Hydrogen Oxidation Reaction Activity Research Articles

Atomically dispersed Iridium on Mo2C as an efficient and stable alkaline hydrogen oxidation reaction catalyst

Hydroxide exchange membrane fuel cells (HEMFCs) have the advantages of using cost-effective materials, but hindered by the sluggish anodic hydrogen oxidation reaction (HOR) kinetics. Here, we report an atomically dispersed Ir on Mo2C nanoparticles supported on carbon (IrSA-Mo2C/C) as highly active and stable HOR catalysts. The specific exchange current density of IrSA-Mo2C/C is 4.1 mA cm−2ECSA, which is 10 times that of Ir/C. Negligible decay is observed after 30,000-cycle accelerated stability test. Theoretical calculations suggest the high HOR activity is attributed to the unique Mo2C substrate, which makes the Ir sites with optimized H binding and also provides enhanced OH binding sites. By using a low loading (0.05 mgIr cm−2) of IrSA-Mo2C/C as anode, the fabricated HEMFC can deliver a high peak power density of 1.64 W cm−2. This work illustrates that atomically dispersed precious metal on carbides may be a promising strategy for high performance HEMFCs.

Balancing the Binding of Intermediates Enhances Alkaline Hydrogen Oxidation on D-Band Center Modulated Pd Sites.

Exploring efficient alkaline hydrogen oxidation reaction (HOR) electrocatalysts is of great concern for constructing anion exchange membrane fuel cells (AEMFCs). Herein, d-band center modulated PdCo alloys with ultralow Pd content anchored onto the defective carbon support (abbreviated as PdCo/NC hereafter) are proposed as highly efficient HOR catalyst. The as-prepared catalyst exhibits exceptional HOR performance compared to the Pt/C catalyst, achieving thermodynamically spontaneous and kinetically preferential reactions. Specifically, the resultant PdCo/NC demonstrates a marked enhancement in alkaline HOR performance, with the highest mass and specific activities of 1919.6 mA mgPd-1 and 1.9 mA cm-2, 51.1 and 4.2 times higher than those of benchmark of Pt/C, along with an excellent stability in a chronoamperometry test. In the analysis of in situ Raman spectra, it was discovered that tetrahedrally coordinated H-bonded water molecules were formed during the HOR process. This indicates that the promotion of interfacial water molecule formation and enhancement of HOR activities in PdCo/NC are facilitated by defect engineering and the turning of d-band center in PdCo alloy. The essential knowledge obtained in this study could open up a new direction for modifying the electronic structure of cost-effective HOR catalysts through electronic structure engineering.

Unraveling Stoichiometry Effect in Nickel‐Tungsten Alloys for Efficient Hydrogen Oxidation Catalysis in Alkaline Electrolytes

Anion‐exchange membrane fuel cells provide the possibility to use platinum group metal‐free catalysts, but the anodic hydrogen oxidation reaction (HOR) suffers from sluggish kinetics and its source is still debated. Here, over nickel‐tungsten (Ni‐W) alloy catalysts, we show that the Ni:W ratio greatly governs the HOR performance in alkaline electrolyte. Experimental and theoretical studies unravel that alloying with W can tune the unpaired electrons in Ni, tailoring the potential of zero charge and the catalytic surface to favor hydroxyl adsorption (OHad). The OHad species coordinately interact with potassium (K+) ions, which break the K+ solvation sheath to leave free water molecules, yielding an improved connectivity of hydrogen‐bond networks. Consequently, the optimal Ni17W3 alloy exhibits alkaline HOR activity superior to the state‐of‐the‐art platinum on carbon (Pt/C) catalyst and operates steadily with negligible decay after 10,000 cycles. Our findings offer new understandings of alloyed HOR catalysts and will guide rational design of next‐generation catalysts for fuel cells.

Unraveling Stoichiometry Effect in Nickel-Tungsten Alloys for Efficient Hydrogen Oxidation Catalysis in Alkaline Electrolytes.

