Alkaline Hydrogen Evolution Reaction Research Articles

How Metal/Insulator Interfaces Enable an Enhancement of the Hydrogen Evolution Reaction Kinetics

AbstractThe nanostructuring of electrodes is a common way of increasing electrocatalytic activity. Yet, the fact that the presence of insulating material in nanostructured composites can have a positive effect on efficiency was an unexpected recent finding. The rate enhancement has been linked to different electric fields at the insulator and metal interfaces, facilitating enhanced transport of reaction products into the bulk electrolyte. In this article, we further uncover the origin of the rate enhancement with parameter studies and simulations. We experimentally investigate various parameter dependencies of the alkaline Hydrogen Evolution Reaction (HER) on well‐defined nanometer‐sized Au arrays embedded in a silicon nitride insulating layer. We find a significant enhancement of the HER for all experimental conditions and opposite activity trends with pH, electrolyte concentration and the cationic species compared to a continuous Au electrode. Using a mean field model, we quantify the electrostatic interfacial pressure above the Au and the insulator patches. Combining the double layer simulations with rate equations, we demonstrate that all parameter variations can be consistently explained by the fact that the double layer structure above the insulator patches is much less rigid than above the metal islands and is independent of the applied potential.

From Quinary Co–Cu–Mo–Pd–Re Materials Libraries to Gas Diffusion Electrodes for Alkaline Hydrogen Evolution

AbstractDeveloping a hydrogen evolution reaction (HER) electrocatalyst that can steadily drive a large current density is of great significance for industrial electrochemical water‐splitting technology. Herein, the compositionally complex noble‐metal‐lean system Co–Cu–Mo–Pd–Re is investigated for alkaline HER by a scanning droplet cell‐assisted high‐throughput screening of co‐sputtered thin‐film material libraries. The identified hit compositions are used to prepare a catalyst‐coated Ni foam‐based layer that is hot‐pressed with a specifically designed PEEK‐covered carbon‐based gas diffusion layer to obtain a novel‐design gas diffusion electrode (GDE). H2 bubbles that collect on the electrode surface are effectively reduced by controlling the hydrophobicity of the catalyst layer of the GDE, hence enabling a high current (−1 A cm−2) operation for HER in alkaline water electrolysis.

Molybdenum-doped tungsten nitride coated with carbon shell and cobalt hydroxide nanosheets for efficient alkaline hydrogen evolution reaction

Water electrolysis is currently the most important way to achieve large-scale hydrogen (H2) production. Although many nonprecious electrocatalysts possess promising catalytic performance at low current density below 50 mA cm−2, it remains a substantial challenge to realize H2 production at industry-compatible current density over 500 mA cm−2. Here we have designed a hierarchical heterostructure of molybdenum-doped tungsten nitride coated with carbon shell and cobalt hydroxide nanosheets (Mo-WN@NC@Co(OH)2) for alkaline hydrogen evolution reaction (HER) with industrial current density and stability. The hybrid exhibits efficient alkaline HER activity, reaching the current density of 500 mA cm−2 at an overpotential of 196 mV. The Co(OH)2 nanosheets and Mo doping endow the composite with more active sites and enhanced intrinsic activity of the catalyst, as well as an appropriate water dissociation energy. In addition, the free energy of activation for each step during the HER process suggests a synergistic effect of Mo doping and Co(OH)2 in Mo-WN@NC@Co(OH)2 promoting surface Volmer and Heyrovsky steps during the HER process. This doping and interfacial engineering methods hold great promise for fabricating efficient nitride-based electrocatalysts for electrochemical energy devices.

Unique sandwich-cookie-like nanosheet array heterojunction bifunctional electrocatalyst towards efficient overall water/seawater splitting

Construction of multi-component heterostructures is an effective strategy for electrocatalysts to improve both the hydrogen evolution reaction (HER) at the cathode and the oxygen evolution reaction (OER) activity at the anode. Herein, an efficient bifunctional electrocatalyst towards overall water/seawater splitting (OW/SS) is reported with strategy of heterostructure construction (ruthenium/nickel phosphorus) on nickel hydroxide (Ni(OH)2). With the unique hydrolysis layer (Ni(OH)2), the processes of H2O hydrolysis and the adsorption/desorption of H*/O-containing intermediates (OH, O, OOH) were greatly boosted by Ru and P sites, which acted as the catalytic active centers of OER and HER, respectively. In addition, the electronic structure reconfiguration was realized through the strong interaction between multi-interfaces. For alkaline HER at the current density of 10 mA cm−2, the overpotential of Ru-P-Ni(OH)2/NF (denoted as RNPOH/NF) was 98 mV, whereas just 230 mV of overpotential was essential to stimulate alkaline OER at the current density of 20 mA cm−2. Specifically, as a bifunctional electrocatalyst towards overall water splitting, RNPOH/NF deserves cell voltages of 1.7/1.92 V and 1.75/1.94 V, respectively, to activate current densities of 50/100 mA cm−2 in alkaline water/seawater systems, together with a good durability of 12 h. This work contributes insights to the development of bifunctional electrocatalysts for overall water/seawater splitting.

