Hydrogen Evolution Reaction Process Research Articles

Polyimide-based triazine-cored covalent organic frameworks supported metal (Fe, Ni, Ru and Rh) nanoparticles for high-efficiency electrocatalytic hydrogen evolution

Covalent organic frameworks (COFs) have great potential in electrocatalytic hydrogen evolution reaction (HER). Nevertheless, it is a challenging task to fabricate COF-based electrocatalysts with low overpotential and high stability for HER in acidic media. Herein, a series of polyimide-based triazine-cored COFs (PIT-COFs) with different aromatic diimides are designed to support metal (Fe, Ni, Ru and Rh) nanoparticles for electrocatalytic HER. PIT-COFs are obtained by the reaction between melamine and aromatic (benzene, biphenyl, naphthalene and perylene) diimides. PIT-COFs based on perylenediimide show the optimal electrocatalytic HER activity in acidic media due to its large π-conjugated structure. Rh@COFMA-PT has a low overpotential value of 70 mV at 10 mA cm−2 and a small Tafel slope of 56.58 mV dec−1, which surpasses numerous previously published HER electrocatalysts. Furthermore, Rh@COFMA-PT exhibits good electrocatalytic stability and still keeps high activity after 3000 cycles. The conjugated nitrogen-rich structures of PIT-COFs and their ability to effectively anchor metal nanoparticles as active sites significantly promote the electron and proton transport during the electrocatalytic HER process. This work offers a guideline for developing effective and stable COF-based HER electrocatalysts with abundant active sites.

Surface-Reconstructed CdNNi3 Antiperovskite Electrocatalyst: Unlocking Ampere-Level Current Density for Hydrogen Evolution.

Developing conductive electrocatalysts is crucial for decreasing the ohmic loss induced by electric resistance of the catalyst layer in the large-current-density hydrogen evolution reaction (HER), which has been overlooked previously. In this study, we screen a highly conductive antiperovskite CdNNi3 with negligible ohmic loss, as a highly active and durable HER electrocatalyst capable of unlocking ampere-scale current densities. CdNNi3 exhibits an impressive activity (an overpotential of 235 mV) at 1 A cm-2 and maintains its performance steadily at an ampere-scale current density (at 1 A cm-2 over 400 h). Besides, the CdNNi3-enabled anion-exchange membrane water electrolyzer outperforms that of the benchmark Pt/C, evidenced by a reduced cell voltage of 160 mV at 1 A cm-2, and presents a favorable stability at 1 A cm-2. Importantly, this study experimentally discovers the dynamic surface reconstruction phenomena of antiperovskite nitrides during alkaline HER. Theoretical analysis suggests that the presence of Cd in the reconstructed surface effectively adjusts the local electronic configuration of active sites, which promotes the adsorption of OH and reduces the binding strength to H, thereby facilitating the water dissociation step and reducing the energy barrier of the potential-determining step in the HER process.

Tuning the Morphology of Transition Metal Disulfides: Advances in Electrocatalysts for Hydrogen Evolution Reaction

The hydrogen evolution reaction (HER) in the renewable energy system has gained a lot of attention from researchers as hydrogen is assumed to be a clean and renewable carrier. Transition metals and their compounds have been used as promising alternatives to precious noble metals for the HER, offering low cost, more availability, and high activity. In this work, we discussed the mechanisms of the HER and how morphology influenced the catalytic performance of transition metal disulfide (TMD), focusing on structures that range from zero-dimensional (0D) to three-dimensional (3D) TMD materials. Notably, two-dimensional (2D) TMDs, like nanosheets, exhibit the lowest overpotential and a very small Tafel slope, which can be ascribed to their inherent layered structure and large surface area. According to recent research reports, the efficacy and efficiency of the HER process are influenced by surface chemistry, electrochemical characteristics, and the existence of active sites.

Hydrogen Spillover-Bridged Interfacial Water Activation of WCx and Hydrogen Recombination of Ru as Dual Active Sites for Accelerating Electrocatalytic Hydrogen Evolution.