Anion-exchange membrane fuel cells provide the possibility to use platinum group metal-free catalysts, but the anodic hydrogen oxidation reaction (HOR) suffers from sluggish kinetics and its source is still debated. Here, over nickel-tungsten (Ni-W) alloy catalysts, we show that the Ni:W ratio greatly governs the HOR performance in alkaline electrolyte. Experimental and theoretical studies unravel that alloying with W can tune the unpaired electrons in Ni, tailoring the potential of zero charge and the catalytic surface to favor hydroxyl adsorption (OHad). The OHad species coordinately interact with potassium (K+) ions, which break the K+ solvation sheath to leave free water molecules, yielding an improved connectivity of hydrogen-bond networks. Consequently, the optimal Ni17W3 alloy exhibits alkaline HOR activity superior to the state-of-the-art platinum on carbon (Pt/C) catalyst and operates steadily with negligible decay after 10,000 cycles. Our findings offer new understandings of alloyed HOR catalysts and will guide rational design of next-generation catalysts for fuel cells.

Unravelling the La dopant induced physicochemical changes and the electrical behaviour on BaFeO3 under oxidising and reducing atmospheres

Electroceramic oxides like La-doped BaFeO3 garner greater interest owing to their tunability of mixed ionic conduction. However, reports on the effect of La on the microstructural changes, the type of conduction mechanism under different atmospheres and the negative charge transfer influenced by the Fe-O hybridization in Ba1−xLaxFeO3−δ are hardly available. Doping La induces cation vacancies and Fe reduction, creating nanorod decorated surface after the high-temperature treatment. Conductivity studies expose the rate-limiting steps for hydrogen oxidation reaction (HOR) and oxygen reduction reaction (ORR) as the ohmic resistances and Ba segregation effects. Among the samples studied, Ba0.9La0.1FeO3−δ performs better at 800 °C with an activation energy of ∼0.35 eV under both oxidizing and reducing atmospheres. Surface analysis after EIS reveals Fe and O with different oxidation states that enhance the total conductivity. The amount of hydroxyl species retained (23.66% for Ba0.9La0.1FeO3−δ ) and the ratio of the adsorbed to the lattice oxygen (15.33% for Ba0.9La0.1FeO3−δ ) gives insight on HOR and ORR activities. Also, computational studies validated the negative charge transfer mechanism of the samples under thermally assisted oxidation. The results indicate Ba0.9La0.1FeO3−δ as a tuneable electrode for solid oxide cells.

Porous Ruthenium-Tungsten-Zinc Nanocages for Efficient Electrocatalytic Hydrogen Oxidation Reaction in Alkali.

With the rapid development of anion exchange membrane technology and the availability of high-performance non-noble metal cathode catalysts in alkaline media, the commercialization of anion exchange membrane fuel cells has become feasible. Currently, anode materials for alkaline anion-exchange membrane fuel cells still rely on platinum-based catalysts, posing a challenge to the development of efficient low-Pt or Pt-free catalysts. Low-cost ruthenium-based anodes are being considered as alternatives to platinum. However, they still suffer from stability issues and strong oxophilicity. Here, we employ a metal-organic framework compound as a template to construct three-dimensional porous ruthenium-tungsten-zinc nanocages via solvothermal and high-temperature pyrolysis methods. The experimental results demonstrate that this porous ruthenium-tungsten-zinc nanocage with an electrochemical surface area of 116 m2 g-1 exhibits excellent catalytic activity for hydrogen oxidation reaction in alkali, with a kinetic density 1.82 times and a mass activity 8.18 times higher than that of commercial Pt/C, and a good catalytic stability, showing no obvious degradation of the current density after continuous operation for 10,000 s. These findings suggest that the developed catalyst holds promise for use in alkaline anion-exchange membrane fuel cells.

Two-dimensional MXene supported Ru-Cr(OH)x clusters as an efficient electrocatalyst for hydrogen oxidation reaction

The development of high-performance non-platinum catalysts remains a key challenge for the practical application of anion-exchange membrane fuel cells due to the sluggish kinetics response of the hydrogen oxidation reaction (HOR) in alkaline electrolytes. Herein, we report an outstanding HOR electrocatalyst using a facile one-step method with the two-dimensional double transition metal MXene (Mo2TiC2Tx) as a carrier mixed with metallic ruthenium and Cr(OH)x clusters (Ru-Cr(OH)x/MXene). Specifically, the as-prepared Ru-Cr(OH)x/MXene electrocatalyst exhibits a high apparent kinetic current (jk) of 18.32 mA cm−2 and exchange current (j0) of 1.64 mA cm−2 at an overpotential of 50 mV, respectively, which are 4.74 and 1.46 times as high as those of Pt/C catalyst. Additionally, mechanism experiments indicated that the Ru-Cr(OH)x/MXene electrocatalyst could attenuate the adsorption of hydrogen intermediate (Had) and enhance the adsorption of hydroxyl species (OHad) to promote CO oxidation, which resulted in a significant increase in the HOR activity and enhanced tolerance to CO. Furthermore, combining theoretical studies via density functional theory calculations, our work confirm that the interaction effect of each components of Ru-Cr(OH)x/MXene can optimize the binding energy of the Had and OHad for the HOR. This work develops a new approach to design of HOR electrocatalyst with MXene-based materials.

