Hydrogen Evolution Reaction Kinetics Research Articles

Ru-regulated electronic structure CoNi-MOF nanosheets advance water electrolysis kinetics in alkaline and seawater media

Herein, an ion-exchange strategy is utilized to greatly improve the kinetics of hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) by Ru-modified CoNi- 1,3,5-Benzenetricarboxylic acid (BTC)-metal organic framework nanosheets (Ru@CoNi-MOF). Due to the higher Ni active sites and lower electron transfer impedance, Ru@CoNi-MOF catalyst requires the overpotential as low as 47 and 279 mV, at a current density of 10 mA/cm2 toward HER and OER, respectively. Significantly, the mass activity of Ru@CoNi-MOF for HER and OER are 25.9 and 10.6 mA mg−1, nearly 15.2 and 8.8 times higher than that of Ni-MOF. In addition, the electrolyzer of Ru@CoNi-MOF demonstrates exceptional electrolytic performance in both KOH and seawater environment, surpasses the commercial Pt/C||IrO2 couple. Theoretical calculations prove that introducing Ru atoms in - CoNi-MOF modulates the electronic structure of Ni, optimizes adsorption energy for H* and reduces energy barrier of metal organic frameworks (MOFs). This modification significantly improves the kinetic rate of the Ru@CoNi-MOF during water splitting. Certainly, this study highlights the utilization of MOF nanosheets as advanced HER/OER electrocatalysts with immense potential, and will paves a way to develop more efficient MOFs for catalytic applications.

Rational Design of Multiple Heterostructures with Synergistic Effect for Efficient and Stable Hydrogen Evolution Toward Industrial Alkaline Water Splitting

AbstractElectrocatalytic hydrogen evolution reaction (HER) via alkaline water splitting holds great promise for industrial clean hydrogen production but is frustrated by limited catalytic activity and inferior stability under high current density. Elaborate manipulating of heterostructure on robust catalytic electrodes is essential but challenging for accelerating HER kinetics with high durability. Herein, a robust nickel mesh electrode, offering high mechanical stability, is directly engineered with catalytic layers of multiple heterostructures (r‐Mn–Ni/CoP) via facile one‐pot electrodeposition followed by surface reconstruction strategy. The abundant heterostructures composed of crystalline CoP, NiP, amorphous region, and additional Mn doping considerably manipulate the electronic structure with optimized charge transfer; while the in situ surface‐reconstructed hydrophilic nanoflakes enable the rapid wetting of active sites to the electrolyte. Consequently, the r‐Mn–Ni/CoP requires only 134 mV overpotential at the current density of 100 mA cm−2, superior to monophasic and undoped samples, and the majority of reported HER catalysts. Remarkably, an electrolyzer with r‐Mn–Ni/CoP on a nickel mesh cathode demonstrates extraordinary activity with a voltage of 1.734 V at 300 mA cm−2 and stable operation of 800 h. The finding provides a feasible strategy for the fabrication of nonprecious‐metal‐based HER electrocatalysts with high activity and stability toward industrial water electrolysis.

Boost alkaline hydrogen evolution reaction by intermetallic charge transfer in perovskite ruthenate encapsulated in ZIF-67 derived cobalt sulfide nanoparticles

Constructing and manipulating heterostructure is an effective strategy to prepare electrocatalysts with excellent performance for water electrolysis. Herein, an efficient alkaline hydrogen evolution reaction (HER) electrocatalysts, Co3S4-embedded in carbon-encapsulated BaRuO3 (BaRuO3@CS-0.1), was synthesized through the sacrificial template method of ZIF-67 encapsulated BaRuO3 precursors. By inheriting the exceptional merits of different ingredients, this heterostructure catalyst BaRuO3@CS-0.1 enables intermetallic charge transfer between Ru and Co with boosted HER kinetics, and thus displaying higher catalytic activity towards HER, as evidenced by the intensively theoretical calculations and experimental measurements. BaRuO3@CS-0.1 exhibits excellent HER performance, with the lowered overpotentials of 26 mV to achieve 10 mA cm−2 in comparison to the pristine BaRuO3 (51 mV), which is also superior to Pt/C catalyst at large current density. Moreover, this heterostructure also demonstrates comparable oxygen evolution reaction (OER) activities with the representative electrocatalysts, delivering current densities of 10 mA cm−2 at a potential of 1.546 V for overall water splitting. These findings provide a rational route to optimize the performance of bulk electrocatalysts and endow them with richer electrochemical activity through this composite strategy.

