Hydrogen Evolution Reaction Activity Research Articles

Evaluation of anion exchange membrane water electrolysis performance using synthesised NiMoO4/Ni cathode via solution combustion synthesis in applied thermal reduction approach

The development of sustainable electrocatalysts is essential for the advancement of anion exchange membrane water electrolysis (AEMWE) technologies. Nickel molybdate-based catalysts may improve the efficiency of hydrogen evolution reaction (HER) during alkaline water electrolysis. This study investigated the influence of thermal reduction temperature on the synthesised NiMoO4-based catalyst via solution combustion synthesis (SCS) and its performance in HER and single-cell AEMWE. The optimal conditions for stable and active HER electrocatalysts were determined by investigating synthesised NiMoO4 catalysts at 450 °C, 550 °C and 750 °C. A NiMoO4 catalyst was characterised at different reduction temperatures through X-ray diffractometer (XRD), field emission scanning electron microscopy (FESEM), energy-dispersive spectroscopy (EDS) and Brunauer–Emmett–Teller (BET) analysis. Results revealed that the NiMoO4-450/Ni cathode became the highest performance 1 A/cm2 current density at 2.2 V and the NiMoO4-550/Ni cathode became the most stable performance among the catalysts, attaining. The average current density of NiMoO4-550/Ni fluctuated by only 22% from 24 h to 100 h.

Dual-doped medium-entropy phosphides for complete urea electrolysis

Developing dual-functional electrocatalysts for urea-water decomposition still faces significant challenges. In this study, the vanadium (V) and cerium (Ce) co-doped FeCoNi medium-entropy phosphide (VCe-FeCoNiP/NF) were effectively fabricated on nickel foam (NF) via “two-step method,” which involved hydrothermal treatment followed by phosphorization. Experimental results indicate that, benefiting from dual-ion doping and medium-entropy configuration, VCe-FeCoNiP/NF demonstrates unique electronic effects among the multimetallic elements, thereby exhibited remarkable catalytic activity for both urea oxidation reaction (UOR) and hydrogen evolution reaction (HER). Under urea-water conditions (1 M KOH with 0.33 M urea), the VCe-FeCoNi/NF catalyst merely required 1.338 V (vs RHE) and an overpotential of 173 mV to attain a current density of 100 mA·cm−2 for UOR and HER, respectively. Moreover, it could stably operate at a current density of 20 mA·cm−2 for 225 h in overall urea-water decomposition. This work provides new insights for designing high-performance urea-water electrolysis catalysts.

Evaluating the effect of different ligands on the supercapacitance and hydrogen evolution reaction studies of Zn-Co MOF

Metal-Organic Frameworks (MOFs) have recently attracted a lot of interest because of their potential uses in energy storage and catalysis. In this study, we investigate the impact of various ligands on the electrochemical performance of Zn-Co MOFs for both energy storage and hydrogen evolution reaction (HER) studies. Specifically, Zn-Co MOFs are synthesized using different ligands, and their structural and electrochemical properties are characterized by a range of analytical techniques. 2,5-dihydroxybenzoic acid (DBA) and benzene-1,2,4,5-tetracarboxylic acid (BTC) are employed due to their distinct structural features and potential effects on MOF performance. Subsequently, electrochemical studies are conducted to assess the supercapattery performance and HER activity of these MOFs. The specific capacitance and overpotential value at 10 mA/cm2 of Zn-Co/DBA MOF is observed to be 1775.3 F/g and 186 mV, whereas that of Zn-Co/BTC MOF is found to be 136.6 F/g and 279 mV. The MOF synthesis using DBA as a ligand is more effective for energy-related applications. This study aims to report a multifunctional MOF composite for energy and environmental applications with better efficiency than other reported systems. Our findings provide insights into how the choice of ligand influences the structural properties and electrochemical behavior of Zn-Co MOFs, shedding light on the potential of these MOFs as versatile materials for energy storage and HER applications.