Tungsten carbide (WCx) is a promising alternative to platinum catalysts for hydrogen evolution reaction (HER). However, strong tungsten-hydrogen bond hinders hydrogen desorption while favoring H+ reduction, thus limiting HER kinetics. Inspired by the phenomenon of hydrogen spillover in heterogeneous catalysis, a ruthenium (Ru) doped-driven activated hydrogen migration from WCx surface to Ru is reported. This approach achieved high activity with an ultralow overpotential of 9.0mV at 10 mA·cm-2 and superior stability at an industrial-grade current density of 1.0 A·cm-2 @ 1.65V. In situ attenuated total reflectance surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS)and operando electrochemical impedance spectra revealed that this exceptional hydrogen production-which surpasses that of previously reported Pt/C catalysts-is attributable to the outstanding ability of WCx to induce water dissociation and hydrogen spillover from WCx to Ru surface. During the HER process, the rigid interfacial water network negatively affected the HER efficiency under alkaline conditions. The WCx sites disrupted this rigid structure, facilitating the contact between activated hydrogen (H*) and WCx sites. Subsequently, H* migrates to Ru surface, where hydrogen recombination occurs to produce H2. This work paves a new avenue for the construction of coupled catalysts at the atomic scale to facilitate HER electrocatalysis.

Polyoxometalate‐Derived Photocatalysts Enabling Progress in Hydrogen Evolution Reactions

AbstractPhotocatalytic water splitting is capable of converting abundant solar energy into environmentally friendly and renewable chemical energy, presenting a promising solution to alleviate the energy crisis and combat environmental pollution. The development of high‐performance photocatalysts is crucial for significantly improving the efficiency of the hydrogen evolution reaction (HER) involved. Polyoxometalate (POM)‐derived materials, known for their tunable compositions, diverse structures, electron storage/release capabilities, as well as quasi‐semiconductor photochemical properties, serve as highly efficient catalysts in sustainable photosynthesis. This comprehensive review navigates the latest advancements in the assembly strategies and HER performance of POM‐based crystalline materials. It also discusses the composite materials formed by infiltrating POM into metal‐organic frameworks (MOF) and examines the roles of transition metal compounds derived from polyoxometalates, such as sulfides and carbides, in photocatalytic HER. Emphasis is placed on the prospects for the future development of POM‐based compounds as photocatalysts, along with several strategies and outlooks that could facilitate their progress. POM‐derived materials are believed to have significant potential to enhance hydrogen production efficiency while maintaining thermal stability in HER processes.

In-situ synthesis nano PtRuW/WC HER catalyst for acid hydrogen evolution by microwave method

Abstract One of the primary challenges in electrocatalysis for the hydrogen evolution reaction (HER) lies in the development of highly efficient catalysts suitable in acidic environments. Tungsten carbide-based materials have long been proposed as potential substitutes for Pt due to their “Pt-like” electronic properties in the HER process. However, tungsten carbide still falls short of the performance exhibited by commercial precious-metal catalysts. Herein, PtRuW/WC was prepared by a microwave heating method and acted as a HER electrocatalyst. The microwave method not only enhances the diffraction peaks of the substrate tungsten carbide, but also facilitates the growth of metal ions at specific sites. The PtRuW/WC catalyst demonstrates outstanding performance in acidic HER, characterized by a minimal overpotential of 40.7 mV at 10 mA/cm2 (η10). Furthermore, it exhibits exceptional stability in acidic solutions, showing no substantial degradation during 20 h at 1000 mA/cm2. The catalyst-assembled PEM electrolytic water electrode further proves that PtRuW/WC has excellent electrolytic water performance and makes some efforts for the development of commercial PEM electrolytic water.

Iron phosphide nanoparticles anchored on 3D nitrogen-doped graphene as an efficient electrocatalysts for hydrogen evolution reaction in alkaline media

Electrocatalysts play a crucial role in hydrogen evolution reaction (HER), facilitating a clean and sustainable generation of hydrogen energy. To promote the HER process, it is imperative to employ highly efficient, stable, and cost-effective electrocatalysts. This research focuses on the design of iron phosphide nanoparticles anchored onto a porous three-dimensional nitrogen-doped graphene (FeP@3DNG). The porous framework of 3DNG serves a multifaceted purpose: it prevents the aggregation of FeP nanoparticles during phosphidation, safeguards the FeP electrocatalyst from oxidation during the HER, and simultaneously enhances electrical conductivity and stability. Notably, the FeP@3DNG nanocomposite demonstrated the efficient activity and highest HER activity with an overpotential of 76 mV to achieve 10 mA cm−2 and a small Tafel slope of 40.2 mV dec−1 as well as good long-term durability for 20 h in 1.0 M KOH solution. The high performance of the FeP@3DNG nanocomposite can be primarily corresponded to the synergistic effects of the highly active of FeP nanoparticles and advantages of porous three-dimensional graphene with excellent electrocatalytic activity, high specific surface area, and chemical stability, thus, resulting in the improvement the overall electrocatalytic activity.

