Electrocatalytic Hydrogen Evolution Research Articles

Unveiling the facet-dependent electrocatalytic activity of a 3D-CoSn(OH)6 perovskite material for overall water splitting: Interfacial engineering with Mn3+ and CH3COO- ions

In this study, we report morphologically dependent electrocatalytic oxygen and hydrogen evolution reactions in an alkaline medium. The bifunctional electrocatalyst such as cobalt tin hydroxide (CoSn(OH)6) was prepared by hydrothermal method. Importantly, tuning the morphological variation of CoSn(OH)6 into cubes, octa- and dodecahedra and their corresponding growth mechanisms are analyzed and explored the electrochemical studies. Among the different morphologies, the CoSn(OH)6 dodecahedron (CTH-DH) displays a substantially enhanced overall electrocatalytic water splitting reaction. It is firmly due to the [Mn3+] and [CH3COO-] ions do enable the morphological progression of the CTH cubic crystals with more facets. The highly active catalytic sites on the facets of CTH-DH permit the adsorption of abundant OH groups during the hydrogen and oxygen evolution reactions. Moreover, in a two-electrode system, the CTH-DH ǁ CTH-DH electrolyzer exhibits a cell potential of 1.60 V at 10 mA cm–2 with a remarkable reliable long-term stability. In addition, the structural transformations of the as-prepared CoSn(OH)6 crystals are monitored before and after electrocatalysis using TEM study. As a result, the study highlights the potential of Mn-containing CTH-DH facets as viable electrocatalysts in efficient H2 production.

U and Co Dual Single-Atom Doped MXene for Accelerating Electrocatalytic Hydrogen Evolution Activity.

A large amount of radioactive waste is accumulated in the process of nuclear fuel preparation, causing serious pollution to the environment and abundant depleted uranium resources to be abandoned. One of the key issues affecting the development of nuclear energy is how to make full use of depleted uranium resources efficiently. Here, U element with unique coordination mode of 5f electron is spacer bonded to transition metal with 3d orbit through the adsorption and anchoring effect of MXene, thus U and Co dual doped MXene catalyst is constructed along with the comprehensive utilization of depleted uranium resources. The as-prepared U-Co/MXene catalyst demonstrates excellent overpotential of only 184mV at -10mA cm-2 and excellent stability up to 150h, significantly surpassing the bare MXene substrate. Theoretical calculations indicate that the U and Co dual doping optimizes the electronic structure of MXene catalyst by forming the U-O-Co network, thereby improving the thermodynamics of H* adsorption during the catalytic transition state. This research opens up a new path for the recovery of depleted uranium resources and the development of functional actinide catalysts.

In-situ exfoliating graphene to anchor Mo2C NPs and modulate crystal planes for hydrogen production

An economical and efficient noble metal-free catalyst is necessary for large-scale hydrogen production. Here, Mo2C nanoparticles (NPs) were well-dispersed on the surface of 2D graphene nanosheets by in-situ propping oxide graphene (GO) layers, anchoring molybdate ions between GO layers and pyrolysis. The exposed crystal planes were also adjusted by above strategy. The results indicate that uniform and well-dispersed Mo2C NPs with a narrow size distribution were anchored on 2D rGO nanosheets and exposed dual crystal planes. The results of hydrogen evolution reaction (HER) show that the optimal Mo2C/rGO catalyst only needs low overpotential (η10, 112 mV) to drive 10 mA cm−2 in alkaline solution, and η10 only increased by 12 mV after 1000 cycles test, indicating high activity and stability for HER. Notably, the overpotential is below than that of Pt/C commercial catalyst when current density is more than 100 mA cm−1. The excellent performance is benefit from low hydrogen adsorption Gibbs free energy (ΔGH∗) on the Mo2C catalyst. Therefore, the proposed strategy is efficient to prepare well-dispersed and dual crystal planes-exposed Mo2C NPs for electrocatalytic hydrogen evolution.