Harnessing the clean energy: Phosphorus-alkynyl covalent organic frameworks for photocatalytic hydrogen production

Given the diminishing reserves of fossil fuels, the development of renewable alternative energy sources is of global importance. Photocatalytic hydrogen (H2) evolution stands out as a promising and cost-effective method to harness sunlight for producing carbon-free H2 fuel. Recently, two-dimensional (2D) covalent organic frameworks (COFs) have garnered considerable research interest in photocatalysis on account of their exceptional surface area and predictable assembly of diverse molecules with adjustable electronic properties. Herein, six 2D COFs are constructed by topologically assembling phosphorus-alkynyl functional moieties and benzene-based building units, including benzene (COF-1), triazine (COF-2), heptazine (COF-3), triphenyl-benzene (COF-4), triphenyl-triazine (COF-5), and triphenyl-heptazine (COF-6), employing first-principles calculations. Our computational results illustrate that the variation of benzene-based building units significantly regulates the electronic structures of COFs, all of which possess semiconductor properties with tunable bandgaps spanning from 1.56 to 2.56 eV. Of particular importance, COF-1, COF-2, COF-4, COF-5, and COF-6 can spontaneously stimulate the hydrogen evolution reaction (HER) under their own light-induced bias without the need for sacrificial agents and co-catalysts. Among them, COF-4 and COF-5 show the best HER activity without light-induced bias, with ΔG values of 0.02 and −0.01 eV, respectively, whose excellent photocatalytic performance can be ascribed to their appropriate electronic band structures, pronounced optical absorption, and low work functions. This finding offers profound insights for exploring other highly efficient HER photocatalysts.

Surface active sites and interphase engineering into metal oxide hydrates enabled by ions substitution for efficient water splitting

The expanding requirement of energy-effective and cost-efficient water electrolysis has prompted studies of earth-abundant metal-based electrocatalysts. In this study, we study the typical substitution strategies of cation (Pt) or anion (Se) for modifying surface active sites or interphase engineering to tune electronic structure of bimetallic nickel molybdenum oxide hydrates (NiMoO4·xH2O), thus effectively improving catalytic properties toward hydrogen evolution reaction (HER) or oxygen evolution reaction (OER). Result of the cation substitution achieves PtSA–NiMoO4·xH2O catalyst with abundant doped Pt single atoms on surface, which promotes high HER activity with a small overpotential of 73 mV at a current yield of 10 mA cm−2 in alkaline medium. Meanwhile, Se–NiMoO4·xH2O catalyst, an outcome of the anion substitution approach, has unique interfaces of NiSe-NiMoO4 heterostructure and thus exhibits a desired overpotential of only 297 mV for OER. The combination of PtSA–NiMoO4·xH2O(–)//Se–NiMoO4·xH2O(+) couple results in a two-electrode electrolyzer cell, which requires a small cell voltage of 1.48, 1.54 and 1.59 V to deliver a response of 10 mA·cm−2 at 75, 50 and 25 °C, respectively, along with negligible performance decay during 50 h operation. These results highlight the potential of our catalyst engineering strategies to achieve high-performance green hydrogen production.

Magnetic Activation: A Novel Approach to Enhance Hydrogen Evolution Activity of Co0.85Se@CNTs Heterostructured Catalyst.

The heterostructure strategy is currently an effective method for enhancing the catalytic activity of materials. However, the challenge that is how to further improve their catalytic performance, based on the principles of material modification is must addressed. Herein, a strategy is introduced for magnetically regulating the catalytic activity to further enhance the hydrogen evolution reaction (HER) activity for Co0.85Se@CNTs heterostructured catalyst. Building on heterostructure modulation, an external alternating magnetic field (AMF) is introduced to enhance the electronic localization at the active sites, which significantly boosts catalytic performance (71 to 43mV at 10mA cm-2). To elucidate the catalytic mechanism, especially under the influence of the AMF, in situ Raman spectroscopy is innovatively applied to monitor the HER process of Co0.85Se@CNTs, comparing conditions with and without the AMF. This study demonstrates that introducing the AMF does not induce a change in the true active site. Importantly, it shows that the Lorentz force generated by the AMF enhances HER activity by promoting water molecule adsorption and O─H bond cleavage, with the Stark tuning rate indicating increased water interaction and bond cleavage efficiency. Theoretical calculations further support that the AMF optimizes energy barriers for key reaction intermediates (steps of *H2O-TS and *H+*1/2H2).