Exploration of transition metal atom-doped NiSe2 electrocatalysts for efficient alkaline hydrogen precipitation using first principles screening

Transition metal (TM) doping exhibits great potential in designing high-performance two-dimensional (2D) NiSe2-based catalysts for electrocatalytic hydrogen evolution reaction (HER). 22 TM atom-doped 2D-NiSe2 catalysts are screened, and the effects of TM doping on the thermal stability and HER catalytic activity are investigated by first-principles calculations. Among them, Cu doped 2D-NiSe2 might exhibit remarkable HER properties with the water dissociation energy of 1.03 eV and H adsorption Gibbs free energy of −0.05 eV. Furthermore, we elucidate the reasons behind the different HER activities. These findings suggest new possibilities for the application of Cu doped 2D-NiSe2 for alkaline HER, offering new perspectives for future research.

Effects of Intrinsic Defects in Pt-Based Carbon Supports on Alkaline Hydrogen Evolution Reaction.

Carbon material has widely been utilized in the synthesis of efficient carbon-supported Pt (Pt/C) catalysts, in which the structural properties greatly influence the electrocatalytic performances of Pt/C catalysts. However, the effects of intrinsic defects in carbon supports on the performance of the alkaline hydrogen evolution reaction (HER) have not been systematically investigated. Herein, porous carbon supports with different degrees of intrinsic defects were prepared by a simple template-assisted strategy, and the resulting samples were systematically studied by various analytical methods. The results suggested that the presence of abundant intrinsic defects (vacancy and topological defects) in the carbon support was advantageous in terms of favoring the dispersion and anchoring of Pt species, promoting electron transfer between Pt atoms and the carbon support, and tuning the electronic states of Pt species. These features improved the HER performance of Pt/C catalysts. Compared to the nontemplate-assisted carbon-supported Pt catalyst (Pt/NTC) with an overpotential of 178 mV, the optimized template-assisted carbon-supported Pt catalyst (Pt/TC) exhibited a lower overpotential of 58 mV at 10 mA cm-2. Besides, the Pt/TC catalyst displayed better HER durability than the Pt/NTC catalyst owing to its strong metal-support interaction. The DFT calculations confirmed the important role played by intrinsic defects (vacancy and topological defects) in stabilizing Pt atoms, with Pt-C3 coordination identified as the most favorable structure for improving the HER performance of Pt. Overall, novel insights on the significant contribution of intrinsic defects in porous carbon supports on the HER performances of Pt/C catalysts were provided, useful for future design and fabrication of advanced carbon-supported catalysts or other carbon-based electrode materials.

Unveiling the effect of solvent for hydrogen evolution in Pt-doped MXenes and corresponding high-entropy phase

Effect of solvent at the water/solid interface plays a non-negligible role in chemical reactions. Explicit solvation has been proved for its important effect on thermodynamics and kinetics of catalytic reactions. However, systematic studies about this perspective are still absence. In this work, using the model of single platinum atom immobilized on the metal vacancies of a series of MXenes, we systematically investigate the implicit/explicit solvent effect on their catalytic performance of the hydrogen evolution reaction (HER). We find that the solvent effect plays a significant role in affecting the calculation results for some systems. For TiNbC–PtNb, the value of ΔGH* decreases from −0.121 to −0.511 (−0.583) eV when considering implicit (explicit) correction, implying the decisive role of solvent effect for calculating HER in this system. Bader charge analysis and AIMD simulations reveal that TiNbC–PtNb surface is sensitive to H2O, thus causing this abnormal case. Surprisingly high-entropy phases of MXene overall are less sensitive to solvent compared to the pure phases, which could be due to their alloyed lattice with a strong ability against electronic and lattice fluctuations induced by solvent. Several systems like V2C–PtV, TiMoC–PtMo, and VNbC–PtV are predicted to be excellent electrocatalysts for alkaline HER with the appropriate Gibbs free energy of hydrogen adsorption and kinetic barrier of water dissociation. The perspective exemplified in this work highlights that more feasible operando should be considered, e.g., influence of water, to better simulate the reaction process. Our work suggests that Pt-doped MXenes are perfect systems for hosting atomic catalyst as well.