Advanced multi-component FeCoCuAlMo intermetallic electrocatalysts for efficient and sustainable hydrogen evolution in alkaline freshwater and seawater

Electrolyzing seawater to produce hydrogen is a promising sustainable energy production technology. The current non-precious metal-based hydrogen evolution reaction (HER) electrocatalysts demonstrate inadequate catalytic activity and poor stability in seawater electrolyte. Therefore, developing stable and efficient non-precious metal-based HER electrocatalysts is a major challenge for achieving sustainable green energy development. This work reports a multi-component intermetallic catalyst FeCoCuAlMo prepared by arc melting and chemical dealloying methods. The electrocatalytic hydrogen evolution performance of catalysts with varying atomic ratios (FeCoCu)20(Al70Mo30)80, (FeCoCu)30(Al70Mo30)70, (FeCoCu)40(Al70Mo30)60, and (FeCoCu)50(Al70Mo30)50 in alkaline seawater and alkaline electrolyte was studied. The findings indicate that these catalysts primarily consist of AlMo3 and (Cu0.35Fe0.35Co0.3)Al, among which the dealloyed (FeCoCu)30(Al70Mo30)70 exhibits excellent catalytic activity with overpotentials of 137.54 and 116.91 mV at a current density of 100 mA/cm2 in alkaline seawater and alkaline electrolyte, respectively, outperforming most catalysts. Additionally, it demonstrated long-term stability in alkaline seawater and alkaline electrolyte for 250 and 400 h without significant decay at overpotentials of 236 mV and 276 mV, respectively. This improved performance can be attributed to the unique structure of the multi-component intermetallic compound, which provides good thermodynamic stability and synergistic effects among its constituents, thereby enhancing HER performance. Within this multi-component intermetallic compound, AlMo3 particles serve as the primary conductive medium to accelerate electron transfer, while (Cu0.35Fe0.35Co0.3)Al serves as the main active site, resulting in a stable structure that provides the catalyst with high catalytic activity and good stability. Thus, the (FeCoCu)30(Al70Mo30)70 electrocatalyst is a promising candidate for seawater electrolysis aimed at hydrogen production.

Research progress in transition metal carbides in electrocatalytic hydrogen evolution reaction

Research progress in transition metal carbides in electrocatalytic hydrogen evolution reaction

Preparation of Ni nanocone/Grid electrodes by laser-electrodeposition combined process as an efficient and stable electrocatalyst for hydrogen evolution reaction

Hydrogen is a renewable and environmentally friendly energy carrier and is considered a viable alternative to fossil fuels. Consequently, developing electrodes with excellent hydrogen evolution electrocatalysis is a top priority in research. However, the use of flat electrodes as cathode substrates by most researchers limits the electrocatalytic active area of the prepared electrode. To address this issue, it is essential to prepare a micro-nano structure on a cathode substrate before electrodeposition. This study introduced a novel Ni nanocone/Grid electrode, obtained through a combined laser-electrodeposition process to investigate its electrocatalytic activity and stability for the hydrogen evolution reaction (HER). Various techniques, including linear sweep voltammetry (LSV), electrochemical impedance spectra (EIS), cyclic voltammetry (CV), and chronopotentiometry (CP) in 1 M KOH solution, were employed to assess the HER electrocatalytic performance of the Ni nanocone/Grid electrodes. The experimental results demonstrated that the electrodes could achieve current densities of -10, -20, and -100 mA/cm2 with corresponding overpotentials of -281, -308, and -390 mV, respectively. Additionally, the Tafel slope of these electrodes was found to be only -82.05 mV/dec. The enhanced catalytic performance of the electrode was attributed to the synergistic effect of the grid-like and nanocone structures, which significantly increased the electrocatalytically active area and improved surface hydrophilicity, thereby boosting electrocatalytic performance. The simplicity of the preparation method and the exceptional performance of the electrode provide a promising new avenue for future research on HER electrocatalysts.