Performance of cobalt doped two dimensional black phosphorus (Co-2D BP) for bifunctional hydrolysis in alkaline solution

The present study contributes to the exploration of transition metal phosphides with specific composition and structure to enhance electrocatalytic ability. Cobalt doped two dimensional black phosphorus (Co-2D BP) with layered structure exhibits excellent electrocatalytic activity for hydrogen evolution reaction (HER) in alkaline solutions, and demonstrates an overpotential of 86.42 mv at a current density of 10 mA cm−2, requiring only 140.29 mv, 198 mv, and 238.89 mv to reach 20, 50, and 100 mA cm−2 respectively. The catalytic performance was stable even after 10 h using in alkaline electrolytes, demonstrating good chemical stability. Co-2D BP can also improve the catalytic performance for oxygen evolution reaction (OER). This study provides a novel strategy for the design of multifunctional 2D BP-based catalytic materials for hydrolysis.

Electrocatalysis of hydrogen and oxygen electrode reactions in alkaline media by Rh-modified polycrystalline Ni electrode

Developing novel electrocatalysts for energy conversion applications is of utmost importance for reaching the energy security of modern society. Here we present a comprehensive investigation of rhodium-modified polycrystalline nickel as an electrocatalyst for hydrogen and oxygen electrode reactions in alkaline media. The surface modification of nickel electrodes was achieved by facile galvanic displacement (up to 30 s) from a highly concentrated acidic Rh3+ solution. The results demonstrate a significant enhancement in the electrocatalytic activity for both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) on the Rh-modified Ni electrodes, positioning galvanic displacement as a viable approach to engineering advanced electrocatalysts for clean energy applications. On the other hand, the hydrogen oxidation (HOR) and oxygen reduction reaction (ORR) activities of the Rh-modified electrodes are lower compared to polycrystalline platinum. It is suggested that semiconducting Rh2O3 has a detrimental role on the HOR and ORR performance, while the activities of HER and OER, dominantly taking place on metallic Rh and conductive RhO2, are very high. This research sheds light on the mechanisms underlying the enhanced electrode kinetics on Rh-modified Ni electrodes and provides insights into the development of efficient and cost-effective electrocatalysts for renewable energy technologies.

Sulfur vacancy riched pure 2H phase VS2 for efficient electrocatalytic hydrogen evolution

Vanadium disulfide (VS2), a typical metallic layered transition metal chalcogenide (TMC), has been widely concerned for its high electrical conductivity and reactivity in electrochemical energy storage and conversion applications. The 2H phase VS2 is expected to exhibit high electrocatalytic activity and be more stable for hydrogen evolution reaction (HER) than the 1T phase structure. But at present, there still lacks a facile method to prepare pure 2H phase VS2. Herein, we successfully prepared pure 2H–VS2 through a simple one-step low-temperature hydrothermal method. We have investigated the effect of the hydrothermal reaction conditions (including the proportion of raw materials and hydrothermal reaction temperatures) on the phase composition and microstructure. Under the optimal condition of 140°C-24 h with a vanadium sulfur ratio of 1:5, a nano-flower-like 2H–VS2 material with high crystallinity and rich sulfur vacancy defects was obtained. Leveraging these structural advantages, as a demonstration, the product exhibits excellent electrocatalytic HER activity (with η10 of 181 mV, Tafel slope of 52 mV dec−1, and J0 of 67.9 × 10−3 mA cm−2) and stability (it can continuously produce hydrogen for 20 h at a current density of 50 mA cm−2 with ultra-small increased potential of less than 5 mV). This work provides a new way for constructing atomic vacancy defects in layered TMCs for efficient electrocatalysis and is also expected to promote the research of the basic properties of high phase purity TMCs.