Modulating electronic by construction WS2/WN heterostructure coupled with N-doped carbon to boost alkaline seawater hydrogen production

The development of an efficient and durable non-precious electrocatalyst for alkaline seawater electrolysis is of great significance. Herein, two-dimensional (2D) lamellar heterostructure WS2/WN was dispersed on the carbon matrix (marked as WS2/WN@CM). The obtained WS2/WN@CM catalysts demonstrate exceptional performance in the hydrogen evolution reaction (HER) in alkaline freshwater (1.0 M KOH), alkaline simulated seawater (1.0 M KOH + 0.5 M NaCl) and alkaline natural seawater (1.0 M KOH + seawater), respectively, which achieved a low overpotential (92 mV, 95 mV and 113 mV) at 10 mA cm−2 and outstanding long-term durability at 200 mA cm−2 for 100 h. The catalyst benefits from the 3D carbon skeleton, which not only effectively prevents stacking of the 2D lamellar WS2/WN to fully utilize the active material, but also provides rapid electron transport. Moreover, stress effects at WS2/WN interfaces lead to distortions of torsion angles in the WS2 lattice, thereby increasing crystal surface defects accompanied by an enhancement of electrical conductivity. Density functional theory (DFT) calculations combined with XPS evidence confirm the electronic structure reorganization of WS2/WN at interfaces, which optimizes the adsorption energy of specific intermediates. Additionally, WN captures many electrons from WS2, so the WN region favors the reduction reaction and thus enhances the HER process.

In situ construction of W-doped Co-P electrocatalyst by electrodeposition for boosting alkaline water/seawater hydrogen evolution reaction

The development of an efficient yet cost-effective non-precious electrocatalyst for the hydrogen evolution reaction (HER) in alkaline water and seawater systems remains a formidable obstacle to the large-scale production of hydrogen energy, stemming from the sluggish kinetics of electron transfer reactions during the HER process. In this article, an amorphous Co-P-W electrocatalyst on nickel foam is prepared using a brief cyclic voltammetry (CV) electrodeposition method. The optimized Co-P-W electrocatalyst exhibits excellent electrocatalytic performance for HER, which only requires overpotentials of 59 and 143 mV to achieve a current density of 10 mA cm−2 in alkaline water (1.0 M KOH) and alkaline seawater (1.0 M KOH + natural seawater), respectively, and remarkable stability and durability. The improved HER performance of the Co-P-W electrocatalyst is attributed to the introduction of W, which modulates the electronic structure of Co and P, optimizes the adsorption/dissociation of H2O, and reduces the charge transfer resistance of the Co-P electrocatalyst, thus improving the kinetics of the HER. Furthermore, the W-doping significantly enhances the hydrophilicity of the Co-P electrocatalyst, which favors rapid and thorough penetration of electrolytes into the electrocatalyst, facilitating the formation of a highly accessible reaction interface, ultimately resulting in excellent HER activity. Our findings demonstrate the feasibility of designing an efficient, durable, and scalable electrocatalyst to significantly boost HER efficiency for practical water electrolysis.

NiCoP/CoP2 nanoparticles supported on sugarcane bagasse carbon as the electrocatalyst with excellent catalytic performance towards the hydrogen evolution reaction

Sugarcane bagasse carbon (SCBC) was synthesized and used to support NiCoP/CoP2 nanoparticles (NiCoP/CoP2-SCBC), and its electrocatalytic performance for the hydrogen evolution reaction (HER) was investigated and compared with that of NiCoP/CoP2 nanoparticles and NiCoP/CoP2 nanoparticles supported on carbon black (NiCoP/CoP2-C). Impressively, NiCoP/CoP2-SCBC shows the best electrocatalytic performance for HER with an over-potential of 159.5 mV at 10 mA cm-2 and a Tafel slope of 67.24 mV dec-1, along with the excellent stability. This outstanding performance is partly attributed to the abundant hydroxyl functional groups in SCBC, which can make the catalyst have better dispersion and a higher proportion of Ni2+. In addition, SCBC can lead to more defects in NiCoP/CoP2, and SCBC contains a large number of P elements, which can increase the catalytic active sites and contribute to the fast HER process to some degree.

