Efficient Catalyst For Hydrogen Evolution Reaction Research Articles

Optimizing interactions for efficient hydrogen evolution reaction by incorporating rhenium nanoparticles on defect-rich carbon

The rich anchoring site on carbon renders it a promising support for catalytically active metal nanoparticles (NPs), thereby enhancing their intrinsic catalytic activity towards hydrogen evolution reaction (HER) through interactions between the support and the metal. However, complex synthesis conditions often compromise the synergy between the metal and support. Herein, we report Re NPs embedded on XC-72 carbon support to investigate the robust interactions in affecting the HER activity. Consequently, Re NPs anchored on defect-rich XC-72 exhibit efficient and robust HER activity in acidic conditions, achieving an extremely low overpotential of 25 mV to deliver a current density of 10 mA cm−2 and a Tafel slope of 78 mV dec−1, surpassing that of Pt/C catalyst. Based on experimental investigations and density functional theory calculations, the high catalytic activities of as-obtained Re/C can be attributed to the enhanced electron transport kinetics facilitated by the interactions between Re NPs and carbon support, the exposure of the active site on Re NPs, and lowered reaction energy barrier towards HER. This study provides valuable insights for the rational development of Re-based efficient catalysts for HER.

Electrodeposition of Nickel–Molybdenum–Phosphide on copper foam electrode for efficient hydrogen evolution reaction

In the quest for efficient and cost-effective catalysts to drive the hydrogen evolution reaction (HER) in electrochemical water splitting, copper foam (CuF) is a favorable candidate for electrode coating. Precious metal catalysts like Pt/C dominate the field but must be improved because of their high cost and scarcity. Therefore, we have synthesized and evaluated a sequence of nickel-originated electrocatalysts (Ni, NiMo, NiP, and NiMoP) with the electrodeposition of CuF to facilitate substantial improvements in HER performance. Herein, the Ni–Mo–P ternary system, owing to its desirable electronic structure and catalytic mechanism, contributes to enhancing the thermodynamics and kinetics of the HER. Performance analysis reveals that all studied catalysts follow the order of Ni/CuF > NiMo/CuF > NiP/CuF > NiMoP/CuF regarding both the Tafel slope and overpotential. Hence, the top performer, NiMoP/CuF, exhibits tremendous thermodynamics with an η10 = 159 mV and Tafel slope kinetics of 126.66 mV·dec⁻1 at 1.0 M KOH in water splitting. Overall, this report presents a well-capable way of optimizing the electrocatalytic function and stability of CuF-electro-coated catalysts for the HER. This research opens new avenues for cost-effective, stable, and efficient HER catalysts, showcasing the potential of NiMoP/CuF in advancing sustainable hydrogen production technologies.

Titanium dioxide heterojunction support design induced robust platinum catalytic hydrogen evolution over wide pH range

The development of efficient hydrogen evolution reaction (HER) electrocatalysts is critical for water splitting. Herein, rutile/anatase titanium dioxide heterojunction supported platinum nanoparticles (Pt-NPs) design with interfacial effect was developed as efficient HER catalyst (Pt@R/A-TiO2) over wide pH range. The R/A-TiO2 support design induces aggregated Pt-NPs on the heterojunction interface. In-situ Raman and in-situ infrared investigations over wide pH range reveal that there exists a strong hydrogen spillover from Pt-NPs to R/A-TiO2 support and fast proton transfer HER kinetics on Pt@R/A-TiO2. Theoretical calculations demonstrate that the R/A-TiO2 heterojunction modulates more electrons transferred from TiO2 support to Pt-NPs, and this electron-rich Pt-NPs weakens H adsorption, thus enhancing the hydrogen spillover effect and improving the HER performance of Pt@R/A-TiO2. In acidic/alkaline/neutral media, Pt@R/A-TiO2 demonstrates excellent HER activity and stability. Especially in acidic media, Pt@R/A-TiO2 exhibits high mass activity of 12.57 A mgPt−1 at an overpotential of 100 mV, which is nearly 11 times higher than Pt/C, and outperforms the recently reported Pt-based catalysts as well. This work advances the design of efficient and stable HER catalysts over wide pH range.