Sn doped cobalt-based phosphide as bifunctional catalyst for ethanol oxidation reaction and hydrogen evolution reaction

The development of non-precious metal bifunctional electrocatalysts is of practical significance to solve resource shortage and energy crisis. In this study, to accelerate mass/electron transfer and maximize the area of exposed active sites, a coral-like Sn–Co–P/NF bi-functional electrocatalyst was synthesized by electrodeposition for total hydrolysis. Ethanol oxidation reaction (EOR) was used to replace oxygen evolution reaction (OER) with hydrogen evolution reaction (HER) to further improve the water electrolysis rate. The catalyst showed great electrochemical activity and stability in both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) under alkaline conditions. At a current density of 10 mA cm−2, the required overpotential for HER is only 59 mV (vs. RHE) and 304 mV (vs. RHE) for OER, and the corresponding Tafel slopes are 42 mV·dec−1 and 67 mV·dec−1, respectively. When EOR was substituted for anodic oxygen evolution, the overpotential could be reduced by 240 mV. In addition, when Sn–Co–P/NF is used as a water-ethanol electrolytic cell assembled with anode and cathode, the current density of 10 mA cm−2 can be reached with only 1.49 V operating voltage, which is 130 mV lower than that of hydrolysis alone, and it also shows good durability in the test of 28 h. Therefore, the experimental results show that it is feasible to use EOR instead of OER to coupling with HER, the catalyst has broad application prospects in industrial electrolysis.

Engineering a Ce Promoter into a Three-Dimensional Porous Mo2C@NC Heterostructure for Hydrogen Evolution Electrocatalysis via Weakening the Mo-H Bond Strength.

The pursuit of highly efficient electrocatalysts for the alkaline hydrogen evolution reaction (HER) is of paramount importance for water splitting. However, it is still a formidable task in Mo2C-based materials because of the agglomeration and strong Mo-H binding of Mo2C units. Herein, a novel CeOCl-CeO2/Mo2C heterostructure nesting within a three-dimensional porous nitrogen-doped carbon matrix has been designed and used for catalyzing HER via simultaneous morphology and heterointerface engineering. As expected, the optimal CeOCl-CeO2(0.2)/Mo2C@3DNC exhibits impressive HER activity, with a low overpotential of 156 mV at a current density of 10 mA cm-2 coupled with a slight Tafel slope of 62.20 mV dec-1. Introducing a Ce promoter, that is CeOCl and CeO2, would endow the interface with an internal electric field and electron redistribution between CeOCl-CeO2 and Mo2C induced by the heterogeneous work function difference. Moreover, experimental investigation and density functional calculations confirm that the CeOCl-CeO2/Mo2C heterointerface can downshift the d-band center of the active Mo center, weakening the strength of the Mo-H coupling. This proposed concept, engineering Ce-based promoters into active entities involved in the heterostructure to modulate intermediate adsorption, offers a great opportunity for the design of superior electrocatalysts for energy conversion.

Beyond S and Se: Electrocatalytic Hydrogen Production by Tellurolate-Bridged Co(III)-Mn(I) Heterodinuclear Complexes.

