pH-universal Hydrogen Evolution Reaction Research Articles

Semi-Ionic F Modified N-Doped Porous Carbon Implanted with Ruthenium Nanoclusters towardHighlyEfficient pH-Universal Hydrogen Generation.

Developing high electroactivity ruthenium (Ru)-based electrocatalysts for pH-universal hydrogen evolution reaction (HER) is challenging due to the strong bonding strengths of key Ru─H/Ru─OH intermediates and sluggish water dissociation rates on active Ru sites. Herein, a semi-ionic F-modified N-doped porous carbon implanted with ruthenium nanoclusters (Ru/FNPC) is introduced by a hydrogel sealing-pyrolying-etching strategy toward highly efficient pH-universal hydrogen generation. Benefiting from the synergistic effects between Ru nanoclusters (Ru NCs) and hierarchically F, N-codoped porous carbon support, such synthesized catalyst displays exceptional HER reactivity and durability at all pH levels. The optimal 8Ru/FNPC affords ultralow overpotentials of 17.8, 71.2, and 53.8mV at the current density of 10mA cm-2 in alkaline, neutral, and acidic media, respectively. Density functional theory (DFT) calculations elucidate that the F-doped substrate to support Ru NCs weakens the adsorption energies of H and OH on Ru sites and reduces the energy barriers of elementary steps for HER, thus enhancing the intrinsic activity of Ru sites and accelerating the HER kinetics. This work provides new perspectives for the design of advanced electrocatalysts by porous carbon substrate implanted with ultrafine metal NCs for energy conversion applications.

Metal hydroxide hybridized Pd catalysts via in-situ etching for high current density and pH-universal hydrogen evolution reaction

The development of highly efficient and innovative electrocatalysts is crucial for the commercialization of the hydrogen evolution reaction (HER) at high current densities. An electrocatalyst consisting of Pd nanoparticles electrodeposited on nickel foam (NF) treated with ferric chloride etching, yielding a Pd content of 0.53 wt%, was synthesized. This PdFe/NF-24 h catalyst demonstrated outstanding HER performance across a wide pH range, requiring overpotentials of only 302 mV, 96.4 mV and 637.9 mV to achieve a current density of 1000 mA/cm2 in 1 M KOH, 0.5 M H2SO4 and 1 M Phosphate Buffer Saline (PBS) electrolytes, respectively. The ferric chloride etching increased the active surface area, while iron doping optimized the hydrogen adsorption free energy on Pd. Furthermore, the presence of metal hydroxides facilitated the dissociation of water into adsorbed hydrogen, which then bound to active sites on the Pd surface to produce hydrogen, thereby enhancing the efficiency of hydrogen production. The catalyst operated at 1000 mA/cm2 in 1 M KOH solution for 222 h without degradation; it maintained stability for 124 h in 30 % KOH solution; in 0.5 M H2SO4 solution, it retained 99.6 % performance for 77 h and it remained stable for 230 h in 1 M PBS solution.

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

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

Self-assembled PtNi layered metallene nanobowls for pH-universal electrocatalytic hydrogen evolution

Compared with layered materials such as graphite and transition metal disulfide compounds with highly anisotropic in-plane covalent bonds, it is inherently more challenging to obtain independent metallic two-dimensional films with atomic thickness. In this study, PtNi layered metallene nanobowls (LMBs) with multilayer atomic-scale nanosheets and bowl-like structures have been synthesized in one step using structural and electronic effects. The material has the advantage of catalyzing pH-universal hydrogen evolution reaction (HER). Compared with Pt/C, PtNi LMBs exhibited excellent HER activity and stability under all pH conditions. The overpotentials of 10 mA cm−2 at 0.5 M H2SO4, 1.0 M phosphate buffer and 1.0 M KOH were 14.8, 20.3, and 34.0 mV, respectively. Under acidic, neutral and alkaline conditions, the HER Faraday efficiencies reach 98.97%, 98.85%, and 99.04%, respectively. This study provides an example for the preparation of unique multilayer nanobowls, and also provides a basic research platform for the development of special HER materials.

In Situ Engineering Multifunctional Active Sites of Ruthenium-Nickel Alloys for pH-Universal Ampere-Level Current-Density Hydrogen Evolution.