Operando Spectroscopic Monitoring of Metal Chalcogenides for Overall Water Splitting: New Views of Active Species and Sites

AbstractMetal‐based chalcogenides exhibit great promise for overall water splitting, yet their intrinsic catalytic reaction mechanisms remain to be fully understood. In this work, we employed operando X‐ray absorption (XAS) and in situ Raman spectroscopy to elucidate the structure–activity relationships of low‐crystalline cobalt sulfide (L−CoS) catalysts toward overall water splitting. The operando results for L−CoS catalyzing the alkaline hydrogen evolution reaction (HER) demonstrate that the cobalt centers in the bulk are predominantly coordinated by sulfur atoms, which undergo a kinetic structural rearrangement to generate metallic cobalt in S−Co−Co−S moieties as the true catalytically active species. In comparison, during the acidic HER, L−CoS undergoes local structural optimization of Co centers, and H2 production proceeds with adsorption/desorption of key intermediates atop the Co−S−Co configurations. Further operando characterizations highlight the crucial formation of high‐valent Co4+ species in L−CoS for the alkaline oxygen evolution reaction (OER), and the formation of such active species was found to be far more facile than in crystalline Co3O4 and Co‐LDH references. These insights offer a clear picture of the complexity of active species and site formation in different media, and demonstrate how their restructuring influences the catalytic activity.

Operando Spectroscopic Monitoring of Metal Chalcogenides for Overall Water Splitting: New Views of Active Species and Sites.

Metal-based chalcogenides exhibit great promise for overall water splitting, yet their intrinsic catalytic reaction mechanisms remain to be fully understood. In this work, we employed operando X-ray absorption (XAS) and in situ Raman spectroscopy to elucidate the structure-activity relationships of low-crystalline cobalt sulfide (L-CoS) catalysts toward overall water splitting. The operando results for L-CoS catalyzing the alkaline hydrogen evolution reaction (HER) demonstrate that the cobalt centers in the bulk are predominantly coordinated by sulfur atoms, which undergo a kinetic structural rearrangement to generate metallic cobalt in S-Co-Co-S moieties as the true catalytically active species. In comparison, during the acidic HER, L-CoS undergoes local structural optimization of Co centers, and H2 production proceeds with adsorption/desorption of key intermediates atop the Co-S-Co configurations. Further operando characterizations highlight the crucial formation of high-valent Co4+ species in L-CoS for the alkaline oxygen evolution reaction (OER), and the formation of such active species was found to be far more facile than in crystalline Co3O4 and Co-LDH references. These insights offer a clear picture of the complexity of active species and site formation in different media, and demonstrate how their restructuring influences the catalytic activity.

Facet‐Junction Induced Strong Metal Support Interaction for Enhanced Alkaline Hydrogen Evolution Reaction

AbstractStrong metal‐support interaction (SMSI) plays a critical role in enhancing the catalytic performance of electrocatalysts. Currently, effective approaches to enhance the SMSI effect in supported electrocatalysts still need to be developed, and a comprehensive atomic‐level understanding of the underlying reaction mechanisms remains unclear. In this study, a novel facet‐junction strategy is proposed to enhance the SMSI between the loaded Ru atoms and the Co3O4 support. By modulating the ratio of exposed facet for (111)/(100) crystal plane in Co3O4, the hydrogen evolution reaction (HER) performance can be dramatically enhanced by 560% and can achieve a Pt‐like HER activity with the overpotential of 45 mV. Detailed analysis with atomic‐resolution integrated differential phase contrast (iDPC)‐scanning transmission electron microscopy (STEM), atomic‐resolution high angle annular dark field (HADDF)‐STEM, and electron energy loss spectroscopy (EELS) further proved that with proper (111)/(100) crystal plane ratio, the intensified charge distribution near the facet‐junction region would modify the electronic structure around the active sites. This work provides new insights to enhance the SMSI and will contribute to the rational design of highly efficient electrocatalysts for water splitting.