Fabricating highly active Pt atomically dispersed catalysts with the co-existence of Pt-O1Ni1 single atoms and Pt sub-nanoclusters for improved hydrogen evolution

Atomically dispersed catalysts (ADCs), including single atoms and sub-nanoclusters, simultaneously, are considered as the most promising candidate to boost the reaction kinetics of hydrogen evolution reaction (HER). However, the correlation between the coordination environment of single atoms and catalytic activity has not been clearly discussed in ADCs system. Herein, Pt ADCs with the different coordination structures were fabricated by a facile sulfurate route coupling deposition strategy. Importantly, Pt ADCs, including Pt-O1Ni1 single atoms and Pt sub-nanoclusters (Pt1+n/Ni3S2), show good basic HER activity, which just need 17 mV at 10 mA cm−2. Meanwhile, the turnover frequency for Pt1+n/Ni3S2 is 0.49 H2 s−1 under the overpotential of 100 mV, which is 8.6 times higher than Pt/C. Besides, the assembled RuO2 || Pt1+n/Ni3S2 system could get 100 mA cm−2 current density under 1.7 V cell voltage in alkaline water electrolyzer. Notably, in-situ Raman and attenuated total reflection-surface enhanced infrared absorption spectroscopy reveal that Pt-O1Ni1 coordination is conducive to promoting the fracture of H-O-H bond, realizing the rapid transform of Pt-H* intermediates. Further, density functional theory calculations confirm Pt single atoms with Pt-O1Ni1 coordination environment in Pt1+n/Ni3S2 serves as the main role for HER because Pt-O1Ni1 are more likely to accelerate the production of Pt-H* at the Pt sites, extremely achieving the rapid HER progress. This work discloses the structure-activity relationship in ADCs system, which is essential for the development of highly active electrocatalysts.

Stainless steel as gas evolving electrodes in water electrolysis: Boosting the electrocatalytic hydrogen evolution reaction on electrodeposited Ni@CoP modified stainless steel electrodes

High efficient and durable electrocatalytic electrodes play a vital role in energy conversion and storage. In this concern, water electrolysis technology needs high performance electrodes with high activity and stability to implement this technology for green hydrogen production. Here, this study reports on the development of self-supported electrodes for the hydrogen evolution reaction (HER) based on sequential electrodeposition technique. First, the CoP has been deposited on stainless steel mesh (SSM) electrode followed by deposition of Ni to form Ni@CoP electrocatalysts standing on SSM. The loading amount of Ni was studied to achieve a high catalytic activity. The developed electrodes have been investigated with FE-SEM, EDX, XRD and XPS to identify their morphological properties as well as their chemical states and compositions. Electrocatalytic activity and durability have been studied in alkaline media by different electrochemical methods, such as LSV, EIS and CP. The results showed that the optimum deposition time of 10 min (10Ni@CoP) exhibited the higher catalytic activity in term of overpotential and Tafel slope giving a overpotential of 188 mV at 10 mA cm−2 with a small Tafel slope of 69 mV.dec−1 compared to CoP electrode with overpotential 266 mV and Tafel slope of 105 mV.dec−1 highlighting the role of Ni in enhancing the catalytic activity of the developed electrodes towards HER. Moreover, the Ni@CoP showed high stability under continues electrolysis at 50 and 100 mA.cm−2. These findings have been discussed in light of porous structure of the electrodes and introducing of Ni particles which led to creating more active sites and enhancing the hydrogen adsorption/desorption and thus facilitating the HER kinetics. The facial preparation method of self-supported electrodes and the obtained activity and stability of Ni@CoP electrodes render them as potent electrodes for HER in alkaline water electrolysis.