In the pursuit of efficient electrocatalysts for the hydrogen evolution reaction (HER), a series of manganese and cobalt heterodinuclear complexes have been synthesized and characterized that have a stark resemblance with the [NiFe]-hydrogenase active site structure. Irradiation of [Mn2(CO)10] in the presence of 1.5 eq of [NaEPh] [E = S, Se, Te] followed by reaction with [Cp*CoCl]2 led to the formation of half-sandwiched trichalcogenate-bridged heterodinuclear complexes [{Mn(CO)3}(μ-EPh)3(CoCp*)] [E = S (C1); Se (C2) and Te (C3)]. The reaction of these heterodinuclear trichalcogenate-bridged complexes with [LiBH4·THF] yielded the corresponding dichalcogenate hydride-bridged heterobimetallic complexes [(CO)3Mn(μ-EPh)2(μ-H)(CoCp*)] [E = S (C5); Se (C6) and Te (C7)], which closely imitate the Ni-R intermediate of [NiFe]-hydrogenase. The resultant complexes (C5-C7) displayed impressive H2 production in DMF in the presence of HBF4, whereas the Te-based complex (C7) showcased the highest TON (184 h-1) with an impressive Faradaic efficiency of >98%. The DFT investigations revealed a unique role of bridging chalcogens in catalysis, wherein, depending on the identity of the chalcogen (S, Se, or Te), protonation could occur via two distinct routes. This study represents a rare example of the full trio of S/Se/Te-based heterodinuclear complexes whose electrocatalytic HER activity has been probed under analogous conditions.

Universal and large-scale transform engineering from commercial metals to micron/nanoporous metals via an induced oxidation-reduction reaction

Three-dimensional (3D) nanoporous metals are being increasingly utilized in various fields such as catalysis, energy storage, and sensing. However, the conventional fabrication approaches for 3D nanoporous metals, such as dealloying and template methods, require additional sacrificial materials and multiple fabrication steps and generate chemical waste. Herein, we propose a novel gaseous (O2 and H2) oxidation-reduction (GOR) method to directly transform various transition metals/alloys into 3D micron/nanoporous materials by utilizing the spontaneous reconstruction of metallic atoms. This method eliminates the need for sacrificial materials and acidic/alkaline solutions, making it facile, cost-effective, and environmentally friendly. The resulting micron/nanoporous Ni/Ni alloy exhibits excellent mechanical properties, atomic hydrogen adsorption capability, and hydrophilicity, leading to outstanding electrocatalytic activity and durability for hydrogen evolution reaction.

Operando Insights on the Degradation Mechanisms of Rhenium‐Doped and Undoped Molybdenum Disulfide Nanocatalysts During Hydrogen Evolution Reaction and Open‐Circuit Conditions

AbstractMolybdenum disulfide (MoS2) nanostructures are promising catalysts for proton‐exchange‐membrane (PEM) electrolyzers to replace expensive noble metals. Their large‐scale application demands high activity for the hydrogen evolution reaction (HER) as well as robust durability. Doping is commonly applied to enhance the HER activity of MoS2‐based nanocatalysts, but the effect of dopants on the electrochemical and structural stability is yet to be discussed. Herein, operando electrochemical measurements to the structural evolution of the materials down to the nanometric scale are correlated by identical location electron microscopy and spectroscopy. The range of stable operation for MoS2 nanocatalysts with and without rhenium doping is experimentally defined. The responsible degradation mechanisms at first electrolyte contact, open circuit stabilization, and HER conditions are experimentally identified and confirmed with the calculated Pourbaix diagram of Re‐doped MoS2. Doping MoS2‐based nanocatalysts is validated as a promising strategy for continuing the improvement of high‐performance and durable PEM electrolyzers.