Spatially confined synthesis of large-sized MoS2 nanosheets in molten KSCN toward efficient hydrogen evolution

Low-temperature KSCN molten salt is a promising technique to synthesize defect-rich MoS2 catalysts for hydrogen evolution reaction (HER). However, owing to the fast ion diffusion rate for rapid crystal growth, the resultant catalysts show a morphology of microsphere, which aggregates from MoS2 nanosheets, to suppress the catalytic performance. In this work, large-sized few-layer MoS2 nanosheets are synthesized via a spatial confinement strategy by adding inert NaCl into the KSCN molten salt. With the NaCl spacer to physically block the long-distance ion diffusion and isolate the chemical reaction, the MoS2 nucleation and subsequent crystal growth could be controlled, guiding the nanosheets to grow along the narrow gap between the NaCl crystals to avoid aggregation. As a result, ultrathin MoS2 nanosheets with a large geometry size are constructed. Profiting from the architecture to expose active sites and boost charge transfer kinetics, the large-sized few-layer MoS2 nanosheets exhibit an impressive HER performance, showing a small η 10 of 160 mV and a low Tafel slope of 53 mV dec−1 with excellent stability. This work provides not only an efficient HER catalyst but also a facile spatial confinement technique to design and synthesize a large spectrum of transition metal sulfides for broad uses.

Rapid Joule-heating fabrication of Ce-doped Co/CoO on carbon nanotubes for efficiently electrocatalytic hydrogen production

In this work, Ce-doped Co/CoO grown on carbon nanotubes was prepared by a novel Joule-heating method. The rapid heating and cooling process caused lattice disorder, which effectively exposed active sites and further improved electrocatalytic activity in the hydrogen evolution reaction (HER). As prepared Ce-Co/CoO@CNTs by the rapid Joule-heating method exhibited excellent performance with an overpotential of only 47.6 mV @10 mA cm−2 in 1 M KOH electrolyte. Furthermore, as-prepared samples maintained exceptional chemical stability, with almost no decay observed even at high current densities (700 mA cm−2) for 200 h. In addition, using Ce-Co/CoO@CNTs catalyst in the alkaline exchange membrane (AEM) electrolyzers, an outstanding operating performance (1.62 V at 10 mA cm−2) was tested for overall water splitting. The formation of a large number of surface defects increased the number of active sites and accelerate the charge transfer. Additionally, the construction of Co/CoO heterojunctions modulated the electronic structure of the interfacial domains, optimizing reaction kinetics and providing a new pathway for designing and synthesizing efficient HER catalysts.

Armchair ReS2 Nanoribbons: A Promising Catalyst for Hydrogen Evolution Reaction

The two-dimensional material rhenium disulphide (ReS2) is currently receiving immense attention due to its applications in electrocatalysis. This is primarily due to ReS2 possessing excellent qualities like stability in air, easy exfoliation, methanol tolerance etc. However, the two-dimensional monolayer of ReS2 is more or less catalytically inert, due to the sulfur layers covering the Re atoms. Modifications of the two-dimensional monolayer like transition metal decoration, metal cluster deposition, nanoribbon formation etc, is found to lead to enhanced activity. Here, we computationally model a particular nanostructure of two-dimensional ReS2 which is in the form of a nanoribbon, for activity directed towards hydrogen evolution reaction (HER). We study the armchair configuration nanoribbons of ReS2 and find that these have a heightened HER activity compared to the basal plane. Through free energy computations, we predict that armchair ReS2 nanoribbons can have activity comparable to platinum and platinum based catalysts, which are ideal for HER. Using the nudged elastic band method, we investigate the probable mechanism of HER, and find that the Heyrovsky reaction has zero activation barrier for armchair ReS2 nanoribbons. Our results indicate that ReS2 nanoribbon is indeed a promising material as a stable and efficient HER catalyst.

Sub-2.5 nm monodisperse Mo2C nanoparticles on N-doped carbon: The facet engineering for boosting electrochemical hydrogen evolution

Molybdenum carbide materials have demonstrated remarkable potential in catalyzing the hydrogen evolution reaction (HER). However, further modulation of their performance through simultaneously engineering the size and surface crystal facets remains challenging. Herein, we report the successful fabrication of N-doped carbon-supported monodisperse Mo2C nanoparticles with a size of ∼2.06 nm, exhibiting co-exposed (101)/(102) facets-heterojunction, derived from annealing glycine and ammonium molybdate tetrahydrate. The optimized Mo2C/NC-Amt catalyst exhibits a low overpotentials of 128 mV to achieve the current density of 10 mA cm−2 and a small Tafel slope of 72 mV dec−1 under alkaline solution. By changing the molybdate precursor, the phase and crystal facet composition of molybdenum carbide can be effectively tuned, which provides a good platform for studying their structure-activity in HER. The theoretical calculations reveal the synergistic effect of (101)/(102) facets-heterojunction accelerates electron transfer and regulates the d band center of Mo2C, reducing the reaction barriers of intermediates in the HER process, thus significantly boosting reaction activity. This work proposes a novel insight into the rational fabrication of efficient HER catalysts through facet engineering toward heterojunction construction under the 2.5 nm region.

