Hydrogen Adsorption Free Energy Research Articles

Self-Reconstructed Amorphous CoOx/NiCoB Heterostructure Catalysts for Enhanced HER Performance.

Amorphous electrocatalysts exhibit potentials as precursors for triggering the in situ reconstruction to generate the real catalytic active species toward electrochemical processes. In this work, a new kind of amorphous Ni-Co-B alloy pre-catalysts for hydrogen evolution reaction (HER) is reported, which is obtained via a facile electroless plating strategy on the nickel foam (NF). Interestingly, X-ray photoelectron spectroscopy, X-ray absorption spectroscopy and morphological characterizations identify the in situ reconstruction process during HER accompanied by the preferential leaching of surface B species and the formation of amorphous CoOx nanosheet arrays as the real active sites. Benefiting from the synergistic effect between the surface CoOx layer and the inner unaltered NiCoB phase, the resultant CoOx/NiCoB heterostructure catalyst achieves a low overpotential of 209mV at the elevated current density of 500mA cm-2 and maintains stability for 300h without significant attenuation. Theoretical calculation reveals the electron reconfiguration at the interfaces between the newly formed CoOx and inner NiCoB phases, which is favorable for the stabilization of reconstructed active oxide layers at the reductive potentials for catalyzing HER. Moreover, the CoOx/NiCoB heterostructure optimizes hydrogen adsorption free energies, thereby enhancing HER catalytic activity.

A strongly coupled 1T'-ReSe2@2H-MoSe2 van der Waals heterostructure for efficient electrocatalytic hydrogen evolution at high current densities.

Developing efficient and durable non-noble metal electrocatalysts for high current-density hydrogen evolution reactions (HER) is a pressing requirement for commercial industrial electrolyzers. In this study, a vertical 1T'-ReSe2@2H-MoSe2 van der Waals heterostructure was developed through interface engineering to enhance the advantages of each component and expose numerous active sites. Experimental investigations and density functional theorycalculations demonstrate significant electronic coupling at the interface between 1T'-ReSe2 and 2H-MoSe2, with suitable Gibbs free energy for hydrogen adsorption. The 1T'-ReSe2@2H-MoSe2 heterostructure catalyst achieves high current density HER with low overpotentials of 191 mV to generate up to 800 mA/cm2 in 0.5 M H2SO4, outperforming commercial 5% Pt/C catalysts. Moreover, this catalyst exhibits rapid reaction kinetics and long-term durability, illustrating a successful approach to designing efficient heterostructure electrocatalysts for hydrogen production through interface engineering.

Mo Migration‐Induced Crystalline to Amorphous Conversion and Formation of RuMo/NiMoO4 Heterogeneous Nanoarray for Hydrazine‐Assisted Water Splitting at Large Current Density

AbstractManipulating the atomic structure of the catalyst and tailoring the dissociative water‐hydrogen bonding network at the catalyst‐electrolyte interface is essential for propelling alkaline hydrogen evolution reaction (HER) and hydrazine oxidation reaction (HzOR), but remains a great challenge. Herein, we constructed an advanced a‐RuMo/NiMoO4/NF heterogeneous electrocatalyst with amorphous RuMo alloy nanoclusters anchored to amorphous NiMoO4 skeletons on Ni foam by a heteroatom implantation strategy. Theoretical calculations and in situ Raman tests show that the amorphous and alloying structure of a‐RuMo/NiMoO4/NF not only induces the directional evolution of interfacial H2O, but also lowers the d‐band center (from −0.43 to −2.22 eV) of a‐RuMo/NiMoO4/NF, the Gibbs free energy of hydrogen adsorption (ΔGH*, from −1.29 to −0.06 eV), and the energy barrier of HzOR (ΔGN2(g)=1.50 eV to ΔGN2*=0.47 eV). Profiting from these favorable factors, the a‐RuMo/NiMoO4/NF exhibits excellent electrocatalytic performances, especially at large current densities, with an overpotential of 13 and 129 mV to reach 10 and 1000 mA cm−2 for HER. While for HzOR, it needs only −91 and 276 mV to deliver 10 and 500 mA cm−2, respectively. Further, the constructed a‐RuMo/NiMoO4/NF||a‐RuMo/NiMoO4/NF electrolyzer demands only 7 and 420 mV to afford 10 and 500 mA cm−2.

