduced graphene oxide (rGO) based electrocatalyst decorated with nickel nanoparticles is described. The voltammetric results and the hydrogen evolution reaction (HER) kinetics showed that the as-prepared nanocomposite is an effective and stable electrocatalyst for hydrogen production with a small Tafel slope of 152 mVdec-1 and long-term continuous durability (over 24 h) in 0.5 M H2SO4 solution. Also, the enhanced HER activity was confirmed by characterization results with the porous/greater electroactive surface area. The remarkable increase in electrocatalytic activity was due to the surface roughness and the synergetic chemical coupling effects between rGO and Ni nanoparticles.

Synergism of 1D CdS/2D Modified Ti3C2Tx MXene Heterojunctions for Boosted Photocatalytic Hydrogen Production

Rational design and controllable synthesis of visible-light-responsive photocatalysts that exhibit both good hydrogen-producing efficiency and stability in the water splitting reaction are undoubtedly a challenge. Here we report an integrated CdS nanorod/oxygen-terminated Ti3C2Tx MXene nanosheet heterojunction with a high catalytic hydrogen evolution reaction (HER) activity. By incorporating one-dimensional (1D) CdS nanorods onto annealed ultrathin two-dimensional (2D) MXene nanosheets, the mixed-dimensional 1D/2D heterojunction achieved a hydrogen-evolving rate of 8.87 mmol·g−1·h−1, much higher than that of bulk CdS and CdS/unmodified MXene hybrid catalysts. The enhanced HER activity and stability of the designed heterojunction catalyst are attributed to the presence of oxygen-containing terminal groups on the surface of thermally treated Ti3C2Tx MXene, extended light absorption spectra as well as the precisely constructed intimate Schottky contact, implying an accelerated interfacial charge transfer and efficient, long-term photocatalytic hydrogen production performance. The results demonstrate that oxygen-terminated 2D MXene can be well utilized as a functional platform for the development of novel heterojunction photocatalysts.

Accelerated mass/electron transfer by self-supporting Ni2P@Cu3P heterostructure array to boost alkaline hydrogen evolution at high current density

The construction of hydrogen evolution reaction (HER) catalysts at high current density (HCD) is challenging. Electron/mass transfer is hindered by the unsatisfied electrical conductivity at the catalyst-support interface and the massive gas bubbles adhered at the electrolyte-catalyst interface at HCD condition. Herein, a non-precious Ni2P@Cu3P heterostructure constructed by in-situ phase conversion is developed as an electrochemical HER catalyst. The Ni(OH)2 decorated Cu(OH)2 nanowire heterostructure is completely converted into the high electrical conductive Ni2P@Cu3P by a simple phosphatizing method, which not only remain the 3D nanowire array structure but also provide the large specific active surface area and plentiful channels for the fast charge/mass transport to accelerate the HER dynamics. Furthermore, density functional theory calculations reveal that the strong electron interaction between the Ni2P and Cu3P, which can regulate the charge density distribution. As-prepared Ni2P@Cu3P heterostructure displays a more moderate free energy (ΔGH2O = -0.37 eV and ΔGH* = −0.01 eV) for alkaline HER. Benefiting from the complementary advantage of Ni2P and Cu3P, the Ni2P@Cu3P heterostructure exhibits an enhanced HER activity with an overpotential of 279 mV, an excellent long-term stability and durability at 1000 mA·cm−2, providing the great potential for large-scale industrial applications.

Recent Advances and Perspectives in Ru Hybrid Electrocatalysts for the Hydrogen Evolution Reaction

The water-splitting reaction for green hydrogen generation requires highly efficient catalysts on the side for the hydrogen evolution reaction (HER), and metal ruthenium (Ru) is considered a promising catalyst as a result of its similar property in hydrogen-bonding ability but low cost compared to Pt-based materials. The performance is further boosted by the recently developed hybrid Ru-based electrocatalysts. To reveal the relationship between the hybrid catalyst systems and activity for Ru-based catalysts, the research progress of heterostructured Ru hybrid catalysts in the HER is reviewed in this effort. The enhancement of HER activity of Ru hybrid catalysts is first described on the basis of the synergistic effect, strain effect, and electronic effect, and then, the latest progress is discussed in three categories of single ruthenium catalysts, ruthenium-related compounds, and ruthenium alloy catalysts. It is concluded that the heterostructured interface engineering strategy plays an important role in enhancing the activity of Ru-based catalysts in the HER. In the end, the actual problems and challenges are discussed, e.g., the intrinsic activity and stability, application in the real device, etc. It is recommended to pay attention to the long-term stability, performance, and structural evolution as well as the application of the catalysts in the devices. It is hoped that this effort will help with understanding the progress of Ru-based hybrid catalysts in the field of HER catalysis.