Pt nanorods supported on Nb-doped ceria: A promising anode catalyst for polymer electrolyte fuel cells

For polymer electrolyte fuel cells (PEFCs), platinum nanoparticles supported on carbon black (Pt/C) serve as the commonly used hydrogen anode catalyst, exhibiting high activity for the hydrogen oxidation reaction (HOR), while the carbon support is susceptible to corrosion under PEFC operation. Here, a highly active HOR anode catalyst of Pt nanorod supported on niobium (Nb)-doped ceria without using corrosive carbon support was developed, which exhibits high durability at high potentials associated with hydrogen starvation. The production of hydrogen peroxide (H2O2), which can degrade the polymer electrolyte membrane, was also found to be significantly suppressed on the Pt nanorod/doped ceria catalyst. Density functional theory (DFT) calculations suggests that the Pt nanorod geometry and interaction with Nb and Ce favor HOR activity and stability while suppressing H2O2 production by modulating the adsorption of key reaction intermediates. This new catalyst has the potential to be used as an anode for high-performance and high-durability PEFCs.

Ultralow-Loading Ruthenium-Iridium Fuel Cell Catalysts Dispersed on Zn-N Species-Doped Carbon.

Developing low-loading platinum-group-metal (PGM) catalysts is one of the key challenges in commercializing anion-exchange-membrane-fuel-cells (AEMFCs), especially for hydrogen oxidation reaction (HOR). Here, ruthenium-iridium nanoparticles being deposited on a Zn-N species-doped carbon carrier (Ru6Ir/Zn-N-C) are synthesized and used as an anodic catalyst for AEMFCs. Ru6Ir/Zn-N-C shows extremely high mass activity (5.87AmgPGM -1) and exchange current density (0.92mAcm-2), which is 15.1 and 3.9 times that of commercial Pt/C, respectively. Based on the Ru6Ir/Zn-N-C AEMFCs achieve a peak power density of 1.50Wcm-2, surpassing the state-of-the-art commercial PtRu catalysts and the power ratio of the normalized loading is 14.01WmgPGM anode -1 or 5.89W mgPGM -1 after decreasing the anode loading (87.49µgcm-2) or the total PGM loading (0.111mgcm-2), satisfying the US Department of Energy's PGM loading target. Moreover, the solvent and solute isotope separation method is used for the first time to reveal the kinetic process of HOR, which shows the reaction is influenced by the adsorption of H2O and OH-. The improvement of the hydrogen bond network connectivity of the electric double layer by adjusting the interfacial H2O structure together with the optimized HBE and OHBE is proposed to be responsible for the high HOR activity of Ru6Ir/Zn-N-C.

One‐Pot Synthesis of Carbon‐Supported Pd Nanoparticles with Ni and Carbon Matrix Protection for Durable Alkaline Hydrogen Oxidation Reaction

Protecting nanoparticles with a carbon matrix can enhance the durability of the catalysts in alkaline fuel cells (AFC) and is well‐documented. While others have tried complex syntheses to produce small nanoparticle catalysts, in this work, in order to scale‐up batches of 15 g or more, carbon‐cap (or carbon‐coating) protected Vulcan XC72‐supported Pd‐Ni (1‐2) nanoparticles (Pd‐Niacc/C) were successfully synthesized via a one‐step dry‐synthesis process. This catalyst was compared with a commercial Pd‐Ni/Vulcan XC72 material (PdNi/C, Premetek) in terms of hydrogen oxidation reaction (HOR) activity and stability. To produce less ordered carbon caps (versus graphite/graphene), a low‐temperature heat‐treatment (below 500°C) was used, resulting in Pd‐Niacc/C of unique electrochemical properties: easily electrochemically activated, this catalyst outperforms PdNi/C for alkaline HOR and proves more durable under highly oxidizing accelerated stress test (AST) conditions. Identical location transmission electron microscopy (ILTEM), X‐ray photoelectron spectroscopy (XPS) and rotating disk electrode (RDE) measurements demonstrate how the Ni‐rich surface plays an important role in HOR activity for both PdNi/C and PdNiacc/C and that the protective carbon‐coating of the latter ensures better durability of performance and better resistance to materials degradation.