Tuning A-Site Cation Deficiency in Pr0.5La0.5BaCo2O5+ δ Perovskite to Realize Large-Scale Hydrogen Evolution at 2000mAcm-2.

Industrial-level hydrogen production from the water electrolysis requires reducing the overpotential (η) as much as possible at high current density, which is closely related to intrinsic activity of the electrocatalysts. Herein, A-site cation deficiency engineering is proposed to screen high-performance catalysts, demonstrating effective Pr0.5- xLa0.5BaCo2O5+ δ (P0.5- xLBC) perovskites toward alkaline hydrogen evolution reaction (HER). Among all perovskite compositions, Pr0.4La0.5BaCo2O5+ δ (P0.4LBC) exhibits superior HER performance along with unique operating stability at large current densities (J = 500-2000mAcm-2 geo). The overpotential of ≈636mV is achieved in P0.4LBC at 2000mAcm-2 geo, which outperforms commercial Pt/C benchmark (≈974mV). Furthermore, the Tafel slope of P0.4LBC (34.1mVdec-1) is close to that of Pt/C (35.6mVdec-1), reflecting fast HER kinetics on the P0.4LBC catalyst. Combined with experimental and theoretical results, such catalytic activity may benefit from enhanced electrical conductivity, enlarged Co-O covalency, and decreased desorption energy of H* species. This results highlight effective A-site cation-deficient strategy for promoting electrochemical properties of perovskites, highlighting potential water electrolysis at ampere-level current density.

VOx-doped CoP catalysts with synergistic dual-active configuration for boosting hydrogen evolution kinetics

Hydrogen evolution reaction (HER), is of great significance to harvest H2 via energy-saving alkaline water electrolysis yet still challenging. Integrating heterogeneous materials is effective in designing favorable electrocatalysts for water dissociation (WD) and H-immediate involved adsorption/desorption behavior and triggering positive interactions to break the kinetics limitation. Herein, a promising configuration of a vanadium-oxide species integrated with cobalt-phosphide plane that grown on the nickel foam (labeled as VOx-CoP/NF), is demonstrated to boost the alkaline HER kinetics comprehensively. The doped vanadium-oxide species preferentially perform the WD process to generate H-intermediates. Meanwhile, interaction between VOx and CoP induce the electronic redistribution that optimizes 3d-2p orbital hybridization state, which balances the adsorption strength of H* to facilitate the hydrogen transfer and enrichment. Eventually, VOx-CoP/NF exhibits supereminent alkaline HER performance with an overpotential of only 65/245mV at 10/400mAcm−2, superior to individual CoP and most representative cobalt-phosphide candidates. A flowing anion exchange membrane (AEM) urea-assisted water electrolyzer with VOx-CoP/NF as a bifunctional catalyst, is assembled and achieves a satisfactory performance, verifying its practical feasibility for efficient H2 production. The concept exemplified in this work is that synchronous optimization of elementary reaction step kinetics of HER through reasonable constructing well-defined configuration is instructive for the design of HER electrocatalysts.

Electron Redistribution of Ru Site on MoO2@NiMoO4 Support for Efficient Ampere-Level Current Density Electrolysis of Alkaline Seawater.

Seawater electrolysis is a promising but challenging strategy to generate carbon-neutral hydrogen. A grand challenge for hydrogen evolution reaction (HER) from alkaline seawater electrolysis is the development of efficient and stable electrocatalysts to overcome the limitation of sluggish kinetics. Here, a 3D nanorod hybrid catalyst is reported, which comprises heterostructure MoO2@NiMoO4 supported Ru nanoparticles (Ru/ MoO2@NiMoO4) with a size of ≈5nm. Benefitting from the effect of strongly coupled interaction, Ru/MoO2@NiMoO4 catalyst exhibits a remarkable alkaline seawater hydrogen evolution performance, featured by a low overpotential of 184mV at a current density of 1.0 A cm-2, superior to commercial Pt/C (338mV). Experimental observations demonstrate that the heterostructure MoO2@NiMoO4 as an electron-accepting support makes the electron transfer from the Ru nanoparticles to MoO2, and thereby implements the electron redistribution of Ru site. Mechanistic analysis elucidates that the electron redistribution of active Ru site enhances the ability of hydrogen desorption, thereby promoting alkaline seawater HER kinetics and finally leading to a satisfactory catalysis performance at ampere-level current density of alkaline seawater electrolysis.