Symbolic transform optimized convolutional neural network model for high-performance prediction and analysis of MXenes hydrogen evolution reaction catalysts

Two-dimensional MXenes materials are expected to be cost-effective and efficient catalysts for hydrogen evolution reaction (HER) due to their tunable surface electronic structure. To optimize its catalytic activity, this study proposes a data-driven framework (CROSST) to generate descriptors through feature engineering and integrate them into a convolutional neural network to predict the HER performance of transition-metal (TM) anchored bis-transition-metal carbon-nitride (TM-M′2M′′CNO2) catalysts. The STCNN model achieves a coefficient of determination of more than 0.93, showing the ability to predict the Gibbs free energy of hydrogen adsorption (ΔGH) with high accuracy. We explored the microscopic mechanisms of HER activity through density functional theory and machine learning analysis. It was found that TM anchoring altered the charge distribution of the MXenes material, elevated the atomic orbital occupancy of neighboring O sites, and weakened the O adsorption of H, thus affecting the HER activity. These results provide a theoretical basis for the design of high-performance MXenes HER catalysts and contribute new research perspectives.

Co-Co6Mo6C2 heterostructure grown on carbon nanofibers as tri-functional electrocatalyst for overall water splitting and rechargeable Zn-air batteries

The advancement of cost-effective and efficient electrocatalysts for the hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and oxygen reduction reaction (ORR) is crucial for the progress of clean energy conversion and storage technologies. In this work, cobalt (Co) and cobalt-molybdenum (Mo) bimetallic carbide (Co6Mo6C2) heterostructure grown on carbon nanofibers (denoted as Co-Co6Mo6C2/CNFs) as tri-functional electrocatalyst were prepared by a four-step method. Benefiting from the electronic structure modulation between the heterostructure to improve the catalytic activity, Co-Co6Mo6C2/CNFs exhibits high catalytic activity for HER (91 mV @ 10 mA cm−2), OER (293 mV @ 10 mA cm−2) and ORR (E1/2=0.80 V). Moreover, Co-Co6Mo6C2/CNFs assembled overall water splitting electrolyzer achieves a current density of 10 mA cm−2 with a battery voltage of only 1.70 V and has long-term durability. Zn-air batteries (ZABs) based on Co-Co6Mo6C2/CNFs has a power density of 156.6 mW cm−2 with good stability. This study contributes to the development of inexpensive and efficient transition metal-based multifunctional electrocatalysts.

Platinum-dependent 2H-to-1T phases conversion of MoS2 nanosheets growing on cross-interlocking porous carbon for boosting hydrogen evolution reaction

Proton exchange membrane water electrolysis (PEMWE) coupled with renewable energy is regarded as a sustainable approach for green hydrogen production. However, the low reserve and high cost of platinum cathode electrocatalysts greatly limit its widespread deployment. Herein, we report a phase conversion strategy to obtain an efficient low-Pt loading electrocatalyst composed of multi-atomic Pt substituted 1T-MoS2 nanosheet grown on a cross-interlocking porous carbon matrix (Pt@1T-MoS2/C). In combination with experimental and theoretical results, the 2H-to-1T phase conversion of MoS2 induced by the Pt substitution is investigated, and the as-formed Pt-S-Mo active site accounts for the excellent hydrogen evolution reaction (HER) performance. Benefiting from the improved electron transfer efficiency and Pt-S-Mo active sites, the Pt@1T-MoS2/C delivers a high mass HER activity of ∼58.9 A·mgPt−1, and an excellent stability of 200 h at 1000 mA∙cm−2 in a practical PEMWE device.

Coupling High-Entropy Core with Rh Shell for Efficient pH-Universal Hydrogen Evolution.

Constructing high-entropy alloys (HEAs) with core-shell (CS) nanostructure is efficient for enhancing catalytic activity. However, it is extremely challenging to incorporate the CS structure with HEAs. Herein, PtCoNiMoRh@Rh CS nanoparticles (PtCoNiMoRh@Rh) with ∼5.7nm for pH-universal hydrogen evolution reaction (HER) are reported for the first time. The PtCoNiMoRh@Rh just require 9.1, 24.9, and 17.1mV to achieve -10mA cm-2 in acid, neutral, and alkaline electrolyte, and the corresponding mass activity are 5.8, 2.79, and 91.8 times higher than that of Rh/C. Comparing to PtCoNiMoRh nanoparticles, the PtCoNiMoRh@Rh exhibit excellent HER activity attributed to the decrease of Rh 4d especially 4d5/2 unoccupied state induced by the multi-active sites in HEA, as well as the synergistic effect in Rh shell and HEA core. Theorical calculation exhibits that Rh-dyz, dx2, and dxz orbitals experience a negative shift with shell thickness increasing. The HEAs with CS structure would facilitate the rational design of high-performance HEAs catalysts.