Theoretical design and synthesis of Co30Ni60/CC for high selective methanol oxidation assisted energy-saving hydrogen production

The integration of methanol oxidation reaction (MOR) with hydrogen evolution reaction (HER) represents an advanced approach to hydrogen production technology. Nonetheless, the rational design and synthesis of bifunctional catalysts for both MOR and HER with exceptional activity, stability and selectivity present formidable challenges. In this work, firstly, density functional theory (DFT) was utilized to design and evaluate material models with high performance for both MOR and HER. Secondly, guided by DFT, Co30Ni60/CC (CC, carbon cloth) composites with a leaf-like nanosheet structure were successfully fabricated via electrodeposition. In the MOR process, Ni acts as the predominant active center, while Co amplifies the electrochemically active surface area (ECSA) and enhances the selectivity of methanol oxidation. Conversely, in the HER process, Co serves as the primary active center, with Ni augmenting the charge transfer rate. The electrochemical results demonstrate that Co30Ni60/CC exhibits exceptional performance in both MOR and HER at a current density (j) of 10 mA cm−2, with peak potentials of 1.323 V and −95 mV, respectively. Additionally, it shows remarkable selectivity for the oxidiation of methanol to high value-added formic acid. Thirdly, following a 100 h chronopotentiometry (CP) test, the required potential demonstrates an increase of 4.9 % (MOR) and 8.1 % (HER), signifying the superior stability of Co30Ni60/CC compared to those reported in the literature. The exceptional performance of Co30Ni60/CC can be primarily attributed to that the leaf-like nanosheets structure not only exposes a plethora of active sites but also facilitates electrolyte diffusion, the monolithic structure prepared by electrodeposition enhances its stability, and the transfer of electrons from Co to Ni regulates its electronic structure, as corroborated by X-ray photoelectron spectroscopy (XPS) and density of states (DOS) analyses. Finally, at the same j, the voltage required by the Co30Ni60/CC||Co30Ni60/CC electrolytic cell, powered by an electrochemical workstation, is 198 mV lower than that required for alkaline water-splitting. Meanwhile, at higher j (100 mA cm−2), the electrolytic cell exhibits sustained and stable operation for 150 h, enabling high-efficiency hydrogen production and the synthesis of high value-added formic acid.

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.

Ultra-Fast Synthesis of Highly Dispersed Pt Nanoclusters Anchored on Sulfur-Doped Porous Carbon Carriers by Nanosecond Pulsed Laser for Hydrogen Evolution Reaction.

Nanosecond pulsed laser irradiation is employed for synthesis of highly active and stable Pt-based electrocatalysts by anchoring Pt nanoclusters on porous sulfur-doped carbon supports (L-Pt/SC). Strong metal-support interaction (SMSI) between Pt and S induces a local charge rearrangement and modulates the electronic structure of Pt surroundings, thus boosting the reaction kinetics and enhancing stability in long-term hydrogen evolution reaction (HER). The L-Pt/SC catalyst exhibits high activity toward HER, with an overpotential of 23 mV at current densities reaching 10 mA cm-2 and a Tafel slope of 24mV dec-1. The unit mass activity of L-Pt/SC is calculated to be -10.8 A cm-2 mgPt -1 at an applied voltage of -0.3V versus RHE. In situ Raman spectra reveals that L-Pt/SC catalyst exhibits fast hydrogen production efficiency and its electrocatalytic HER process is determined by the Tafel step. Density functional theory calculations suggest the strong bonding energy between SC and Pt induces the formation of smaller nanoclusters of L-Pt/SC during fast pulsed laser preparation, which increases the effective contact area during the HER process thereby increasing the activity per unit mass.

Electrodeposition of Ni–MoS2 as effective hydrogen evolution reaction catalysts in alkaline media

Highly active, long-lasting, and economically feasible nonprecious metal-based electrocatalysts are urgently required for the slow hydrogen evolution reaction (HER) in alkaline conditions. Direct current (DC) electrodeposition was used to develop the highly active Ni–MoS2 composite coatings for efficient hydrogen generation. Scanning electron microscopy (SEM), Energy Dispersive X Ray Spectroscopy (EDS), X-ray diffraction (XRD), and linear sweep voltammetry (LSV) were used to evaluate the coatings. Ni–MoS2 composite coatings behaved almost identically to pure platinum metal. The Ni–MoS2 coating produced 1.0 g/l demonstrated a low overpotential for HER. The HER process's analyzed from Volmer-Tafel mechanistic route has an extremely low slope of 56.5 mV/dec. All the coated samples were subjected to chronopotentiometry (CP). This catalyst's high HER performance shows that it has significant potential for practical applications.