Intensifying the Supported Ruthenium Metallic Bond to Boost the Interfacial Hydrogen Spillover Toward pH‐Universal Hydrogen Evolution Catalysis

AbstractThe effectuation of pH‐universal electrocatalysis is highly attractive but still challenging for the hydrogen evolution reaction (HER). It appeals for not only the facilitated electron transport but also the kinetical proton mass transfer. In this study, a via‐hole Ru/MoO2 confined heterostructure is profiled as a metal‐support platform for the electron/mass transfer‐boosted pH‐universal HER studies. It is indicated that the as‐formed Ru─O─Mo bridge can modulate the electronic transport at the interface, and the proton adsorption and transfer are kinetically derived by the intensified metallic Ru─Ru bond. Resultantly, the Ru/MoO2 heterostructure stably attains the Pt‐beyond HER activity with an ultralow overpotential of 9.2 mV at 10 mA cm−2 in 1 m KOH, and also achieves the competitive HER activity and stability in the acidic/neutral electrolytes. Both the experimental and computational results reveal the accelerated HER kinetics is attributable to the intensive mass transfer through the interfacial Ru→MoO2 hydrogen spillover effect. This work opens up the opportunities to rationalize the advanced metal‐support HER electrocatalysts through the interfacial hydrogen spillover effect and metallic bond engineering.

A Sustainable Route to Ruthenium Phosphide (RuP)/Ru Heterostructures with Electron-Shuttling of Interfacial Ru for Efficient Hydrogen Evolution.

Ruthenium (Ru) is a promising electrocatalyst for the hydrogen evolution reaction (HER), despite suffering from low activity in non-acidic conditions due to the high kinetic energy barrier of H2O dissociation. Herein, the synthesis of carbon nanosheet-supported RuP/Ru heterostructures (RuP/Ru@CNS) from a natural polysaccharide is reported and demonstrates its behavior as an effective HER electrocatalyst in non-acidic conditions. The RuP/Ru@CNS exhibits low overpotential (106mV at 200 mA·cm-2) in alkaline electrolyte, exceeding most reported Ru-based electrocatalysts. The electron shuttling between Ru atoms at the RuP/Ru interface results in a lowered energy barrier for H2O dissociation by electron-deficient Ru atoms in the pure Ru phase, as well as optimized H* adsorption of electron-gaining Ru atoms in the neighboring RuP. A low H* spillover energy barrier between Ru atoms at the RuP/Ru interface further boosts HER kinetics. This study demonstrates a sustainable method for the fabrication of efficient Ru-based electrocatalysts and provides a more detailed understanding of interface effects in HER catalysis.

Platinum Surface Water Orientation Dictates Hydrogen Evolution Reaction Kinetics in Alkaline Media.

The fundamental understanding of sluggish hydrogen evolution reaction (HER) kinetics on a platinum (Pt) surface in alkaline media is a topic of considerable debate. Herein, we combine cyclic voltammetry (CV) and electrical transport spectroscopy (ETS) approaches to probe the Pt surface at different pH values and develop molecular-level insights into the pH-dependent HER kinetics in alkaline media. The change in HER Tafel slope from ∼110 mV/decade in pH 7-10 to ∼53 mV/decade in pH 11-13 suggests considerably enhanced kinetics at higher pH. The ETS studies reveal a similar pH-dependent switch in the ETS conductance signal at around pH 10, suggesting a notable change of surface adsorbates. Fixed-potential calculations and chemical bonding analysis suggest that this switch is attributed to a change in interfacial water orientation, shifting from primarily an O-down configuration below pH 10 to a H-down configuration above pH 10. This reorientation weakens the O-H bond in the interfacial water molecules and modifies the reaction pathway, leading to considerably accelerated HER kinetics at higher pH. Our integrated studies provide an unprecedented molecular-level understanding of the nontrivial pH-dependent HER kinetics in alkaline media.