Ingenious regulation and activation of sites in the 2H-MoS2 basal planes by oxygen incorporation for enhanced photocatalytic hydrogen evolution of CdS

The 2H phase of MoS2 has the advantages of stable phase structure and tunable preparation approach, while the unfavorable H adsorption ability at the basal plane sites hinders the H2 evolution performance. Here, we developed an effective strategy for the regulation of the basal plane properties of MoS2 via oxygen doping. It is demonstrated that the Gibbs free energy of hydrogen adsorption (ΔGH*) at the sites in the basal plane can be effectively optimized. Using oxygen-doped MoS2 (OMoS) as a cocatalyst, the constructed OMoS/CdS heterojunction photocatalyst shows a stronger built-in electric field and improved photocatalytic H2 production activity. The optimized OMoS/CdS sample with only 0.3 wt% OMoS loading amount achieved an H2 evolution rate of 58.47 mmol g-1h−1 under AM 1.5 light irradiation, which is significantly superior to that of conventional MoS2 modified CdS and even higher than the 1 wt% Pt modified CdS. Our results not only highlighted the significant potential of OMoS as a photocatalyst for hydrogen production, but also proposed a superior to and effective conception for optimizing the H2 evolution activity at the basal plane sites of 2H-MoS2.

Designing Mo-based transition metal dichalcogenides for sustainable hydrogen production: Anionic substitution and DFT insight

Anionic substitution is an effective approach to optimize the catalytic activity of Mo based transition metal dichalcogenide (TMD)- MoS2 towards hydrogen evolution reaction (HER). By optimizing the S-to-Se ratio, materials with the ideal Gibbs free energy of hydrogen adsorption (ΔGH) values are synthesized (MoS2, MoS1.4Se0.6, MoS1.2Se0.8, MoSSe, MoSe2) and their HER performance is examined in 0.5 M H2SO4 solution. Density functional theory calculations of hydrogen adsorption energy on the surface of the electrocatalysts show that Se substitution facilitates electron transfer between the catalyst surface and the hydrogen donor, thereby lowering the additional potential required for water splitting, making MoS1.2Se0.8 the most favorable HER electrocatalyst with the lowest value of adsorption energy. Further enhancement in the electrocatalytic activity of mixed anion TMDs has been achieved by the incorporation of carbon nanotubes (CNTs). MoS1.2Se0.8-CNT nanocomposite exhibits superior HER performance with an overpotential of 118 mV and a Tafel slope of 63 mV/decade as compared to MoS1.2Se0.8 sample owing to the synergetic effect from CNTs and MoS1.2Se0.8.

Enhancing HER catalyst screening of modified MXenes through DFT and machine learning integration

AbstractMXenes doped with non‐metallic and transition metal elements exhibit remarkable potential as catalysts in the hydrogen energy. Nonetheless, efficiently identifying viable materials from a vast array of candidates remains a formidable challenge. Here, we conducted density functional theory (DFT) calculations to obtain the hydrogen adsorption free energy () of 78 types of doped TiVCO2 MXene catalysts. Then we employed machine learning models to categorize the values of the 78 catalysts, resulted in an accurate model which only uses 7 readily available elemental features but has an impressive accuracy of 93.6%. Our model successfully predicting 5 TiVCO2 catalysts doped with S with superior performance, subsequently validated through DFT calculations. This classification methodology not only evaluates the range of effectively but also facilitates qualitative prediction and screening of catalysts, presenting a novel approach for catalytic systems with limited available data.

Rh–Ni(OH)2/NF via hydrolysis galvanic replacement of boride: Unveiling an exceptional electrocatalyst for high-current alkaline hydrogen evolution

The efficient and high-quality production for hydrogen through water electrolysis at high current densities is crucial for commercial utilization. However, the performance of existing hydrogen evolution reaction (HER) electrocatalysts is far from satisfactory. In this regard, we proposed a method to prepare Rh–Ni(OH)2 catalyst based on Nickel foam (NF). The hydrolysis galvanic replacement of nickel boride with RhCl3 led to produce a lattice contraction in Ni(OH)2 due to the rigid pressure generated, resulting in outstanding HER performance at high current densities. It achieves an industrial current density of 500 mA cm−2 with an overpotential of 130 mV. Furthermore, at the industrially prefer temperature of 80 °C, only 67 mV overpotential is required. The catalyst also demonstrated exceptional stability, maintaining excellent performance even after a stability test of 100 days with a current density of 200 mA cm−2. Through Density-functional theory (DFT) calculations, Rh series reduced the hydrogen adsorption free energy.