Cerium single atom anchored silver selenide: A high-performance catalyst for hydrogen evolution reaction with ultra-low activation energy and enhanced stability

Single-atom catalysts (SAC) have enabled high electrocatalytic activity production because of the enormous active sites bearing catalysts for hydrogen evolution reaction (HER). Herein, we report cerium single atom (Cesa) anchored silver selenide (Ag2Se) via metal-chalcogenide interaction for high-performance HER evolution. The designed electrocatalyst possesses extraordinary electrochemical and optical properties, thus the Cesa-Ag2Se could be a potential catalyst for the photo-electrochemical HER process. The sluggish diffusion rate of the Ce atom within the Ag2Se facilitates the high stability and the dispersed Cesa displayed ∼2 eV of energy differences with the Ce dimer proving the formation of dispersed Cesa over Ag2Se is potentially favorable. The minimum energy pathway (MEP) suggested the Cesa-Ag2Se system established only 0.003 eV as an ultra-low activation energy barrier in order to produce H2, which is by far the finest performance of Ag2Se-based thermodynamically favourable catalysis. The accumulated electron density due to the presence of Cesa enabled the presence of a large number of potential active sites (Ce and Ag) for hydrogen adsorption, in addition, the supportive zero band gap of the Ag2Se accelerated the kinetics for HER. Ultimately, we employed the Wentzcovitch cell dynamics-based molecular dynamics study for H* adsorbed Cesa-Ag2Se that suggests the stability of the catalyst for 500 fs. The in-depth HER modelling using the Lennard-Jones force field demonstrated the insightful dynamics behaviour of the catalytical system.

The interfacial engineering of seaurchin-like CoP/Ni2P heterostructure for highly efficient alkaline hydrogen evolution

Creating efficient, cost-effective catalysts for the hydrogen evolution reaction (HER) with low overpotential is crucial for advancing the hydrogen energy cycle. Herein, the CoP is introduced into the Ni2P system to attract the transfer of electrons from Ni2P to the CoP. Interfacial electronic structure optimization enabled the binder-free sea urchin-like CoP/Ni2P/NF electrocatalysts present superb performance in HER within 1.0 M KOH, characterized by a minimal overpotential of 67.4 mV and a reduced Tafel slope of 73.9 mV dec-1 under a current density of 10 mA cm−2. The as-fabricated catalyst also demonstrates significant long-term HER stability. The reallocation of charge across the heterogeneous interface of CoP/Ni2P catalyst was further investigated via DFT calculation. The addition of CoP effectively accelerates the electron transfer and optimized the heterogeneous interface inside CoP/Ni2P for *H adsorption/H2 desorption, reduced the water decomposition energy barrier, thereby, promoting the HER process. The microstructural construction as well as synergistic effect of interfacial electrons of CoP/Ni2P catalyst paves the way to design electrocatalysts with highly HER activity.

A "Two-Pronged" Strategy to Boost Hydrogen Evolution Kinetics on NiFe-Based (Oxy)hydroxides via Oxygen Deficient Ni-Mo-Fe Coordinate Structures for Ultra-Stable Ampere-Level Alkaline Overall Water Splitting.

NiFe (oxy)hydroxides have been regarded as one of the state-of-the-art catalysts for oxygen evolution reaction (OER). Unfortunately, the sluggish hydrogen evolution reaction (HER) kinetics limit its application as bifunctional electrocatalyst for alkaline overall water splitting (OWS). Herein, a "two-pronged" strategy is proposed to construct highly active oxygen deficient Ni-Mo-Fe coordinate structures in NiFe (oxy)hydroxide (NFM-OVR/NF), which simultaneously reduces the energy barrier of Volmer and Heyrovsky steps during alkaline HER process and significantly accelerate the reaction kinetics. Consequently, NFM-OVR/NF delivers overpotentials as low as 25 and 234mV to achieve 10 and 1000mA cm-2 in 1.0M KOH, respectively. Furthermore, benefiting from excellent HER and OER activity, NFM-OVR/NF exhibits a remarkable OWS activity with cell voltages of 1.44V and 1.77V at 10 and 1000mA cm-2 in 1.0M KOH, and displays ultralong-term stability for 600h at 500mA cm-2, while remaining durable for 300h in an alkaline water electrolyzer in 30% KOH at 80°C. The calculated price per gallon of gasoline equivalent for the produced H2 is $ 0.92, which is much lower than 2026 U.S. Department of Energy target ($ 2.00), demonstrating feasibility and practicability of NFM-OVR/NF for industrial applications.