Ru2P/Ir2P Heterostructure Promotes Hydrogen Spillover for Efficient Alkaline Hydrogen Evolution Reaction

AbstractEfficient and durable electrocatalysts toward alkaline hydrogen evolution reaction (HER) are of great significance for the widespread application of anion‐exchange membrane water electrolyzer (AEMWE). Numerous single‐phase catalysts, such as Ru2P, have been explored as efficient HER catalysts; however, many have failed to overcome the inherent sluggish kinetics of the two separate steps involved in the alkaline HER: water dissociation and hydrogen production. In this study, density functional theory calculations are conducted to identify promising combinations of Ir2P and Ru2P materials that promote fast cascade water dissociation and H2 production via kinetically favorable hydrogen spillover from the Ru2P surface to the adjacent Ir2P. An unprecedented construction of Ir2P cluster‐decorated Ru2P hollow nanotubes (c‐RP/IP HNTs), which feature a cooperative heterostructural synergy are developed. This configuration shows greater performance than commercial Pt/C, achieving an overpotential of 23.2 mV at 10 mA cm−2 and maintaining long‐term stability for 55 h in half‐cell tests. Furthermore, the practical AEMWE test, incorporating c‐RP/IP HNTs, demonstrated a remarkable single‐cell performance of 12.23 A cm−2 at 2.0 V and operated stably under 1.0 A cm−2 for over 250 h. This surpasses that of the state‐of‐the‐art proton‐exchange membrane WE.

Material Engineering Strategies for Efficient Hydrogen Evolution Reaction Catalysts.

Water electrolysis, a key enabler of hydrogen energy production, presents significant potential as a strategy for achieving net-zero emissions. However, the widespread deployment of water electrolysis is currently limited by the high-cost and scarce noble metal electrocatalysts in hydrogen evolution reaction (HER). Given this challenge, design and synthesis of cost-effective and high-performance alternative catalysts have become a research focus, which necessitates insightful understandings of HER fundamentals and material engineering strategies. Distinct from typical reviews that concentrate only on the summary of recent catalyst materials, this review article shifts focus to material engineering strategies for developing efficient HER catalysts. In-depth analysis of key material design approaches for HER catalysts, such as doping, vacancy defect creation, phase engineering, and metal-support engineering, are illustrated along with typical research cases. A special emphasis is placed on designing noble metal-free catalysts with a brief discussion on recent advancements in electrocatalytic water-splitting technology. The article also delves into important descriptors, reliable evaluation parameters and characterization techniques, aiming to link the fundamental mechanisms of HER with its catalytic performance. In conclusion, it explores future trends in HER catalysts by integrating theoretical, experimental and industrial perspectives, while acknowledging the challenges that remain.

Silk derived electrospun carbon nanofibers loaded with CoS nanoparticles as efficient hydrogen evolution reaction catalysts in acidic and alkaline media

The design of a stable and efficient hydrogen evolution catalyst across the entire pH range is of significant importance for the development of hydrogen production technology by electrocatalytic water splitting. This study chose biomass silk fibroin protein as the electrospinning raw material, synthesizing a hybrid membrane of CoS@carbon nanofibers (CNF) with a layered core–shell structure through simple carbonization and hydrothermal treatment. The CoS nanoparticles can grow uniformly and densely on the CNF. By varying the concentrations of hexahydrate cobalt nitrate (Co(NO3)2·6H2O) and thiourea (CH4N2S), the morphology of the synthesized CoS nanoparticles on CNF can be controlled. Different microscopic morphologies lead to differences in the activity of the hydrogen evolution reaction (HER), attributed to variations in the exposed active sites for different morphologies. Compared to pure CNF, the CoS-2@CNF hybrid membrane exhibits excellent HER activity in both acidic and alkaline electrolytes. This highlights the synergistic catalytic effect between CNF and CoS particles. This work provides guidance for the rational design of bio-based catalysts with excellent performance.