Mo Migration-Induced Crystalline to Amorphous Conversion and Formation of RuMo/NiMoO4 Heterogeneous Nanoarray for Hydrazine-Assisted Water Splitting at Large Current Density.

Manipulating the atomic structure of the catalyst and tailoring the dissociative water-hydrogen bonding network at the catalyst-electrolyte interface is essential for propelling alkaline hydrogen evolution reactions (HER) and hydrazine oxidation reaction (HzOR), but remains a great challenge. Herein, we constructed an advanced a-RuMo/NiMoO4/NF heterogeneous electrocatalysts with amorphous RuMo alloy nanoclusters anchored to amorphous NiMoO4 skeletons on Ni foam by a heteroatom implantation strategy. Theoretical calculations and in-situ Raman tests show that the amorphous and alloying structure of a-RuMo/NiMoO4/NF not only induces the directional evolution of interfacial H2O, but also lowers the d-band center (from -0.43 to -2.22 eV) of a-RuMo/NiMoO4/NF, the Gibbs free energy of hydrogen adsorption (ΔGH*, from -1.29 to -0.06 eV), and the energy barrier of HzOR (ΔGN2(g) = 1.50 eV to ΔGN2* = 0.47 eV). Profiting from these favorable factors, the a-RuMo/NiMoO4/NF exhibits excellent electrocatalytic performances, especially at large current densities, with an overpotential of 13 and 129 mV to reach 10 and 1000 mA cm-2 for HER. While for HzOR, it needs only -91 and 276 mV to deliver 10 and 500 mA cm-2, respectively. Further, the constructed a-RuMo/NiMoO4/NF||a-RuMo/NiMoO4/NF electrolyzer demands only 7 and 420 mV to afford 10 and 500 mA cm-2.

Boosting hydrogen adsorption via manipulating interfacial electronic structure of NiPx for enhanced alkaline seawater electrolysis

The development of transition metal phosphides (TMPs) electrocatalysts with appropriate binding strength towards intermediates and resistant to chlorine in alkaline seawater electrocatalysis remains a formidable challenge. Herein, an approach for manipulating electron redistribution in Ni2P/Ni5P4 treated by Co cationic doping engineering (denoted as Act-Co-NiPx) is proposed, exhibiting excellent catalytic activities and stability toward HER in alkaline seawater solution. First-principles calculations demonstrate that the Co doping can effectively adjust the electron redistribution of Ni2P/Ni5P4, resulting in a reduction in the hydrogen adsorption free energy for HER and an acceleration in the interfacial charge transfer. Furthermore, the enhanced Cl- adsorption energy avoids the toxicity of Cl- to the active sites in alkaline seawater splitting. Consequently, the resulting Act-Co-NiPx catalyst demonstrates remarkable HER performance with low overpotentials of 77 and 97 mV at a current density of 10 mA cm−2 in both 1.0 M KOH and 1.0 M KOH+Seasalt electrolytes. Furthermore, the seasalt electrolyzer assembled from Act-Co-NiPx achieves the low cell voltage of 1.63 V at 10 mA cm−2. This work demonstrates a feasible method for designing cost-effective and stable catalysts with excellent selectivity via regulating the electronic structure of TMPs for seawater electrolysis.