Novel BDD-loaded bimetallic phosphide electrodes enable interesting bifunctional seawater electrolysis

The direct electrolysis of seawater for the production of green hydrogen energy is an economically attractive approach. However, this technique confronts technical problems because to the oxygen evolution reaction (OER) weak stability and inadequate selectivity due to competition with the chlorine evolution process. This work focuses on improving the stability of the electrode and electrolysis efficiency. The phosphating NiCoP active layer with 3D porous morphology was created by electrodeposition on the B-doped diamond (BDD) as an electrode inspired by the bifunctional catalysis strategy. The successfully constructed unique cube-on-nanosheets structure in the NiCoP active layer enables the electrode to exhibit excellent electrocatalytic performance. The porous NiCoP/BDD (Por-NiCoP/BDD) electrodes showed good catalytic activity in alkaline-simulated seawater with the OER and hydrogen evolution reaction (HER) overpotentials of 400 and 261 mV, respectively, at a current density of 100 mA cm−2. More importantly, the electrode exhibits interesting stability of the catalytic performance and structural in alkaline-simulated seawater electrolysis, with the current density decaying by only 1.52 % and 4.06 % after OER and HER processes for 50 h, respectively. This work expands the valuable application scenarios of BDD electrode and provides novel ideas for the development of seawater electrolysis.

Vertically-stacked W/W2C heterojunctions with high electrocatalytic capability for the hydrogen evolution reaction in a wide pH range

The hydrogen evolution reaction (HER) in water splitting is among the foremost methods to produce clean and green hydrogen from renewable sources. The practical use of the HER technology is however hindered by the high price and/or the relatively low efficiency of the currently used catalysts. Herein, we report a heterostructured W/W2C electrocatalyst featuring vertically stacked interfaces and embedded in N-doped porous graphitic carbon (denoted as W/W2C@N-PGC) as a high-performance electrocatalyst for the HER in a wide pH range. The catalyst synthesis, accomplished through a straightforward one-pot method, is both facile and highly efficient, involving freeze-drying a suspension of the starting materials followed by pyrolyzing the obtained dry gel. Density functional theory calculations revealed the crucial role of the W/W2C heterojunction in promoting the two key steps of the HER, viz. HOH bond scission and H2 emission. Electrochemical data confirmed the excellent electrocatalytic capability of W/W2C@N-PGC toward the HER process in a wide pH range including alkaline, acidic, and neutral electrolytes. In 1.0 M KOH, we measured a low overpotential of 102 mV to drive a current density of 10 mA cm−2; a long-term stability (up to 24 h) was also realized. The data presented in this work highlight the importance of electrocatalysts with heterojunctions for the HER and the methodology presented in this work may be extended to other contemporary energy-related technologies such as CO2 reduction, oxygen evolution, and oxygen reduction reactions.

Microwave‐Assisted PtRu Alloying on Defective Tungsten Oxide: A Pathway to Improved Hydroxyl Dynamics for Highly‐Efficient Hydrogen Evolution Reaction

AbstractPlatinum (Pt)‐based compounds are the benchmarked catalysts for hydrogen evolution reaction (HER) but exhibit slow kinetics in alkaline environments. The *OH accumulation on Pt surface can block active sites, affecting proton reduction and water re‐adsorption. Alloying Ruthenium (Ru) with Pt sites can significantly modulate the adsorption and desorption of water dissociation intermediates. Choosing suitable supports and utilizing metal‐support interaction (MSI) is crucial for active site optimization. PtRu alloy anchored on tungsten oxide (WO3) with rich oxygen vacancies (OV) is prepared through an ultrafast microwave‐assisted approach. Benefiting from the coupling effects between alloying and MSI, PtRu/WO3‐OV exhibits exceptionally high HER activity. In 1 m KOH, 1 m KOH + seawater, and 0.5 m H2SO4, it requires ultralow overpotentials of 9, 26, and 6 mV to achieve 10 mA cm−2, respectively. The designed catalyst surpasses commercial Pt/C in mass activity and demonstrates considerable potential for intermittent energy integration. Density functional theory reveals that alloying Ru with Pt sites significantly reduces the energy barrier of dissociating *OH, modulating blockage on the surface and then promoting the overall alkaline HER process. This study offers insights into the rapid synthesis of non‐carbon supported catalysts with Pt site modulation for alkaline hydrogen generation.