Rationally designing of Co-WS2 catalysts with optimized electronic structure to enhance hydrogen evolution reaction

Designing and developing cost-effective, high-performance catalysts for hydrogen evolution reaction (HER) is crucial for advancing hydrogen production technology. Tungsten-based sulfides (WSx) exhibit great potential as efficient HER catalysts, however, the activity is limited by the larger energy required for water dissociation under alkaline conditions. Herein, we adopt a top-down strategy to construct heterostructure Co-WS2 nanofiber catalysts. The experimental results and theoretical simulations unveil that the work functions-induced built-in electric field at the interface of Co-WS2 catalysts facilitates the electron transfer from Co to WS2, significantly reducing water dissociation energy and optimizing the Gibbs free energy of the entire reaction step for HER. Besides, the self-supported catalysts of Co-WS2 nanoparticles confining 1D nanofibers exhibit an increased number of active sites. As expected, the heterostructure Co-WS2 catalysts exhibit remarkable HER activity with an overpotential of 113 mV to reach 10 mA cm−2 and stability with 30 h catalyzing at 23 mA cm−2. This work can provide an avenue for designing highly efficient catalysts applicable to the field of energy storage and conversion.

Promoted Catalytic Activity of CoSx@MoSx/MoOx Supported on Carbon Papers for Electrocatalytic Hydrogen Evolution Reaction

Developing cost-effective and stable materials for the electrocatalysis of hydrogen evolution reaction (HER) remains challenging. In this study, efficient catalysts for HER were synthesized by integrating the cobalt and molybdenum oxides via electrodeposition, followed by subsequent sulfurization of the as-prepared oxides using chemical vapor deposition (CVD). This methodology allowed the incorporation of both cobalt and molybdenum components into the catalyst in a single step. The as-synthesized CoSx@MoSx/MoOx-based catalysts exhibited excellent hydrogen production performance in acidic media owing to the presence of Co-S and Mo-S bonds in the hybrid structure. Particularly, CoSx@MoSx/MoOx(90@360) and MoSx@CoOx(180@180) displayed the best HER performances with low overpotentials of 80 mV and 150 mV, respectively. The catalysts were highly stable, with their stability preserved for over 1000 cycles with marginal reduction in overall efficiency. Therefore, these findings suggest the potential of CoSx@MoSx/MoOx and MoSx@CoOx composites as ideal candidates for developing low-cost catalysts for electrochemical hydrogen production.

Unravelling the role of work function difference on supported Ru nanoclusters for alkaline hydrogen evolution reaction

Fine tuning the work function difference (ΔΦ) between support and Ru which in turn affects the electron distribution of Ru is an effective method for the design of high-performance alkaline hydrogen evolution reaction (HER) catalysts. However, it remains a challenge to understand the intrinsic relationship between HER activity and ΔΦ at the atomic level. Herein, taking N doped graphene supported Ru nanoclusters (Ru/CxNy) as the theoretical model, we demonstrate that the HER activity can be correlated with the variation of ΔΦ. For Ru/C50 with smaller ΔΦ, we find that the Ru atoms located at the top layer of Ru nanoclusters (Ru-t) with lower coordination numbers are the main reaction sites. For Ru/C30N20 with larger ΔΦ, the stronger charge redistributions of Ru is observed, and the electron-deficient Ru atoms closing to the interface (Ru-i) are the main reaction sites with significant improvement HER activity. Our findings demonstrate the role of ΔΦ on Ru/CxNy systems for the alkaline HER, which can provide valuable theoretical guidance for the design of high efficient HER catalysts.

Toward boosted alkaline hydrogen evolution reaction: Covalent organic framework-derived N-doped carbon for highly dispersed cobalt nanoparticles

The preparation of renewable hydrogen via electrocatalytic water splitting is a burgeoning strategy in developing sustainable energy. However, it is still a great challenge to prepare an efficient non-precious metal based electrocatalyst for hydrogen evolution in alkaline electrolysis. Herein, we describe a functional hydrogen evolution reaction (HER) electrocatalyst by the combination of soaking metal ions in covalent organic framework (COF) and high temperature calcination. Especially, the 2Co-NC-700 catalyst possesses large specific surface area, appropriate defective nature and structural distortion, thus it embodies outstanding HER catalytic activity with only an overpotential of 303 mV at the current density of 10 mA cm−2 in the solution of 1.0 M KOH. Moreover, the kinetics and durability are also confirmed. Theoretical calculations not only indicates that the stable configuration combined small-sized cobalt nanoparticles and nitrogen-doped carbon but also reveals the synergistic effect of multiple active sites, while the optimal active location that shows the lowest hydrogen adsorption free energy is a major contributor for excellent HER. This work not only offers a highly efficient HER catalyst in alkaline environment but also provides a novel approach to develop non-precious metal nitrogen-doped carbon materials derived from COF as HER electrocatalysts in alkaline media.