Symbolic transform optimized convolutional neural network model for high-performance prediction and analysis of MXenes hydrogen evolution reaction catalysts

Two-dimensional MXenes materials are expected to be cost-effective and efficient catalysts for hydrogen evolution reaction (HER) due to their tunable surface electronic structure. To optimize its catalytic activity, this study proposes a data-driven framework (CROSST) to generate descriptors through feature engineering and integrate them into a convolutional neural network to predict the HER performance of transition-metal (TM) anchored bis-transition-metal carbon-nitride (TM-M′2M′′CNO2) catalysts. The STCNN model achieves a coefficient of determination of more than 0.93, showing the ability to predict the Gibbs free energy of hydrogen adsorption (ΔGH) with high accuracy. We explored the microscopic mechanisms of HER activity through density functional theory and machine learning analysis. It was found that TM anchoring altered the charge distribution of the MXenes material, elevated the atomic orbital occupancy of neighboring O sites, and weakened the O adsorption of H, thus affecting the HER activity. These results provide a theoretical basis for the design of high-performance MXenes HER catalysts and contribute new research perspectives.

Rationally constructed CuS1-x/SnS2 Ohmic junction for enhanced photocatalytic H2 evolution under visible-light irradiation

SnS2 is a promising material for photocatalytic hydrogen (H2) evolution under visible-light irradiation. However, its efficiency is limited by the insufficient separation of photogenerated carriers and the few number of catalytic reaction sites on the surface. Herein, CuS1-x/SnS2 photocatalysts were successfully constructed and synthesized via a two-step hydrothermal process. Metallic CuS1-x nanosheets with S vacancy grow on the surface of SnS2 nanosheets form the Ohmic junction with an internal electric field (IEF). The 9% CuS1-x/SnS2 composite obtains the optimal H2-production rate of 742.3 μmolh−1g−1 under visible light irradiation, which is 4.5 times higher than pure SnS2. Systematic experimental investigations reveal CuS1-x/SnS2 Ohmic junction enhances absorbance in the visible light region and facilitates the transfer and separation of photoexcited carriers, thus improving hydrogen production. Density functional theory (DFT) calculations shown CuS1-x/SnS2 has an optimal hydrogen adsorption free energy (ΔGH*) of −0.22 eV. This research provides guidance to design SnS2-based heterojunction photocatalysts to realize efficient solar-to-hydrogen fuel conversion.

Superaerophobic Ni3N/Ni@W2N3 multi-heterointerfacial nanoarrays for efficient alkaline electrocatalytic hydrogen evolution reaction

The hydrogen evolution performances of electrocatalysts are greatly restricted by their unfavorable hydrogen evolution kinetics and the undesirable accumulation of as-evolved gas bubbles on the electrocatalysts surface. Herein, we present the fabrication of self-supporting multi-heterointerfacial nanoarrays electrode toward addressing these challenges simultaneously. A monolith Ni3N/Ni@W2N3 electrode is prepared, which exhibits a multi-heterojunction interface between the different components. The construction of this multi-heterojunction interface allows for the redistribution of the electrons, thus alleviating the strong Ni-H bond and optimizing the hydrogen adsorption free energy toward more efficient HER catalysis. Moreover, by virtue of the distinct nanoarray structure, the Ni3N/Ni@W2N3 nanoarrays exhibit improved hydrophilicity and superaerophobicity compared with Ni/Ni3N, facilitating water contact and enabling more efficient detachment of the as-evolved H2 bubbles from the surface. Benefiting from these attractive features, the Ni3N/Ni@W2N3 nanoarrays deliver an attractive alkaline HER catalytic activity with a low overpotential of 66 mV to achieve a current density of 10 mA cm−2, which is comparable with that of the benchmark Pt/C electrode. Moreover, the electrode exhibits remarkable stability during long-term electrolysis. The simultaneous interface and nanostructure engineering provide a feasible pathway for obtaining high-performance electrodes and beyond for various electrochemical reactions.

Enhancement of hydrogen evolution activity of CoS2/MoS2 heterostructure catalysts by electronic structure modulation

MoS2 exhibits high catalytic ability; however, its wide band gap (1.73 eV) and poor intrinsic conductivity significantly restrict the enhancement of its catalytic activity. To enhance the electron transfer between the interface of heterojunctions and improve the hydrogen evolution reaction (HER) performance, the paper constructs a CoS2/MoS2 heterostructures by growing CoS2/MoS2-X on carbon cloth (CC) using a straightforward one-step method. It investigates the HER properties of the heterojunctions of various molar ratios of ammonium molybdate to cobalt nitrate. The results indicate that the CoS2/MoS2-X catalyst exhibits excellent electrocatalytic activity (73 mV@10 mA cm−2) and Tafel slope (80.42 mV dec−1) at 1.0 M KOH when the molar ratio of ammonium molybdate to cobalt nitrate is 1:1 (X = 5). CoS2/MoS2-5 exhibits good durability of over 100 h when current densities are 10 and 100 mA cm−2. Density functional theory (DFT) calculations indicate that heterostructures present an optimized Gibbs free energy of hydrogen adsorption (ΔGH*) close to zero, providing insight into the exceptional HER performance. This work provides a simple, effective and innovative strategy for preparing high-activity CoS2/MoS2 catalysts by modulation of electronic 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.