Well-defined ternary metal phosphide nanowires with stabilized Pt nanoclusters to boost alkaline hydrogen evolution reaction

Designing low-content and high-activity Pt-based catalysts with the high durability for the electrochemical hydrogen production remains a challenge. In this study, a ternary metal phosphide (NiCoP) with 1D nanowire (NW) and 2D nanosheet (NS) morphologies incorporating Pt clusters (denoted as Ptcluster-NiCoP@NF NWs and Ptcluster-NiCoP@NF NSs, respectively) was prepared using a hydrothermal–phosphorization–electrodeposition method. Based on the “tip effect” of NWs and a high electrochemical surface area, the as-prepared Ptcluster-NiCoP@NF NWs display better hydrogen evolution reaction (HER) performance, with a low overpotential of 65 mV at a high current density of 100 mA cm−2 and a low Tafel slope of 38.86 mV dec−1, than the Ptcluster-NiCoP@NF NSs, with an overportential of 95 mV at 42.53 mV dec−1. This indicates that the NiCoP NW-based support exhibits faster HER kinetics. The mass activity (11.47 A mgPt−1) of the Ptcluster-NiCoP@NF NWs is higher than that of commercial Pt/C catalysts. Significantly, the Ptcluster-NiCoP@NF NWs display excellent cyclic stability with negligible losses for 5000 cycles and 30-h tests at a high current of 500 mA cm−2.

Hydrogen spillover in Pt/Ni(OH)2/Mo2TiC2Tx electrocatalyst improves pH-universal hydrogen evolution reaction

Electrocatalytic hydrogen evolution reaction (HER) shows potential to transition from fossil fuels to green renewable energy. Designed for high efficiency and stability electrocatalyst in pH-universal electrolyte is of great significance but challenging. Herein, a novel electrocatalyst of two-dimensional (2D) Mo2TiC2Tx MXene supported Pt/Ni(OH)2 (denoted as Pt/Ni(OH)2/Mo2TiC2Tx) is reported by hydrogen spillover effect for efficient HER in the full-pH range. The operando electrochemical characterization reveals that the hydrogen spillover phenomenon interactions between multi-functional catalytic sites, e.g. Pt, Ni(OH)2 and Mo2TiC2Tx, are used to enhance HER performance and expedite HER kinetics. Moreover, theoretical calculation via density functional theory demonstrates the Pt/Ni(OH)2/Mo2TiC2Tx possess free energy of absorbed hydrogen close to zero (≈– 0.09 eV), which leads to optimal activity. As expected, the electrocatalyst necessitates the overpotential of 25, 33 and 36 mV at 10 mA cm−2 in acidic, alkaline, and neutral conditions, respectively, which are outperforming Pt/C. This work furtherly demonstrates a new way to design a powerful electrocatalyst for pH-universal HER based hydrogen spillover phenomenon.

Cooperative Effect of Cations and Catalyst Structure in Tuning Alkaline Hydrogen Evolution on Pt Electrodes.

The kinetics of hydrogen evolution reaction (HER) in alkaline media, a reaction central to alkaline water electrolyzers, is not accurately captured by traditional adsorption-based activity descriptors. As a result, the exact mechanism and the main driving force for the water reduction or HER rate remain hotly debated. Here, we perform extensive kinetic measurements on the pH- and cation-dependent HER rate on Pt single-crystal electrodes in alkaline conditions. We find that cations interacting with Pt step sites control the HER activity, while they interact only weakly with Pt(111) and Pt(100) terraces and, therefore, cations do not affect HER kinetics on terrace sites. This is reflected by divergent activity trends as a function of pH as well as cation concentration on stepped Pt surfaces vs Pt surfaces that do not feature steps, such as Pt(111). We show that HER activity can be optimized by rationally tuning these step-cation interactions via selective adatom deposition at the steps and by choosing an optimal electrolyte composition. Our work shows that the catalyst and the electrolyte must be tailored in conjunction to achieve the highest possible HER activity.