Reduced graphene oxide supported meso-pyridyl BODIPY-Cobaloxime complexes for electrocatalytic hydrogen evolution reaction

Creating innovative catalysts utilizing nonprecious metals for the electrocatalytic hydrogen evolution reaction (HER) poses a significant difficulty. We present a cobaloxime (Cox) complex having pyridine (2-Cox) and tetrafluorophenyl-thio-pyridine (4-Cox) functional groups, which contains a 4,4-Difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) moiety. This combination serves as a catalyst for proton reduction and is immobilized onto reduced graphene oxide (rGO) by π–π stacking between the cobaloxime complex and rGO. Moreover, the unique complex's structures were determined through the application of ultraviolet–visible spectroscopy (UV–Vis), Fourier Transform Infrared spectroscopy (FT-IR), X-ray diffraction spectroscopy (XRD), and scanning electron microscopy (SEM). The electrocatalytic activity of the two rGO/2-Cox and rGO/4-Cox electrodes towards hydrogen (H2) were examined under both alkaline and acidic conditions. The cobaloxime-modified rGO electrodes demonstrate superior electrocatalytic performance for the HER under acidic conditions compared to alkaline conditions. The overpotential at a current density of 10 mA cm−2 for rGO/2-Cox in 0.5 M H2SO4 is −0.342 V, which is notably lower than the overpotential of rGO/4-Cox (−0.496 V). The Tafel slope for the rGO/2-Cox electrode in a 0.5 M H2SO4 solution is 111 mV.dec−1, but for the rGO/4-Cox electrode it is 156 mVdec−1. This discrepancy suggests that the rGO/2-Cox electrode demonstrates better performance in the HER compared to the rGO/4-Cox electrode.

Covalent organic framework-derived C@COF core-shell microspheres for electrocatalytic hydrogen evolution

Although hydrogen represents a vital source of clean energy, the development of cost-effective, durable materials for use as catalysts in the hydrogen evolution reaction (HER) remains a challenge. In this work, covalent organic framework (COF) - derived core-shell microspheres were prepared as novel electrocatalysts. The previously prepared COF microspheres were pyrolyzed into nitrogen-doped porous carbon (N–C) as the core for enhanced electrocatalytic conductivity. With the assistance of a dual-ligand, the COF shell grew on the surface of N–C to form a core-shell microsphere, which was named N–C@COF. The surface morphology and core-shell structure of N–C@COF were characterized by SEM and TEM. FT-IR, TGA, and XPS were utilized to ascertain the synthesis of COF and the composition of the core-shell microspheres. The N–C@COF core-shell microspheres exhibited excellent HER performance in 1 M KOH electrolyte, demonstrating a low overpotential of 104 mV @ 10 mA cm−2, significantly outperforming pure COF and N–C. Furthermore, the N–C@COF demonstrated excellent HER stability over a 24 h period and retained its HER activity following 2000 consecutive cycles of electrolysis. The presence of the N–C core in the N–C@COF enhanced the electrical conductivity of the catalyst, while the COF shell provided abundant active sites for the HER, resulting in a synergistic improvement in the catalytic efficiency. This work presents a straightforward strategy for synthesizing COF-based multicomponent core-shell microspheres, which provides a promising pathway for the development of available and cost-effective electrocatalysts.

Boosted Electrochemical Hydrogen Evolution Activity via the Core-Shell Heterostructure of Nickel Sulfide Nanoframe-Supported Layered Rhenium Disulfide.

The strategic design of a heterostructure catalyst with a core-shell nanoarchitecture is imperative for enhancing the efficiency of the electrocatalytic hydrogen evolution reaction (HER). Herein, the core-shell catalyst comprising the rhenium disulfide nanosheets was vertically integrated onto a hollow nickel sulfide (NiS@ReS2) via coprecipitation and hydrothermal treatment. The morphology involves the sulfurization of a nickel-based Prussian blue analogue, effectively mitigating the aggregation of ReS2 nanosheets and maximizing the exposed active sites. By the synergistic effect of morphological design and heterostructure formation, the overpotential of NiS@ReS2 is 136 mV at 10 mA cm-2 in an alkaline electrolyte, and the rapid kinetics is confirmed by the small Tafel slope and low charge transfer resistance during the HER process. Moreover, the electrocatalytic durability of NiS@ReS2 is elucidated, and the boosted catalytic activity of NiS@ReS2 is confirmed by density functional theory. This study unveils a promising method for advancing ReS2-based electrocatalysts with potential implications for producing hydrogen.