Activating CoP via spontaneous atomic palladium doping for efficient hydrogen evolution

Electrocatalytic hydrogen evolution is an efficient and clean hydrogen production technology with simple process and high product purity. Searching for inexpensive alternatives to platinum will help popularize proton exchange membrane water electrolysis (PEMWE) technology. However, the alternative catalytic materials are essentially limited by low catalytic efficiency. Herein, we address this challenge through chemically activating cobalt phosphide (CoP) by doping a small amount of atomic palladium. Palladium substitution occurs at the cobalt site of CoP. Theoretical calculations manifest that the phosphorus atoms near the palladium sites exhibit almost zero hydrogen adsorption free energy. The final cobalt phosphide doped with only 2 wt% of palladium shows wonderful HER performance. Specifically, its overpotential at a current density of 10 mA cm−2 is only 37.5 mV in an acidic medium, and the corresponding Tafel slope is 56 mV dec−1. This work provides a reference for preparing high performance non-platinum catalysts.

Ternary conjugated microporous polymer boosted photocatalytic hydrogen evolution via dual heterocyclic strategy

Heterocyclic organic semiconductors have attracted significant attention as photocatalysts for hydrogen evolution due to excellent absorbency and abundant active sites. Herein, we developed a dual heterocyclic (O/S) conjugated microporous polymer Py-Th-Fu, consisting of both the furan and thiophene heterocycles, for photocatalytic H2 evolution. Compared with the furan O-heterocycle Py-Fu and thiophene S-heterocycle Py-Th, the Py-Th-Fu with the dual heterocyclic structure is more outstanding in regulating the optoelectronic properties, morphological properties, electric charge shift kinetics, and photocatalytic H2 evolution activity. Computational analysis also elucidates the smallest hydrogen adsorption free energy of Py-Th-Fu, which suggests it is the most advantageous for hydrogen mass transfer in this dual heterocycle polymer. As a result, the synergistic combination of two different heteroatom catalytic sites enables the dual heterocycle Py-Th-Fu to afford enhanced catalytic activity with an optimal rate of 23.28 mmol g−1 h−1, which is nearly equal to 5.06 and 1.58 times that of the corresponding O- and S-containing single heterocycles Py-Fu and Py-Th under visible lighting (λ > 420 nm). Our study demonstrates that the dual heterocyclic strategy using ternary copolymerization to tune the optoelectronic properties may open the horizon for fabricating high-performance photocatalytic water splitting via sunlight-driven hydrogen evolution.

Oxygen-Vacancy-Induced Enhancement of BiVO4 Bifunctional Photoelectrochemical Activity for Overall Water Splitting.

Hydrogen generation via photoelectrochemical (PEC) overall water splitting is an attractive means of renewable energy production so developing and designing the cost-effective and high-activity bifunctional PEC catalysts both for the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) has been focused on. Based on first-principles calculations, we propose a feasible strategy to enhance either HER or OER performance in the monoclinic exposed BiVO4 (110) facet by the introduction of oxygen vacancies (Ovacs). Our results show that oxygen vacancies induce charge rearrangements, which enhances charge transfer between active sites and adatoms. Furthermore, the incorporation of oxygen vacancies reduces the work function of the system, which makes charge transfer from the inner to the surface more easily; thus, the charges possess stronger redox capacity. As a result, the Ovac reduces both the hydrogen adsorption-free energy (ΔGH*) for the HER and the overpotential for the OER, facilitating the PEC activity of overall water splitting. The findings provide not only a method to develop bifunctional PEC catalysts based on BiVO4 but also insight into the mechanism of enhanced catalytic performance.