Regulation of hydrogen binding energy via oxygen vacancy enables an efficient trifunctional Rh-Rh2O3 electrocatalyst for fuel cells and water splitting

Developing multi-functional electrocatalysts is of great practical significance for fuel cells and water splitting. Herein, Rh-Rh2O3 nanoclusters are prepared and the surface oxygen vacancy content is regulated elaborately by post-treatment. The optimized Rh-Rh2O3/C-400 exhibits superior trifunctional catalytic activity for hydrogen oxidation reaction (HOR), hydrogen evolution reaction (HER) and hydrazine oxidation reaction (HzOR), i.e., the mass activity for HOR is 2.29 mA μgRh-1, and the overpotential for HER and HzOR at 10 mA cm−2 is as low as 12 mV and 31 mV, respectively, superior to the benchmark Pt/C. Rh-Rh2O3/C-400 also displays promising performance in practical devices, with the H2-O2 anion-exchange-membrane fuel cell delivering a peak power density of 0.66 W cm−2, and the hydrazine-assisted water splitting electrolyzer requiring a low electrolysis voltage of 0.161 V at 0.1 A cm−2. The experimental and theoretical investigations discover that the hydrogen binding energy (HBE) is linearly depended on surface oxygen vacancy contents, and the HBE directly determines the catalytic activity for HOR, HER and HzOR. This work not only innovates an efficient Rh-based nanocluster tri-functional electrocatalyst, but also eludicates the intrinsic relationship of surface structure-intermediate adsorption-catalytic activity.

High‐Performance Anion Exchange Membrane Fuel Cells Enabled by Nitrogen Configuration Optimization in Graphene‐Coated Nickel for Enhanced Hydrogen Oxidation

Anion exchange membrane fuel cell (AEMFC) technology is attracting intensive attention, due to its great potential by using non‐precious‐metal catalysts (NPMCs) in the cathode and cheap bipolar plate materials in alkaline media. However, in such case, the kinetics of hydrogen oxidation reaction (HOR) in the anode is two orders of magnitude sluggish than that of acidic electrolytes, which is recognized as the grand challenge in this field. Herein, we report the rationally designed Ni nanoparticles encapsulated by N‐doped graphene layers (Ni@NG) using a facile pyrolysis strategy. Based on the density functional theory calculations and electrochemical performance analysis, it is witnessed that the rich Pyridinic‐N within the graphene shell optimizes the binding energy of the intermediates, thus enabling the fundamentally enhanced activity for HOR with robust stability. As a proof of concept, the resultant Ni@NG sample as the anode with a low loading (1.8 mg cm−2) in AEMFCs delivers a high peak power density of 500 mW cm−2, outperforming all of those of NPMC‐based analogs ever reported.

Pd-Based Bimetallic Electrocatalysts for Hydrogen Oxidation Reaction in 0.1 M KOH Solution.

A series of carbon black-supported 7.5 wt.% Pd-2.5 wt.% M/C (M: Ag, Ca, Co, Cu, Fe, Ni, Ru, Sn, Zn) electrocatalysts, synthesized via the wet impregnation method, and reduced at 300 °C, were compared in terms of their hydrogen oxidation reaction (HOR) activity in a 0.1 M KOH solution using the thin-film rotating-disk electrode technique. Moreover, 10 wt.% Pd/C and 10 wt.% Pt/C electrocatalysts were prepared in the same manner and used as references. The 7.5 wt.% Pd-2.5 wt.% Ni/C electrocatalyst exhibited the highest HOR activity among the Pd-based electrocatalysts, although it was lower than that of the 10 wt.% Pt/C. Its activity was also found to be higher than that of Pd-Ni electrocatalysts of the same total metal loading (10 wt.%) and reduction temperature (300 °C) but of different Pd to Ni atomic ratio. It was also higher than that of 7.5 wt.% Pd-2.5 wt.% Ni/C electrocatalysts that were reduced at temperatures other than 300 °C. The superior activity of this electrocatalyst was attributed to an optimum value of the hydrogen binding energy of Pd, which was induced by the presence of Ni (electronic effect), as well as to the oxophilic character of Ni, which favors adsorption on the Ni surface of hydroxyl species that readily react with adsorbed hydrogen atoms on neighboring Pd sites in the rate-determining step.