Micelle-assisted electrodeposition of mesoporous PtCo nodular films and their electrocatalytic activity towards the hydrogen evolution reaction in acidic media

Hydrogen has received extensive attention in the energy field due to its high energy density and environmental friendliness. However, the large overpotential and slow kinetics limit the development of green water electrolysis technology. Rational design and construction of efficient and economical electrocatalysts are essential for sustainable hydrogen production. In this work, mesoporous PtCo films are successfully prepared by micelle-assisted electrodeposition using Pluronic F127 as a soft template. The optimal electrodeposition conditions of the film such as temperature and potential are determined. The composition of the films can be adjusted with the deposition potential to a Co content up to 45 at.%. The mesoporosity is clearly present at T=45 °C and E= − 0.6 V with a pore diameter of around 5–10 nm. The mechanism for the mesoporous PtCo films is proposed and the electrocatalytic activity in H2SO4 is evaluated. Mesoporous PtCo film with 45 at.% Co exhibits excellent electrocatalytic hydrogen evolution performance over commercial Pt/C, with an overpotential of − 22 mV at a current density of − 10 mA cm−2, and exhibits remarkable durability in the 24 h long-term aging stability test.

Laser-Induced Vertical Graphene Nanosheets for Electrocatalytic Hydrogen Evolution.

Efficient and affordable electrocatalysts are fundamental for the sustainable production of hydrogen from water electrolysis. Here, an approach for the rapid production of laser-induced vertical graphene nanosheets (LIVGNs) through the exfoliation of the graphite foil under laser irradiation is presented. The density of the formed LIVGNs is ∼3 per 100 μm2. On leveraging the inherent flexibility and conductivity of the graphite foil substrate, the resulting LIVGNs exhibit a 2.2-fold increase in capacitance, making them promising candidates for electrode applications. The laser-induced surface reconstruction introduces abundant sharp edges to the LIVGNs, enhancing their electrocatalytic potential for hydrogen evolution. In electrocatalytic hydrogen evolution tests in acidic media, the LIVGNs demonstrate superior performance with a remarkable decrease in the required overpotential at 10 mA cm-2, from -555 mV for the pristine graphite foil to -348 mV for LIVGNs. This improvement is attributed to the active sites provided by the sharp edges, facilitating hydrogen species adsorption. Furthermore, the hydrophilic behavior of LIVGNs is enhanced through the anchoring of oxygen-containing groups, promoting the rapid release of the produced hydrogen bubbles. Importantly, the modified LIVGN electrode exhibits long-term stability across a wide range of current densities during chronoamperometry tests. This research introduces a transformative strategy for the efficient preparation of vertical graphene sheets on conductive graphite foils, showcasing their potential applications in electrocatalysis and energy storage.

Ruthenium-doped dual-phase cobalt catalysts for enhanced electrocatalytic hydrogen evolution

Controlling the structural sensitivity and selectivity of metal catalysts in reactions, such as the hydrogen evolution reaction (HER) on cobalt crystals, remains a challenging issue in heterogeneous catalysis. In this study, we introduced a straightforward approach to tuning the phase composition of hexagonal close-packed cobalt (HCP-Co) and face-centered cubic cobalt (FCC-Co) in a core–shell Co/C catalyst through the incorporation of Ru atoms. The HER performance was evaluated by controlling the contents of HCP-Co and FCC-Co phases in the catalysts. Single-atom Ru-doped cobalt catalysts containing dual-phase HCP and FCC were prepared by a mechanical ball-milling zeolitic imidazolate framework (ZIF-67) with appropriate ruthenium chloride, followed by a pyrolysis process. The doping of Ru resulted in changes in the contents of the HCP-Co and FCC-Co phases, which significantly boosted the HER activity of the catalysts. The obtained biphasic Ru-Co/C catalyst demonstrated ultra-low HER overpotential and promising stability in alkaline and acidic media, outperforming single-phase cobalt and commercial Pt/C catalysts. Theoretical calculations revealed the synergistic catalysis effect of biphasic cobalt on HER. These findings, which indicated that significant activity dependence on the crystallographic structure, may inspire new design concepts for efficient metal electrocatalysts.