Laser-thermal reduction synthesis of high-entropy alloys towards high-performance pH universal hydrogen evolution reaction

Owing to their multi-elemental compositions and unique high-entropy mixing states, high-entropy alloy (HEA) nanoparticles (NPs) displaying tunable activities and enhanced stabilities thus have become a rapidly growing area of research in recent years. However, the integration of multiple elements into HEA NPs at the nanoscale remains a formidable challenge, especially when it comes to the precise control of particle size, elemental composition and content. Herein, a simple and universal high-energy laser assisted reduction approach is presented, which achieves the preparation of HEA NPs with a wide range of multi-component, controllable particle sizes and constitution on different substrates within seconds. Laser on carbon nanofibers induced momentary high-temperature annealing (>2000 ​K and ramping/cooling rates > 105 ​K ​s−1) to successfully decorate HEA NPs up to twenty elements with excellent compatibility for large-scale synthesis (20.0 ​× ​20.0 ​cm2 of carbon cloth). The IrPdPtRhRu exhibit robust electrocatalytic hydrogen evolution reaction (HER) activities and low overpotentials of 16, 28, and 12 ​mV at a current density of 10 ​mA ​cm−2 in alkaline (1.0 ​M KOH), alkaline simulated seawater (1.0 ​M KOH ​+ ​0.5 ​M NaCl), and acidic (0.5 ​M ​H2SO4) electrolytes, respectively, and excellent stability (7 days and >2000 cycles) at the alkaline HER.

Three‐dimensional‐printed Ni‐based scaffold design accelerates bubble escape for ampere‐level alkaline hydrogen evolution reaction

AbstractAlkaline hydrogen evolution reaction (HER) for scalable hydrogen production largely hinges on addressing the sluggish bubble‐involved kinetics on the traditional Ni‐based electrode, especially for ampere‐level current densities and beyond. Herein, 3D‐printed Ni‐based sulfide (3DPNS) electrodes with varying scaffolds are designed and fabricated. In situ observations at microscopic levels demonstrate that the bubble escape velocity increases with the number of hole sides (HS) in the scaffolds. Subsequently, we conduct multiphysics field simulations to illustrate that as the hole shapes transition from square, pentagon, and hexagon to circle, where a noticeable reduction in the bubble‐attached HS length and the pressure balance time around the bubbles results in a decrease in bubble size and an acceleration in the rate of bubble escape. Ultimately, the 3DPNS electrode with circular hole configurations exhibits the most favorable HER performance with an overpotential of 297 mV at the current density of up to 1000 mA cm−2 for 120 h. The present study highlights a scalable and effective electrode scaffold design that promotes low‐cost and low‐energy green hydrogen production through the ampere‐level alkaline HER.

Two-dimensional flake Co/Co2N0.67 modified by molybdenum oxides achieves enhancement of bifunctional hydrogen electrocatalysis

To address the urgent need for non-precious metal-based catalysts in the industrial preparation and application of hydrogen energy, we present a secondary hydrothermal strategy to prepare a Mo-modified cobalt carbonate precursor, resulting in the Mo–Co/Co2N0.67 catalyst. The cobalt-based materials exhibit a layered flake structure due to molybdenum modification, exposing more active sites, while molybdenum oxide modification enhances hydrogen evolution reaction (HER) and hydrogen oxidation reaction (HOR). In alkaline HER measurements, Mo–Co/Co2N0.67 achieves a remarkable current density of 10 mA cm−2 at only 27 mV. The overall water splitting of Mo–Co/Co2N0.67 + RuO2 can reach 10 mA cm−2 at 1.52 V voltage. In alkaline HOR measurements, it exhibits the current density of 2.92 mA cm−2@0.1 V vs. RHE and an exchange current density (J0) of 2.96 mA cm−2. This work highlights the effective regulation of non-noble metal-based electrocatalysts through Mo modification, providing valuable insights for the development of efficient non-precious metal-based hydrogen electrocatalysis within the context of anion exchange membrane unitized reversible fuel cells (AEM-URFC).