Boosting hydrogen production from alkaline water splitting by regulating interlayer stress via lattice mismatch in NiS/MoS2

Alkaline water splitting currently represents one of the most promising routes for sustainable hydrogen production. However, the key challenge with this method lies in the development of low-cost catalysts showing high-performance for hydrogen evolution reaction (HER). Given the rapid advances in the structural design of HER catalysts, a potential procedure to boost their performance is introduced herein. A controllable interlayer stress is generated at the homojunction NiS/NiS interface of electrodeposited hybrid transition metal sulphide NiS/MoS2, by precisely regulating lattice mismatches of NiS nanostructures, achieve a precise control over its charge transfer resistance and the effective balance of electrochemical area. Accordingly, an optimal design, NM5030 (NiS(50 mA/cm2)-NiS(20 mA/cm2)/MoS2/CC), showing an excellent HER performance in alkaline electrolyte is produced. It can drive a high current density of 10 mA/cm2, 100 mA/cm2 and 400 mA/cm2 at a low overpotential of 18 mV, 93 mV and 161 mV, respectively. Under chronoamperometric test, no obvious reduction in current density is observed after 48 h, indicating its high stability. Overall, this work demonstrates the feasibility and effectiveness of the strategy of fabricating lattice mismatch to find an optimal layered structure based catalyst for efficient HER.

A Cluster-Type Self-Healing Catalyst for Stable Saline–Alkali Water Splitting

In electrocatalytic processes, traditional powder/film electrodes inevitably suffer from damage or deactivation, reducing their catalytic performance and stability. In contrast, self-healing electrocatalysts, through special structural design or composition methods, can automatically repair at the damaged sites, restoring their electrocatalytic activity. Here, guided by Pourbaix diagrams, foam metal was activated by a simple cyclic voltammetry method to synthesize metal clusters dispersion solution (MC/KOH). The metal clusters-modified hydroxylated Ni-Fe oxyhydroxide electrode (MC/NixFeyOOH) by a facile Ni-Fe metal–organic framework-reconstructed strategy, exhibiting superior performance toward the oxygen evolution reaction (OER) in the mixture of MC/KOH and saline–alkali water (MC/KOH+SAW). Specifically, using a nickel clusters-modified hydroxylated Ni-Fe oxyhydroxide electrode (NC/NixFeyOOH) for OER, the NC/NixFeyOOH catalyst has an ultra-low overpotential of 149 mV@10 mA cm−2, and durable stability of 100 h at 500 mA cm−2. By coupling this OER catalyst with an efficient hydrogen evolution reaction catalyst, high activity and durability in overall SAW splitting is exhibited. What is more, benefiting from the excellent fluidity, flexibility, and enhanced catalytic activity effect of the liquid NC, we demonstrate a self-healing electrocatalysis system for OER operated in the flowing NC/(KOH+SAW). This strategy provides innovative solutions for the fields of sustainable energy and environmental protection.

An in situ phase transformation induced mesoporous heterointerface for the alkaline hydrogen evolution reaction.

The phase structure of a catalyst plays a crucial role in determining the catalytic activity. In this study, a facile phosphorization process is employed to achieve the in situ phase transformation from single-phase Co3O4 to CoO/CoP hybrid phases. Characterization techniques, including XRD, BET, SEM, and TEM, confirm the retention of the mesoporous nature during the phase transformation, forming porous CoO/CoP heterointerfaces. Strong charge transfer is observed across the CoO/CoP heterointerface, indicating a robust interaction between the hybrid phases. The CoO/CoP hybrid exhibits significantly enhanced catalytic activity for the alkaline hydrogen evolution reaction (HER) compared to pristine Co3O4. Density Functional Theory (DFT) calculations reveal that the elimination of the band gap in the spin-down band of Co in CoO/CoP contributes to the observed high HER activity. The findings highlight the potential of CoO/CoP hybrids as efficient catalysts for HER, and contribute to the advancement of catalyst design for sustainable energy applications.