Charge distribution modulation of hollow flower-like tungsten doped nickel nitride for alkaline hydrogen oxidation

Exploring efficient nickel (Ni)-based catalysts for alkaline hydrogen oxidation reaction (HOR) to replace platinum group metal (PGM) is highly essential for the development of anion exchange membrane fuel cells. Nevertheless, the HOR activity of Ni is far away from PGM owing to the strong hydrogen adsorption. Herein, the tungsten-doped nickel nitride (W-Ni3N) with modulated local charge distribution and hollow flower structure is presented to improve the HOR performance. Mechanism studies reveal that W doping induces the redistribution of local charge around Ni sites due to the electron transfer from Ni to W, which strengthens the hydroxyl adsorption and simultaneously weakens hydrogen adsorption. Benefitting from the optimized adsorption of HOR intermediates and hollow flower structure, W-Ni3N exhibits improved intrinsic activity and mass activity, which are 1.7 and 10 times higher than that of pure Ni3N, respectively. This work presents a promising way to design cost-effective electrocatalysts by fine-tuning the electronic structure.

Cation Effects on Hydrogen Oxidation Reaction on Pt Single-Crystal Electrodes in Alkaline Media.

The exact mechanism behind the cation-assisted hydrogen oxidation reaction (HOR) on platinum electrodes in alkaline media remains disputed. We show that the cation effects at platinum display a remarkable structure sensitivity: not only the H adsorption but also the HOR activity on (111) terrace sites are independent of the nature of cation and cation concentration. On (110) step sites, at low cation concentration and mildly alkaline media, cations promote the HOR, whereas at more alkaline pH and consequently higher near-surface cation concentrations, the HOR is inhibition by the cations. Moreover, the role of the cation on terrace-OHad is different from that on step-OHad, as can also be observed from the inhibition of the HOR current by terrace-OHad at higher potentials. These results suggest that near the onset potential, HOR mainly takes place on steps, but under diffusion-limited conditions at higher overpotential, HOR mainly takes place on terraces.

Activating and Identifying the Active Site of RuS2 for Alkaline Hydrogen Oxidation Electrocatalysis.

Searching for highly efficient and economical electrocatalysts for alkaline hydrogen oxidation reaction (HOR) is crucial for the development of alkaline polymer membrane fuel cells. Here, we report a valid strategy to active pyrite-type RuS2 for alkaline HOR electrocatalysis by introducing sulfur vacancies. The obtained S-vacancies modified RuS2-x exhibits outperformed HOR activity with a current density of 0.676 mA cm-2 and mass activity of 1.43 mA μg-1, which are 15-fold and 40-fold improvement than those of Ru catalyst. In situ Raman spectra demonstrate the formation of S-H bond during the HOR process, identifying the S atom of RuS2-x is the real active site for HOR catalysis. Density functional theory calculations and experimental results including in situ surface-enhanced infrared absorption spectroscopy suggest the introduction of S vacancies can rationally modify the p orbital of S atoms, leading to enhanced binding strength between the S sites and H atoms on the surface of RuS2-x, together with the promoted connectivity of hydrogen-bonding network and lowered water formation energy, contributes to the enhanced HOR performance.

Activating and Identifying the Active Site of RuS2 for Alkaline Hydrogen Oxidation Electrocatalysis

AbstractSearching for highly efficient and economical electrocatalysts for alkaline hydrogen oxidation reaction (HOR) is crucial for the development of alkaline polymer membrane fuel cells. Here, we report a valid strategy to active pyrite‐type RuS2 for alkaline HOR electrocatalysis by introducing sulfur vacancies. The obtained S‐vacancies modified RuS2−x exhibits outperformed HOR activity with a current density of 0.676 mA cm−2 and mass activity of 1.43 mA μg−1, which are 15‐fold and 40‐fold improvement than those of Ru catalyst. In situ Raman spectra demonstrate the formation of S−H bond during the HOR process, identifying the S atom of RuS2−x is the real active site for HOR catalysis. Density functional theory calculations and experimental results including in situ surface‐enhanced infrared absorption spectroscopy suggest the introduction of S vacancies can rationally modify the p orbital of S atoms, leading to enhanced binding strength between the S sites and H atoms on the surface of RuS2−x, together with the promoted connectivity of hydrogen‐bonding network and lowered water formation energy, contributes to the enhanced HOR performance.