In situ construction of layered transition metal phosphides/sulfides heterostructures for efficient hydrogen evolution in acidic and alkaline media

Construction of electrocatalysts with exceptional intrinsic activity and rich active sites has proved to be an effective strategy for remarkably enhancing the activity of the hydrogen evolution reaction (HER). In this work, durable and highly efficient layered Re2P/ReS2 (RePS) heterostructures were successfully fabricated by an in-situ phosphating layered ReS2. Taking advantage of the unique layered structure can provide abundant reaction active sites and the strong electronic interaction between ReS2 and Re2P can enhance the intrinsic activity, the optimized RePS electrocatalysts show superior catalytic activities of 69 and 57 mV at 10 mA cm−2 for HER in alkaline and acidic media, respectively. The density functional theory results suggest that the formed heterostructures between ReS2 and Re2P play an important role in optimizing the catalytic kinetics of the electrocatalysts. This work not only demonstrates that modulation of the electronic structure of catalysts is an efficient way to improve the HER activity but also confirms that the layered RePS heterostructure is a promising candidate for robust and high performance HER catalysts.

Cu-based bubble and ion sieve for ampere-level hydrogen evolution

Designing cheap, efficient, and stable electrocatalysts for hydrogen evolution reaction (HER) under ampere-level current density is essential for the industrial water electrolysis technique. However, the large H2 bubbles produced at high current density decrease the activity and stability of the catalyst. Here, a self-supported electrode with porous yolk-shell CuNi@Cu electrocatalyst is obtained via an alternant electrodeposition and replacement reaction during the pulse electrodeposition process. The porous Cu shell can boost electrolyte diffusion and serve as an H2 bubble fining sieve to enhance the activity and stability of alkaline HER at high current density with the low overpotential of 326 mV @1 A cm−2. The CuNi@Cu electrocatalyst can work steadily for 1000 h at 1 A cm−2 with negligible attenuation. The porous Cu shell can also repel cations in natural seawater owing to the positively charged surface. The spontaneous alternant reaction paves an avenue to design electrocatalysts with porous yolk-shell structures for large-scale industrial applications.

Co-Ni co-sputter deposited bimetallic thin film catalysts for alkaline hydrogen and oxygen evolution reactions

Co-Ni bi-metallic thin films with different stoichiometries have been deposited by magnetron co-sputtering technique on Ni foam (NF), Si and carbon paper substrates. The structural and morphological characterisations of these films have been done by X-ray diffraction, X-ray absorption spectroscopy and Field Emission Scanning Electron Microscope measurements. The performances of these films for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) have been evaluated through electrochemical measurements like Linear Sweep Voltammetry, Cyclic Voltammetry and Electrochemical Impedance Spectroscopy measurements. Operando X ray absorption near edge spectroscopy measurements have also been carried out during HER and OER to decipher the redox reaction mechanisms. It has been observed that the HER and OER performance of all the Co Ni bi-metallic thin films on NF are found to be better than that of bare NF. The CoNi sample with composition of 58.7 % Co and 41.3 % Ni shows the best catalytic activity and stability towards HER and OER reactions. Though the HER activity is not the best but is comparable to many results reported in the literature, however the catalyst shows excellent OER activity with overpotential of 214 mV for 10 mA/cm2 current density. This is much better than that of the OER benchmark catalyst RuO2 and most of those reported in the literature. The OER is kinetically slower than HER and requires more overpotential, hence a significant improvement in the catalytic OER activity will definitely enhance the overall water splitting activity and hydrogen production efficiency. Thus the Co-Ni bi-metallic catalyst prepared by an easily scalable and highly reproducible magnetron co-sputtering technique has significant potential to emerge out as a technologically viable water splitting catalyst.

Nanoporous NiPt alloy by dealloying of amorphous NiZrPt metallic glass for alkaline hydrogen evolution reaction

The development of high-performance and low-cost alkaline hydrogen precipitation catalysts is critical for the large-scale application of hydrogen energy. In this work, the nanoporous alloy catalysts were synthesized by dealloying melt-spun NiZrPt ribbons. The optimal sample after dealloying shows excellent HER performance in alkaline medium, with a small overpotential of 15 mV to deliver 10 mA cm−2 and a low Tafel slope of 20 mV/dec. The material characterization reveals that the incorporation of Ni modulates the electronic structure of Pt. After selective dealloying of Zr and Ni, a Pt-enriched nanoporous structure was formed on the catalyst surface. Meanwhile, the remaining Ni sites acted as synergistic sites to activate the Pt sites, which allowed for better hydrogen adsorption energy and faster kinetics of the catalytic reaction. Besides, the favorable mechanical flexibility of the material makes it potential for self-supporting electrode. This work presents a way to prepare low-Pt efficient catalysts by amorphous alloy dealloying.