Developing robust non-platinum electrocatalysts with multifunctional active sites for pH-universal hydrogen evolution reaction (HER) is crucial for scalable hydrogen production through electrochemical water splitting. Here ultra-small ruthenium-nickel alloy nanoparticles steadily anchored on reduced graphene oxide papers (Ru-Ni/rGOPs) as versatile electrocatalytic materials for acidic and alkaline HER are reported. These Ru-Ni alloy nanoparticles serve as pH self-adaptive electroactive species by making use of in situ surface reconstruction, where surface Ni atoms are hydroxylated to produce bifunctional active sites of Ru-Ni(OH)2 for alkaline HER, and selectively etched to form monometallic Ru active sites for acidic HER, respectively. Owing to the presence of Ru-Ni(OH)2 multi-site surface, which not only accelerates water dissociation to generate reactive hydrogen intermediates but also facilitates their recombination into hydrogen molecules, the self-supported Ru90Ni10/rGOP hybrid electrode only takes overpotential of as low as ≈106mV to deliver current density of 1000mAcm-2, and maintains exceptional stability for over 1000h in 1 m KOH. While in 0.5 m H2SO4, the Ru90Ni10/rGOP hybrid electrode exhibits acidic HER catalytic behavior comparable to commercially available Pt/C catalyst due to the formation of monometallic Ru shell. These electrochemical behaviors outperform some of the best Ru-based catalysts and make it attractive alternative to Pt-based catalysts toward highly efficient HER.

Rational fabrication of metal phosphide nanoparticles immobilized in electrospun carbon nanofibers for efficient pH-universal hydrogen evolution and overall water splitting

Design and preparation of bifunctional electrocatalysts with optimized structures and abundant electrocatalytic active sites are significant for hydrogen generation in electrocatalytic water splitting. Herein, we have elaborately prepared Fe-doped CoP nanoparticles encapsulated in porous electrospun carbon nanofibers for bifunctional electrocatalysis on both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). The morphologies, components, and properties of the prepared electrocatalysts are influenced by the introduction of a facile air calcination treatment. Porous nanostructure as well as the full conversion of metal active sites are simultaneously achieved. Owing to the protective electrospun carbon nanofibers as well as the abundant exposed active sites, the optimized electrocatalyst exhibits excellent pH-universal HER activities with small overpotentials (99 mV, 159 mV, and 185 mV) at 10 mA cm−2 in acidic, alkaline, and neutral electrolytes, and also presents remarkable OER performance. Moreover, a water electrolyzer cell, using the optimized electrocatalyst as the electrodes, manifests both a high efficiency (1.63 V@10 mA cm−2) and robust stability. This work provides a convenient route for the controllable fabrication of transition metal-based electrocatalysts toward energy conversion.

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.

Ru Regulated Electronic Structure of PdxCuy Nanosheets for Efficient Hydrogen Evolution Reaction in Wide pH Range.

The development of highly effective catalysts for hydrogen evolution reaction (HER) in a wide pH range is crucial for the sustainable utilization of green energy utilization, while the slow kinetic reaction rate severely hinders the progress of HER. Herein, the reaction kinetic issue is solved by adjusting the electronic structure of the Ru/PdxCuy catalysts. The champion catalyst displays a remarkable performance for HER with the ultralow overpotential (27, 28, and 97mV) in 1.0m KOH, 0.5m H2SO4, and 1.0m PBS at 10mA cm-2 and high the mass activity (3036 A g-1), respectively, superior to those of commercial Pt/C benchmarks and most of reported electrocatalysts, mainly due to its low reaction activation energy. Density functional theory (DFT) calculations indicate that Ru doping contributes an electron-deficient 3d band, which promotes water adsorption. Additionally, this also leads to an upward shift of the d-band center of Pd and a downward shift of the d-band center of Cu, further optimizing the adsorption/dissociation of H2O and H*. Results from this work may provide an insight into the design and synthesis of high-performance pH-universal HER electrocatalysts.

Porous core–shell structured MoO2–Mo2C@C electrocatalysts for pH-universal hydrogen evolution reaction

We have synthesized an ultra-highly active and stable hydrogen evolution catalyst, MoO2–Mo2C@C, with a porous core–shell structure which can be used under both acidic and alkaline conditions.

Photochemical engineering unsaturated Pt islands on supported Pd nanocrystals for a robust pH-universal hydrogen evolution reaction.

The rational design of heterostructured nanocrystals (HNCs) is of great significance for developing highly efficient hydrogen evolution reaction (HER) electrocatalysts. However, a significant challenge still lies in realizing the controllable synthesis of desired HNCs directly onto a support and exploring their structure-activity-dependent HER performance. Herein, we reported various controllable Pd7@Ptx core-shell HNCs with optimal hybrid structures via a photochemical deposition strategy. The growth patterns of a Pt shell can be finely controlled by adjusting the growth kinetics, resulting in a varying deposition rate. In particular, the as-prepared Pd7@Pt3 HNCs with a Pt shell in the Stranski-Krastanov mode showed the best performances over a wide pH range media, delivering low overpotentials of 33, 18 and 49 mV, resulting in a catalytic current density of 10 mA cm-2 at a low effective catalyst loading of 0.021 mg cm-2. The resulting Tafel slopes were 23.1, 52.6 and 42.7 mV dec-1 in 0.5 M H2SO4, 1.0 M phosphate-buffered saline (PBS) and 1.0 M KOH electrolyte, respectively. It was found that the increased fraction of unsaturated coordination of Pt islands in the resultant material is the key to the enhanced and robust HER activity, which has been confirmed through density functional theory (DFT) calculations. This strategy could be extended to the rational design and synthesis of other heterostructured catalysts for energy conversion and storage.