Constructing WS2/WO3-x heterostructured electrocatalyst enriched with oxygen vacancies for accelerated hydrogen evolution reaction

H2 produced through hydrogen evolution reaction (HER) is a shining star in the field of clean energy. Significant efforts have been dedicated to develop efficient and stable electrocatalysts to reduce the energy barrier and accelerate the kinetics of Hydrogen evolution reaction (HER) under various environments. Herein, we propose a strategy to accelerate the kinetics of HER under acid and alkaline environments by combining heterostructure engineering with defect engineering. We have successfully synthesized a series of WS2/WO3-x heterostructured catalysts, accompanied with substantial oxygen vacancies using a two-step synthesis method. With the partially sulfurization of WO3-x, the heterojunction interface of WS2 and WO3-x was formed along with the appearance of oxygen vacancies, which can facilitate the migration of electrons. The heterostructured catalyst enriched with oxygen vacancies (defined as WS2/WO3-x-2) demonstrates superior HER performance in acidic and alkaline electrolytes. At a current density of 10 mA cm−2, the WS2/WO3-x-2 heterostructured catalyst manifests an overpotential of 120 mV in the acidic electrolytes and a slightly higher overpotential of 150 mV in an alkaline environment. The overpotentials offer an improvement compared to reported W-based catalysts in terms of HER performance. This work provides guiding significance on the design of heterostructured catalysts with promising performance for HER in acidic and alkaline environments.

Modulate the surface charge toward efficient hydrogen evolution reaction: Electronic structure engineering of MoB-Ni3B interface

Rationally regulated the surface electronic structure of catalysts hold the key to enhance the kinetics of hydrogen evolution reaction (HER). Herein, we propose an electronic structure engineering strategy to modulate the surface charge of Ni3B by introducing MoB for high-efficient HER. The MoB-Ni3B interface exhibits characteristic lattice expansion and results in electron modulation between the Ni3B and MoB. Density functional theory calculations further indicate that the introduction of MoB leads to electron enrichment around Ni sites, which further activate Ni sites, weaken the adsorption of hydrogen intermediates and thus facilitate the unfavorable hydrogen desorption, resulting in the Gibbs free adsorption energy closer to zero. As expected, the hierarchical MoB-Ni3B displays an ultra-low overpotential (η10 = 35 and 57 mV for reaching a current density of −10 mA cm−2) in 1.0 M KOH and 0.5 M H2SO4, which is comparable to the commercial Pt catalyst and confirms the positive effect of the modulation of electronic structure on the kinetics and catalytic activity. The effectiveness of the electronic structure engineering strategy is expected to shed light on the construction of more advanced electrocatalysts.

Laser-Synthesized Ru-Anchored Few-Layer Black Phosphorus for Superior Hydrogen Evolution: Role of Acoustic Levitation.

Electrochemical water splitting, driven by processed catalysts, is the most reasonable method for hydrogen production. This study demonstrates an activation phenomenon with ruthenium (Ru) nanoclusters on few-layered black phosphorus (BP), greatly enhancing the electrocatalytic hydrogen evolution reaction (HER). Efficient BP exfoliation was achieved using acoustic levitators and pulsed laser irradiation in liquids (PLIL), yielding charge-transfer Ru-nanoclusters on modulated surfaces. Various PLIL parameters were examined for the optimal BP sheet size. After ruthenization, Ru's d-band center facilitated hydrogen adsorption via Ru-H bonding. Synergy between BP's charge-carrier properties and Ru's active sites boosted HER kinetics with an ultralow overpotential of 84 mV at 10 mA/cm2 in KOH. Additionally, the RuO2 || RuBP-2 electrolyzer demonstrated remarkable overall water splitting performance at ∼1.60 V at 10 mA/cm2. These results highlight the pivotal role of metal nanoclusters on exfoliated BP surfaces and offer a refined strategy for high-density electrocatalysts in energy conversion.