Photo- and Electrocatalytic Hydrogen Evolution by Heteroleptic Dirhodium(II,II) Complexes: Role of the Bridging and Diimine Ligands.

A series of heteroleptic Rh2(II,II) complexes, cis-[Rh2(μ-DPhF)2(μ-bncn)2]2+ (1; bncn = benzo[c]cinnoline), cis-[Rh2(μ-DPhF)(μ-OAc)(μ-bncn)2]2+ (2), and cis-[Rh2(μ-OAc)2(μ-bncn)2]2+ (3), is presented, and the excited state and redox properties of each complex was characterized for the photo- and electrocatalytic production of H2. The oxidation potentials shift anodically from 1 to 3, consistent with a highest occupied molecular orbital (HOMO) with significant metal-ligand mixing, Rh2(δ*)/DPhF(π/nb). In contrast, modest differences in the first two bncn-localized reversible reduction potentials were observed in 1 - 3. The lowest energy metal/ligand-to-ligand charge transfer (1ML-LCT) transition, Rh2(δ*)/DPhF(π/nb) → bncn(π*), shifts from 633 nm in 1 to 553 nm in 2, and the metal-to-ligand charge transfer (1MLCT) Rh2(π*) → bncn(π*) absorption in 3 appears at 462 nm in CH3CN. Although the 3ML-LCT excited state of 2 is shorter lived than that of 1, 2.7 ns as compared to 19 ns, respectively, photocatalytic hydrogen generation is observed for the former upon 595 nm irradiation in the presence of 0.1 M TsOH (p-tolylsulfonic acid) and 0.1 M BNAH (1-benzyl-1,4-dihydronicotinamide). The temperature dependence of the 3ML-LCT lifetimes of 1 and 2 shows the presence of a thermally accessible deactivating state. In addition, the singly reduced intermediate, [2]-, is photoactive and able to generate hydrogen in the presence of TsOH. Importantly, the electrocatalytic currents generated by equimolar concentrations of 1 - 3 in CH3CN are nearly identical, consistent with a mechanism of catalysis that is localized on the bncn ligand and does not require a Rh-H hydride intermediate. This finding can be used to develop earth-abundant first-row transition metal complexes for photo- and electrocatalytic H2 production.

Research on the synthesis of transitional metal and post-transitional metal doping eolitic imidazolate framework-based electrocatalysts and electrocatalytic hydrogen evolution reaction

Hydrogen, as a sustainable and green energy source, has gained significant attention in the context of the global energy crisis. The challenge underlying the hydrogen evolution reaction in electrochemical water splitting is to replace the noble metal-based electrocatalysts with effective low overpotential and kinetically favorable electrocatalysts. This research focused on the synthesis and modification of non-noble metal zeolitic imidazolate framework-based electrocatalysts. Using the heteroatom metal doping to improve electrocatalysts, Ni, Ce, Bi, and In are investigated as possible dopants. Herein, we successfully synthesized electrocatalysts combining CoM nanoalloy (M = Ni/Ce/In/Bi) with N-doped carbon nanostructure, denoted as CoM@NC. Among all synthesized electrocatalysts, CoNi@NC demonstrates to be the best HER electrocatalyst, with the lowest overpotential of 454.5mV at 10 mA cm-2 current density, Tafel slope of 86.3 mV dec-1, and stability for more than 10 hours. The composition and structures of CoNi@NC optimize its electron structure, increase active sites, and improve its onductivity and stability, which makes it a possible effective nonnoble metal HER electrocatalyst. This electrocatalyst provides a possible method to design and synthesize hydrogen evolution electrocatalysts that can replace noble metal-based electrocatalysts.