Optimizing Nickel Orbital Occupancy via Co‐Modulation of Core and Shell Structures to Accelerate Alkaline Hydrogen Electro‐Oxidation Reaction

AbstractNickel‐based catalysts are recognized as a promising alternative to platinum‐based catalysts for the alkaline hydrogen oxidation reaction (HOR) yet suffer from poor stability and relatively low activity. Herein, a nitrogen ligand‐assisted approach is reported to encapsulate nickel‐copper nanoparticles within few carbon layers, and by modulating the core and shell components/structure, the charge distribution in the nanostructures can be finely regulated. The optimized Ni93Cu7@NC catalyst exhibits outstanding HOR activity with an intrinsic activity of 61.0 µA cm−2 and excellent stability, which is among the most advanced Ni‐based HOR catalysts. Notably, an alkaline exchange membrane fuel cell utilizing this catalyst achieves a peak power density of 381 mW cm−2 and maintains stability at 100 mA cm−2 for over 24 h. Experimental and theoretical investigations unveil that the electron re‐distribution at the interface of NiCu core and nitrogen‐doped carbon reduces the electron occupancy in Ni 4s‐H 1s bonding orbitals and Ni 3dz2/yz‐O 2p antibonding orbitals, leading to a weakened hydrogen binding energy and enhance hydroxide binding energy. Consequently, the limiting energy for the HOR is reduced following a bifunctional mechanism on the Ni93Cu7@NC. This work provides a core‐shell co‐modulation strategy to accurately regulate the electronic structure of transition metals to design robust catalysts.

Single-metal-atom-anchored RuN2 monolayers: A high-performance electrocatalyst for alkaline hydrogen oxidation reactions

The development of alkaline exchange membrane fuel cells (AEMFCs) is severely hampered by the scarcity of efficient Pt-free catalysts for the anodic hydrogen oxidation reaction (HOR). In this work, we systematically explored the HOR performance of single 3d transition metal atom-doped RuN2 monolayers (TM-RuN2, TM = Ti-Zn) by density functional theory calculations. Formation energy, oxidation potential, and electronic structure analyses indicate that the Ti, V, Fe, Co, and Ni-doped RuN2 not only have a good conductivity, but also possess strong thermodynamic and electrochemical stability. For TM-RuN2, the ortho-N and metal (TM or ortho-Ru) atoms form a dual-active site for the adsorption of H* and OH*, respectively, where the adsorption strength is fine-tunable via the TM-modulated electronic structure. The HOR occurs preferentially through the H2 + OH*-H* + OH* mechanism on the pristine and Co, Ni, Cu, and Zn-doped RuN2, and the Tafel − H* + OH* mechanism on the Ti, V, Cr, Mn, and Fe-doped RuN2. The precisely balanced H* and OH* adsorption strength of Fe-RuN2 results in the ultra-low free energy barriers to HOR. Benefiting from the strong thermodynamic and electrochemical stability, good conductivity, and excellent HOR activity, Fe-RuN2 exhibits a huge potential as HOR electrocatalysts for AEMFCs.

Construction of Heterostructure between Ni17W3 and WO2 to Boost the Hydrogen Oxidation Reaction in Alkaline Medium.

The inferior intrinsic performance of Ni-based catalysts for the hydrogen oxidation reaction (HOR) in an alkaline medium seriously restricts the utilization of emerging anion-exchange membrane fuel cells (AEMFCs). This is because the hydrogen and hydroxyl binding energies on Ni need to be optimized. Although electrocatalysts obtained by alloying Ni with Mo or W reportedly exhibit enhanced activity, they are still far from industrial requirements based on unbalanced HBE and OHBE. Herein, we report to further enhance alkaline HOR activity by constructing a heterostructure between NiW alloy and metal oxide (Ni17W3/WO2), which is synthesized through solvothermal treatment combined with annealing. The as-fabricated reduced graphene oxide (rGO)-supported Ni17W3/WO2 (Ni17W3/WO2/rGO) exhibits state-of-the-art catalytic activity (current density of 2.9 mA cm-2 at 0.1 V vs RHE), faster kinetics (geometric kinetics current density of 4.0 mA cm-2 that can be comparable to Pt/C), and high stability (maintaining the current density for more than 80 h) toward HOR in alkaline media. The detailed characterizations reveal that the charge transfer across the boundary arising from constructing the as-prepared heterostructure tunes the electronic structures, ultimately facilitating the HOR process.