Atomic-scale Ru anchored on chromium-shavings as a precursor for a pH-universal hydrogen evolution reaction electrocatalyst.

In the leather manufacturing industry, the management of substantial quantities of solid waste containing chrome shavings remains a formidable challenge. Concurrently, there is a pressing need for the development of pH-universal and economically viable electrocatalysts for the hydrogen evolution reaction (HER). In response to these intertwined challenges, this study proposes an innovative approach wherein the amino groups present on the surface of chrome shavings are utilized to immobilize single ruthenium atoms during pyrolysis, thereby facilitating the synthesis of hydrogen evolution electrocatalysts. The optimized sample, denoted as CN/Cr2O3/Ru-1, demonstrates exceptional electrocatalytic performance, exhibiting an ultra-low overpotential of -28 mV in 1.0 M KOH at a current density of 10 mA cm-2, and it also exhibits good performance in acidic and neutral electrolytes. Importantly, these overpotentials surpass those reported for many previous ruthenium-based catalysts. Density functional theory (DFT) calculations elucidate that both oxygen (O) and chromium (Cr) moieties within Cr2O3 can engage in favorable interactions with the coordination patterns of the ruthenium (Ru) atoms, thereby elucidating the synergistic enhancement conferred by the chromium element in CN/Cr2O3/Ru, which ultimately facilitates and promotes the catalytic activity of the ruthenium atoms serving as the catalytic center. This facile synthesis route not only presents a green solution for addressing waste chromium pollutants but also offers a promising avenue for the development of high-performance, cost-efficient electrocatalysts.

Free-standing multi-hierarchical MoC-based catalyst for pH-universal hydrogen evolution reaction at ultra-high current density

Free-standing multi-hierarchical MoC@C shell-supported P-MoC/Ni@NCNT nanoarrays for pH-universal hydrogen evolution reaction at ultra-high current density.

(Invited) MOF-Derived Nanosheet Arrays As Advanced Electrocatalysts for Water Splitting

Developing efficient, nanostructured electrocatalysts with desired compositions and structures is of great significance for improving the efficiency of water splitting toward hydrogen production. In this regard, metal organic framework (MOF) derived nanoarrays have attracted great attention as promising electrocatalysts because of their diverse compositions and adjustable structures. This presentation summarizes our recent work on the design and fabrication of MOF-derived nanosheet arrays toward enhanced catalytic activity for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) as well as overall water splitting.First, heterostructured inter-doped ruthenium-cobalt oxide ((Ru-Co)Ox) hollow nanosheet arrays were prepared on carbon cloth for efficient overall water splitting. Benefiting from the desirable compositional and structural advantages of more exposed active sites, optimized electronic structure, and interfacial synergy effect, the (Ru-Co)Ox nanoarrays exhibited outstanding performance as a bifunctional catalyst. Particularly, they showed a remarkable hydrogen evolution reaction (HER) activity with an overpotential of 44.1 mV at 10 mA cm–2 and a small Tafel slope of 23.5 mV dec–1, as well as an excellent oxygen evolution reaction (OER) activity with an overpotential of 171.2 mV at 10 mA cm−2. As a result, a very low cell voltage of 1.488 V was needed at 10 mA cm–2 for alkaline overall water splitting.Second, Mo-doped ruthenium–cobalt oxide (Mo-RuCoOx) nanosheet arrays were produced for high-efficiency water splitting through combining electronic and vacancy engineering. The unique Mo-RuCoOx nanosheet arrays were able to act as a high-performance bifunctional electrocatalyst toward both HER and OER. Theoretical calculations and experimental results reveal that the incorporation of Ru and Mo can effectively tune the electronic structure, and the controllable Mo dissolution coupling with the oxygen vacancy generation during surface reconstruction is able to optimize the adsorption energy of hydrogen/oxygen intermediates, thus greatly accelerating the kinetics for both HER and OER. As a result, the Mo-RuCoOx nanoarrays exhibit remarkably low overpotentials of 41 mV and 156 mV at 10 mA cm–2 for HER and OER in 1 M KOH, respectively. Furthermore, the two-electrode electrolyzer assembled by the Mo-RuCoOx nanoarrays requires a cell voltage as low as 1.457 V to achieve 10 mA cm–2 for alkaline overall water splitting.Third, hollow nanosheet arrays assembled by ultrafine ruthenium-cobalt phosphide nanocrystals were fabricated toward exceptional pH-universal hydrogen evolution. The development of high-efficiency electrocatalysts for pH-universal HER is promising for constructing feasible water splitting systems at all pH values, but it remains challenging. A facile approach toward hollow nanosheet arrays assembled by ultrafine ruthenium-cobalt phosphide (Ru-CoxP) nanocrystals was developed through conversion from the MOF template. The synergic effects of optimized electronic structure, increased active sites, and rapid charge/mass transfer endowed the Ru-CoxP nanoarrays with outstanding electrocatalytic performance toward pH-universal HER. While exhibiting remarkably low overpotentials of 34.6 mV and 22.7 mV at 10 mA cm–2 in 1 M KOH and 0.5 M H2SO4, respectively, the Ru-CoxP nanoarrays showed an extremely low overpotential of 21.6 mV at 10 mA cm–2 in 1 M phosphate buffer solution (PBS). Furthermore, they were able to stably drive a Pt-free neutral electrolyzer for overall water splitting at 10 mA cm−2 with a cell voltage as low as 1.557 V.