Wafer scale and substrate-agnostic growth of MoS2 nanowalls for efficient electrocatalytic hydrogen generation in acidic and alkaline media

Emerging as a promising alternative to expensive platinum-based catalysts for electrocatalytic hydrogen evolution reaction (HER), molybdenum disulfide (MoS2) stands out for its favourable thermodynamic properties. However, the catalytic activity of MoS2 is mostly confined to its edges while the basal plane remains inactive, limiting practical applicability. Fabrication of stable MoS2 structures with enhanced active sites on a given surface area still remains a complex task. Here we introduce a substrate-agnostic, metal-organic chemical vapour deposition (MOCVD) method for large-area 3D dendritic nanostructures of 2D MoS2, termed as “MoS2 nanowalls”. Using scanning and transmission electron microscopy (SEM/TEM), we elucidate the growth mechanism of the MoS2 nanowalls and their branched dendritic structure. Even subjected to extreme pH environments (0 and 14) during the HER, the grown MoS2 nanowalls show remarkable stability even after >170 hours of continuous operation and exhibit excellent catalytic activity with 10 mAcm−2 current density achievable by applying low overpotentials (309±2 mV at pH = 0 and 272±2 mV at pH = 14). The presented large-area growth method for inexpensive MoS2 nanowall based catalyst can pave the way for practical applications of water electrolysis cells operating at low voltages (≤1.5 V).

Defect engineering via gamma irradiation in scalable mechanical exfoliation TMDs thin films for improved electrocatalytic hydrogen evolution

This study explores a novel and efficient van der Waals thin-film deposition method, called Automatic Mechanical Exfoliation (AME), and its application in hydrogen evolution reaction (HER). Compared to traditional physical deposition techniques, AME offers significant advantages: it is simpler, more cost-effective, and significantly faster, enabling the deposition of large-area (>5 cm2) coatings exhibiting superior catalytic activity towards HER. To demonstrate its versatility, we comprehensively characterized large-area TMD thin films (MoS2/NbS2, NbS2, TiS2, MoSe2, MoS2, and WS2) using various techniques. Our AME-grown TMD thin films delivered improved HER performance, with lower Tafel slopes compared to previously reported values. To further enhance their activity, we irradiated the films with gamma radiation, leading to a remarkable improvement across all studied TMDs materials (e.g., an average increase of 30 % in exchange current density). Notably, NbS2 thin films and MoS2/NbS2 heterostructures exhibited excellent performance after irradiation, achieving low Tafel slopes (81 mV/dec and 85 mV/dec, respectively), starting overpotentials (−56 mV and −24 mV vs RHE, respectively), high exchange current densities (10.39 µA cm–2 and 625.2 µA cm–2, respectively), and turnover frequencies (0.021 s–1 and 0.95 s–1, respectively). These findings suggest that gamma irradiation can be a powerful tool for defect engineering in TMDs, creating additional active sites and demonstrably enhancing their catalytic efficiency for HER.

Constructing high efficient carrier channels in double ternary compounds MoSSe/CdSSe heterojunction for photoelectrochemistry and electrocatalytic hydrogen production