Exploring the role of redox-active species on NiS-NiS2 incorporated sulfur-doped graphitic carbon nitride nanohybrid as a bifunctional electrocatalyst for overall water splitting

The advancement of effective and robust catalysts that can replace the precious-metal-based benchmarks for electrocatalytic overall water splitting is a highly fashionable approach to exploring sustainable energy utilization and addressing environmental issues. Herein, we demonstrate a facile single-step fabrication of NiS-NiS2 nanoparticles in situ grown on the layered porous sulfur-doped graphitic carbon nitride nanosheets (NiS-NiS2/SGCN) act as bifunctional electrocatalysts for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in an alkaline medium.Further, an increasing the Ni precursor (fixed sulfur source) increases the formation of NiS-NiS2 on the surface of SGCN (labeled as NS-1.0, NS-2.0, and NS-3.0). Structural and morphological studies such as PXRD, XPS, FTIR, HR-TEM, etc., revealed a uniform distribution of NiS/NiS2 on the surface of S-g-C3N4 nanosheets. The OER and HER activity of NiS-NiS2/SGCN nanohybrid were significantly enhanced by increasing the affinity of accessible surface-active edge sites, interfacial contact allows effective modification of electronic structure, high structural porosity, redox-active centers of Ni2+/Ni3+, and rich in sulfur vacancy. In addition, the enhancement of the exposure of the edge sites is improved by their attachment to a sulfur-doped g-C3N4 framework. As a result, in the half-cell experiments, the NiS-NiS2/SGCN (NS-3.0) catalyst exhibited enhanced performance in both OER and HER, requiring an overpotential of 298 mV to reach 50 mA/cm2 for OER and −144 mV to reach 10 mA/cm2 for HER. Furthermore, the constructed electrolyzer using Ni-S 3.0 as the cathode and anode required a cell voltage of 1.66 V to yield 50 mA/cm2 in overall water splitting. This study may inspire the in-situ synthesis of different metal sulfides on SGCN to provide a unique interfacial approach for improving the performance of bifunctional non-precious electrocatalysts.

Deep Reconstruction of Ruthenate Perovskite Oxide Enables Efficient pH-Universal Hydrogen Evolution Reaction.

Designing highly efficient, stable, and pH-universal perovskites for hydrogen evolution reaction (HER) is urgently needed yet remains a grand challenge. Herein, a titanium-containing strontium ruthenate (SrTi0.5Ru0.5O3, STRO) is developed as an excellent HER electrocatalyst in a wide pH range. The introduction of Ti into SrRuO3 significantly reduces the size of STRO, endowing with a high reactivity that facilitates a deep surface-reconstruction during HER. Furthermore, Sr2+ leaching triggered reconstruction leads to STRO breaking into tiny nanoparticles accompanied by high-valence ruthenium (Ru) species reducing to metallic Ru. The generated active species, increased accessible sites, and improved electrical conductivity greatly boost HER. The reconstructed STRO displays remarkable HER activities with exceptional low overpotentials of 18, 24, and 55mV at 10mA cm-2 in 1m KOH, 0.5m H2SO4, and 1m PBS, respectively, surpassing most perovskites reported previously and comparable to or even outperforming that of commercial Pt/C. Moreover, the STRO exhibits excellent stabilities over 200h in alkaline and acidic media, superior to that of Pt/C. This work not only provides insights into structure reconstruction of perovskites during HER, but also opens new perspectives for developing high-efficiency and pH-universal electrocatalysts for future energy applications.