New Mechanistic Insights into Electrokinetic Competition Between Nitrogen Reduction and Hydrogen Evolution Reactions

AbstractAchieving both high activity and selectivity presents a significant challenge for electrochemical N2 reduction (eNRR) due to the competing hydrogen evolution reaction (HER). Although density functional theory‐based computations can identify eNRR‐favored electrocatalysts, there is a significant gap between theoretical predictions and experimental observations. In this work, a comprehensive analysis of the kinetic competition between eNRR and HER at the electrode‐electrolyte interface (EEI) from three perspectives: kinetic N2 adsorption, *N2 hydrogenation, and corresponding potential‐dependent kinetics is presented. This data reveals that N2 adsorption at EEI is kinetically facile. Upon *N2 adsorption, the subsequent hydrogenation is influenced by electrode potentials. At lower overpotentials, *N2 hydrogenation is more facile than HER. However, at higher overpotentials, eNRR becomes kinetically disadvantaged due to limited N2 availability at the EEI, while HER kinetics accelerate and eventually dominate. Therefore, the electrochemical eNRR potential window for different catalysts is identified. A compelling evidence is presented that enhancing N2 concentration near the EEI is the key to improving eNRR activity. These findings offer critical fundamental insights for future strategies aimed at making green ammonia synthesis more efficient.

Phase-Transition of Mo2 C Induced by Tungsten Doping as Heterointerface-Rich Electrocatalyst for Optimizing Hydrogen Evolution Activity.

Electrochemical hydrogen evolution reaction (HER) from water splitting driven by renewable energy is considered a promising method for large-scale hydrogen production, and as an alternative to noble-metal electrocatalysts, molybdenum carbide (Mo2 C) has exhibited effective HER performance. However, the strong bonding strength of intermediate adsorbed H (Hads ) with Mo active site slows down the HER kinetics of Mo2 C. Herein, using phase-transition strategy, hexagonal β-Mo2 C could be easily transferred to cubic δ-Mo2 C through electron injection triggered by tungsten (W) doping, and heterointerface-rich Mo2 C-based composites, including β-Mo2 C, δ-Mo2 C, and MoO2 , are presented. Experimental results and density functional theory calculations reveal that W doping mainly contributes to the phase-transition process, and the generated heterointerfaces are the dominant factor in inducing remarkable electron accumulation around Mo active sites, thus weakening the Mo─H coupling. Wherein, the β-Mo2 C/MoO2 interface plays an important role in optimizing the electronic structure of Mo 3d orbital and hydrogen adsorption Gibbs free energy (ΔGH* ), enabling these Mo2 C-based composites to have excellent intrinsic catalytic activity like low overpotential (η10 = 99.8mV), small Tafel slope (60.16 dec-1 ), and good stability in 1m KOH. This work sheds light on phase-transition engineering and offers a convenient route to construct heterointerfaces for large-scale HER production.

Double‐Walled Tubular Heusler‐Type Platinum–Ruthenium Phosphide as All‐pH Hydrogen Evolution Reaction Catalyst Outperforming Platinum and Ruthenium

AbstractNanostructured ionic compounds have driven major technological advancements in displays, photovoltaics, and catalysis. Current research focuses on refining the chemical composition of such compounds. In this study, a strategy for creating stoichiometrically well‐defined nanoscale multiple‐cation systems, where the atomically precise structure maximizes the synergistic cooperation between cations at the atomic scale is reported. The unprecedented construction of Heusler‐type PtRuP2 double‐walled nanotubes through sequential anion/cation exchange reactions is demonstrated. The PtRuP2 catalyst exhibits record‐high catalytic performance and durability for the hydrogen evolution reaction (HER) in alkaline electrolytes and anion‐exchange membrane water electrolyzers. The investigations highlight the crucial role of Pt/Ru dual centers, providing multiple active sites that accelerate the HER kinetics within a single phosphide material, in the sequential operation of H2O activation/dissociation at Ru and H2 production at adjacent Pt sites. These findings open new avenues for optimizing ionic compound‐based HER electrocatalysts, offering platinum‐metal alternatives in acidic and alkaline media.