A catalyst family of high-entropy alloy atomic layers with square atomic arrangements comprising iron- and platinum-group metals.

We report a catalyst family of high-entropy alloy (HEA) atomic layers having three elements from iron-group metals (IGMs) and two elements from platinum-group metals (PGMs). Ten distinct quinary compositions of IGM-PGM-HEA with precisely controlled square atomic arrangements are used to explore their impact on hydrogen evolution reaction (HER) and hydrogen oxidation reaction (HOR). The PtRuFeCoNi atomic layers perform enhanced catalytic activity and durability toward HER and HOR when benchmarked against the other IGM-PGM-HEA and commercial Pt/C catalysts. Operando synchrotron x-ray absorption spectroscopy and density functional theory simulations confirm the cocktail effect arising from the multielement composition. This effect optimizes hydrogen-adsorption free energy and contributes to the remarkable catalytic activity observed in PtRuFeCoNi. In situ electron microscopy captures the phase transformation of metastable PtRuFeCoNi during the annealing process. They transform from random atomic mixing (25°C), to ordered L10 (300°C) and L12 (400°C) intermetallic, and finally phase-separated states (500°C).

Unveiling the enhanced hydrogen evolution performance of ternary heterostructures Mo5O14-Y(OH)3-CoMoO4/CF electrocatalysis

The challenge in electrocatalysis lies in finding stable and efficient catalysts for hydrogen evolution, especially those based on non-noble metals. Herein, the Mo5O14-Y(OH)3-CoMoO4/CF (CF stands for cobalt foam) catalyst rich in ternary heterostructures have been successfully synthesized. The catalyst is composed of cumin-like nanoparticles randomly dispersed on microcolumns. This unique structure ensures both its electrocatalytic activity and structural stability. Electrochemical tests demonstrate exceptional water splitting capabilities, with overpotentials of just 40 mV at 10 mA cm−2 (j10) and 219 mV at 1000 mA cm−2 (j1000). Furthermore, the catalyst shows minimal performance degradation after long-term testing, maintaining stable electrochemical performance for 60 h at j10 and 18 h at j800. Surface energy calculations and scanning electron microscopy (SEM) indicate that yttrium(Y) promotes the formation of cumin-like nanoparticles. Density functional theory (DFT) analysis, along with in situ Raman spectroscopy, suggests that the interaction among the three metals forms Mo5O14-Y(OH)3-CoMoO4 ternary heterostructures, effectively reducing the energy barrier for the hydrogen evolution reaction (HER). Notably, the Y sites in the CoMoO4-Y(OH)3 heterostructure exhibit the lowest hydrogen adsorption free energy (ΔGH⁎: −0.31 eV), making them the primary active sites for Mo5O14-Y(OH)3-CoMoO4/CF.

Ru-doping W4.6N4 nanoparticles anchored on N-doped graphene tubes as efficient hydrogen evolution electrocatalyst

Designing efficient electrocatalysts for hydrogen evolution reaction (HER) is essential to facilitate hydrogen energy applications. Herein, efficient strategies of doping with metal atoms (Ru) and incorporating with conductive carbon-based material (N-doping graphene tubes) have been developed to construct the hybrid electrocatalyst RuW4.6N4@N-GTs, in which, Ru-doped W4.6N4 nanoparticles integrated on the surface of N-doped graphene tubes. RuW4.6N4@N-GTs reveals superior HER activity and good stability, with a low overpotential of 29 mV to deliver the current density of 10 mA cm−2 and a low Tafel slope of 57 mV dec−1. The unique 3D nano-structure morphology of abundant homogeneous RuW4.6N4 nanoparticles supported on conductive N-GTs network carrier contributes to expose more electrochemical active sites, promoting electrolyte transport and gas emission. At the same time, the N-GTs skeleton could prevent the RuW4.6N4 particles from agglomerating and collapsing, thus leading to the superior stability during HER process. The in situ Ru heteroatom doping could cause the directional electron transfer and more nitrogen vacancies, thus modulating the electron structure of catalysts and optimizing the hydrogen adsorption free energy. The synergistic effect of the above merits endows RuW4.6N4@N-GTs with outstanding HER performance for potential applications in the hydrogen production field.