Single Ru atoms dispersed on MoSe2/MXene nanosheets with multiple interfaces for enhanced acidic hydrogen evolution

Exposing more catalytic active sites is an effective strategy to enhance the catalyst activity for hydrogen evolution reaction (HER). Herein, Ti3C2Tx MXene served as a substrate to load thin and curved 2H–MoSe2 nanosheets by a typical hydrothermal method, forming MoSe2/MXene heterointerface with the fully exposed Mo edge sites. And then, atomically dispersed Ru single atoms (RuSAs) were successfully anchored on the MoSe2/MXene (RuSAs@MoSe2-MXene). The X-ray absorption near edge structure (XANES) demonstrates that Ru is loaded as single atoms on MoSe2 and MXene. The prepared sample exhibits improved catalytic activity with a small overpotential of 49 mV at 10 mA cm−2 and a low Tafel slope of 52 mV dec−1 for HER in 0.5 M H2SO4. It also exhibits excellent stability with a small attenuation voltage of 10 mV for 120 h at 10 mA cm−2 in 0.5 M H2SO4. When assembled into a two-electrode system of RuSAs@MoSe2-MXene||RuO2, it only requires a relatively low potential of 1.626 V at 10 mA cm−2 to drive overall water splitting (OWS). Control experiments disclose the highly improved performance can be primarily attributed to the introduced RuSAs and MoSe2/MXene heterointerfaces exposing more active sites of Ru and Mo. Moreover, the high conductivity of MXene can increase charge transfer in HER process. The interface engineering with multiple interfaces can provide fresh impetus for the development of efficient HER catalysts.

Directed Dual Charge Pumping Tunes the d-Orbital Configuration of Pt Cluster Boosting Hydrogen Evolution Kinetic.

Achieving high catalytic activity with a minimum amount of platinum (Pt) is crucial for accelerating the cathodic hydrogen evolution reaction (HER) in proton exchange membrane (PEM) water electrolysis, yet it remains a significant challenge. Herein, a directed dual-charge pumping strategy to tune the d-orbital electronic distribution of Pt nanoclusters for efficient HER catalysis is proposed. Theoretical analysis reveals that the ligand effect and electronic metal-support interactions (EMSI) create an effective directional electron transfer channel for the d-orbital electrons of Pt, which in turn optimizes the binding strength to H*, thereby significantly enhancing HER efficiency of the Pt site. Experimentally, this directed dual-charge pumping strategy is validated by elaborating Sb-doped SnO2 (ATO) supported Fe-doped PtSn heterostructure catalysts (Fe-PtSn/ATO). The synthesized 3%Fe-PtSn/ATO catalysts exhibit lower overpotential (requiring only 10.5mV to reach a current density of 10mAcm- 2), higher mass activity (28.6 times higher than commercial 20wt.% Pt/C), and stability in the HER process in acidic media. This innovative strategy presents a promising pathway for the development of highly efficient HER catalysts with low Pt loading.

Aluminum-incorporation activates vanadium carbide with electron-rich carbon sites for efficient pH-universal hydrogen evolution reaction

Vanadium carbide (VC) is the greatest potential hydrogen evolution reaction (HER) catalyst because of its platinum-like property and abundant earth reserves. However, it exhibits insufficient catalytic performance due to the unfavorable interaction of reaction intermediates with catalysts. In this work, using NH4VO3 as the main raw material, the flow ratio of CH4 to Ar was accurately controlled, and a non-transition metal Al-doped into VC (100) nano-flowers with carbon hybrids on nickel foams (Al-VC@C/NF) was prepared for the first time as a high-efficiency HER catalyst by chemical vapor carbonization. The overpotential of Al-VC@C/NF catalysts in 0.5 M H2SO4 and 1 M KOH at a current density of 10 mA cm−2 are only 58 mV and 97 mV, respectively, which are the best HER performance among non-noble metal vanadium carbide based catalysts. Simultaneously, Al-VC@C/NF exhibits small Tafel slope (45 mV dec-1 and 73 mV dec-1) and excellent stability in acidic and alkaline media. Theoretical calculations demonstrate that doped Al atoms can induce electron redistribution on the vanadium carbide surface to form electron-rich carbon sites, which significantly reduces the energy barrier during the HER process. This work provides a new tactic to modulate vanadium-based carbons as efficient HER catalysts through non-transition metal doping.