Here is a demonstration of constructing MoSSe/CdSSe heterojunction catalyst from bimetallic selenium sulfides. CdSSe has a high conduction band position of −0.65 eV, resulting in a strong reduction potential of photogenerated electrons. However, the high resistance of CdSSe affects the transport of charge carriers. In addition, experiments have confirmed that the presence of S and Se in MoSSe and CdSSe enhances their chemical activity and facilitates bonding. A better connection can be formed between MoSSe and CdSSe, resulting in high carrier transport efficiency. In the X-ray photoelectron spectroscopy results, the Mo and Se signals showed a large shift nearly 1 eV which confirms the strong binding between MoSSe and CdSSe. In the photoelectrochemical tests, the MoSSe/CdSSe heterojunction demonstrated a photocurrent density of 3.097 mA/cm2 at 0 V (RHE) which is 2.7 and 2.9 times that of MoSSe (1.227 mA/cm2) and CdSSe (1.127 mA/cm2) respectively with a low resistance of 161 Ω. Moreover, the MoSSe/CdSSe also has good electrocatalytic hydrogen evolution performance with an overvoltage of 180 mV and Tafel slope of 69 mV/dec. Fluorescence and photocurrent response tests confirmed its higher carrier separation efficiency. This work demonstrates the application of ternary metal selenium sulfide heterojunctions in catalytic energy materials.

High Mass Transfer Rate in Electrocatalytic Hydrogen Evolution Achieved with Efficient Quasi-Gas Phase System.

The adhesion of H2 bubbles on the electrode surface is one of the main factors limiting the performance of H2 evolution of electrolytic water, especially at high current density. To overcome this problem, here a "quasi-gas phase" electrolytic water reaction system based on capillary effect is proposed for the first time to improve the mass transfer efficiency of H2. The typical feature of this reaction system is that the main site of H2 evolution reaction is transferred from the bulk aqueous solution to the gas phase environment above the bulk aqueous solution, thus effectively inhibiting the aggregation of H2 bubbles and reducing the resistance of their diffusion away. Electrochemical test results show that the proposed quasi-gas phase system can significantly reduce the potential required in H2 evolution reaction process at high current density compared with the conventional electrolytic reaction system. Specifically, the overpotential potential is reduced by 0.31 V when the H2 evolution current density of 250 mA cm-2 is achieved.

High Mass Transfer Rate in Electrocatalytic Hydrogen Evolution Achieved with Efficient Quasi‐Gas Phase System

The adhesion of H2 bubbles on the electrode surface is one of the main factors limiting the performance of H2 evolution of electrolytic water, especially at high current density. To overcome this problem, here a "quasi‐gas phase" electrolytic water reaction system based on capillary effect is proposed for the first time to improve the mass transfer efficiency of H2. The typical feature of this reaction system is that the main site of H2 evolution reaction is transferred from the bulk aqueous solution to the gas phase environment above the bulk aqueous solution, thus effectively inhibiting the aggregation of H2 bubbles and reducing the resistance of their diffusion away. Electrochemical test results show that the proposed quasi‐gas phase system can significantly reduce the potential required in H2 evolution reaction process at high current density compared with the conventional electrolytic reaction system. Specifically, the overpotential potential is reduced by 0.31 V when the H2 evolution current density of 250 mA cm‐2 is achieved.

C60 Fullerene-Induced Reduction of Metal Ions: Synthesis of C60-Metal Cluster Heterostructures with High Electrocatalytic Hydrogen-Evolution Performance.

Metal clusters, due to their small dimensions, contain a high proportion of surface atoms, thus possessing a significantly improved catalytic activity compared with their bulk counterparts and nanoparticles. Defective and modified carbon supports are effective in stabilizing metal clusters, however, the synthesis of isolated metal clusters still requires multiple steps and harsh conditions. Herein, we develop a C60 fullerene-driven spontaneous metal deposition process, where C60 serves as both a reductant and an anchor, to achieve uniform metal (Rh, Ir, Pt, Pd, Au and Ru) clusters without the need for any defects or functional groups on C60. Density functional theory calculations reveal that C60 possesses multiple strong metal adsorption sites, which favors stable and uniform deposition of metal atoms. In addition, owing to the electron-withdrawing properties of C60, the electronic structures of metal clusters are effectively regulated, not only optimizing the adsorption behavior of reaction intermediates but also accelerating the kinetics of hydrogen evolution reaction. The synthesized Ru/C60-300 exhibits remarkable performance for hydrogen evolution in an alkaline condition. This study demonstrates a facile and efficient method for synthesizing effective fullerene-supported metal cluster catalysts without any pretreatment and additional reducing agent.