Coupling Interaction between Precisely Located Pt Single‐Atoms/Clusters and NiCo‐Layered Double Oxide to Boost Hydrogen Evolution Reaction

AbstractCatalysts based on Pt single atom (SA) on metal oxides have shown tremendous potentials for alkaline hydrogen evolution reaction (HER), but they are severely limited by insufficient electron interactions of Pt sites and supports. Herein, a new methodology is developed to precisely locate Pt SAs and Pt clusters into NiCo layered double oxide (LDO) nanosheets, achieved using a dual‐ion etching process with subsequent phase transformation method. Uniquely, the Pt SAs are inserted into LDO layers to form Pt─Co bonds by occupying partial Ni positions, significantly strengthening electron interactions with NiCo LDO and promoting activity of HER. Results from density functional theory calculations indicate that the H* species are preferentially absorbed onto O sites on top of these Pt SAs, which are coupled with their adjacent Pt clusters to accelerate water dissociation in the Volmer step. As‐obtained Pt─NiCo LDO exhibits a low overpotential of 92 mV at 10 mA cm−2 and a Tafel slope of 73 mV dec−1, an excellent stability over 105 hours at 60 mA cm−2, and its mass activity is 6 times higher than commercial 20% Pt/C. This study highlights essential functions of coupling interactions between Pt SAs/clusters and LDOs to boost HER for hydrogen energy production.

MoS2 supported Ruthenium nanoparticles with abundant sulfur vacancies significantly improved hydrogen evolution reaction

The electrochemical hydrogen evolution reaction (HER) has become one of effective ways to produce hydrogen. MoS2 is a promising electrocatalyst for the HER, and loading noble metal atoms on MoS2 support can further enhance its HER activity. In present work, the CO was employed as a structure-directing agent to in situ synthesize MoS2-n (n = 0, 0.5, 1.0, 1.4 and 2.0 MPa, representing the CO pressure). Among them, the MoS2-1.4 with highest amounts of sulfur vacancies and superior alkaline HER performance was selected as the support for Ru loadings. Sulfur vacancies can stabilize Ru nanoparticles, prevent nanoparticles from aggregating, and facilitate the formation of small-sized nanoparticles. By optimizing the loading amounts of Ru, the 5Ru@MoS2-1.4 with the Ru loading of 5 wt.% and nanoparticle size of 2 nm exhibits the best alkaline HER activity by displaying a low overpotential of 55 mV and Tafel slope of 68.6 mV dec−1 at a current density of 10 mA cm−2 in 1.0 M KOH medium. This can be majorly related to the synergistic effect of MoS2-1.4 support and small-sized Ru nanoparticles, wherein the CO plays a significant role in regulating the structure of MoS2-1.4 support that favors dispersion of Ru nanoparticles. Generally, present work provides a strategy to enhance the HER catalytic performance of MoS2, which is favorable for other highly-efficient catalyst design.

Multistage structural self-supported electrode via structural engineering on carbon nanofibers for efficient hydrogen evolution reaction at high current density

Pt-based catalysts suffered from the wastage of active sites, resulting in unsatisfactory actual catalytic performance and poor durability as non-self-supporting catalysts for alkaline hydrogen evolution reaction (HER). In this work, we designed a self-supporting electrode material with multi-level structure that utilized carbon nanofibers anchored with cobalt to load and stabilize Pt nanoparticles (Pt@Co/CNFs) for achieving high activity and stability in alkaline HER. The carbon nanofibers served as a framework, with cobalt nanoparticles as an electron donor that can transfer electrons to the metal Pt to accelerating water splitting. In addition, the morphology of the multi-level structure surface was controlled by the content of the reducing agent to giving the material excellent superhydrophilic/underwater superaerophobic properties with ultra-low Pt load (0.29 mg cm−2), which was beneficial for HER. HER test results showed that Pt@Co/CNFs exhibited great catalytic activity, with η10 = 15 mV and η100 = 101 mV. Besides, the stable mechanical structure and the stability of the designed catalytic surface and electron donor in the multi-level structure gave the material exceptional stability. During the 100-hour stability test at 100 mA cm−2, the voltage change was only 50 mV. Besides, utilizing the Pt@Co/CNFs self-supporting electrode directly in the AEM water electrolysis system, a cell voltage as low as 2.18 V was achieved at 500 mA cm−2. Impressively, it demonstrated operational stability for over 200 h without noticeable decay. This work provides a promising approach for the development of advanced self-supporting electrode catalysts.