Metallic Mo, Ru coupled with graphitic carbon dots to activate inertness 1D copper-based nanowires as efficient electrocatalyst for pH-universal hydrogen evolution reaction

Designing efficient and robust pH-universal electrocatalysts for hydrogen evolution reaction (HER) is the key to boost the development of eco-friendly hydrogen energy. Herein, metallic Mo, Ru coupled with graphitic carbon dots (GQDs) activate inertness 1D copper-based nanowires (GQDs@ Ru, Mo-Cu2O/CF) by surface chemical oxidation, solvothermal and low temperature calcination. The metals of Mo, Ru favor the water-dissociation and optimize the hydrogen adsorption/desorption. In addition, GQDs owns edge effect and good conductivity, and then benefiting electron transport and active sites exposure. Therefore, the synthesized GQDs@ Ru, Mo-Cu2O/CF requires only 30, 39, 17 and 55 mV in alkaline, acidic, alkaline seawater and neutral to achieve 10 mA cm−2. Moreover, the assembled electrolyzer requires 1.58 V to reach 10 mA cm−2 in alkaline seawater, and maintained well at 200 mA cm−2 for 100 h. This research opens a new avenue for designing efficient catalysts on energy-relation applications through introducing both metal and non-metal.

1D/3D dual carbon-supported Mott-Schottky-type Co-Co2P heterojunctions for pH-universal hydrogen evolution

The rational design of low-cost, efficient, and stable heterojunction catalysts for pH-universal hydrogen evolution is attracting increasing attention towards a sustainable hydrogen economy. Herein, a sequential spatial restriction-pyrolysis route is developed to confine Mott-Schottky-type Co-Co2P heterojunctions embedded in the one-dimensional (1D) carbon nanotube-modified three-dimensional (3D) N,P dual-doped carbon matrix (Co-Co2P@CNT//CM). The synergistic effect between the abundant Mott-Schottky heterointerfaces and the 1D/3D dual carbon confinement system enables fully exposed active sites and facilitated charge transfer dynamics, thus triggering favorable electronic structures of Co-Co2P@CNT//CM. As a result, Co-Co2P@CNT//CM heterojunctions exhibit excellent pH-universal hydrogen evolution reaction (HER) performance with overpotentials of 142, 205, and 262 mV at 10 mA cm−2 in 0.5 M H2SO4, 1.0 M KOH, and 1.0 M phosphate buffer saline (PBS), respectively. The theoretical results demonstrated that the Mott-Schottky effect can induce an oriented interfacial charge exchange between Co and Co2P. This can lower the reactive kinetic barrier and endow Co-Co2P@CNT//CM with ideal hydrogen adsorption free energy, which efficiently drives the production of H2 from electrolytic water.

Interface regulation of Zr-MOF/Ni2P@nickel foam as high-efficient electrocatalyst for pH-universal hydrogen evolution reaction

Currently, the development of economical and effective non-noble metal electrocatalysts is vital for advancing hydrogen evolution reaction (HER) and enabling its widespread applications. The customizable pore structure and enormous surface area of metal–organic frameworks (MOFs) have made them to become promising non-noble metal electrocatalysts for HER. However, MOFs have some challenges, including low conductivity and instability, which can result in them having high overpotentials and slow reaction kinetics in electrocatalytic processes. In this work, we present an innovative approach for synthesizing cost-effective and high-efficient Zr-MOF-derived pH-universal electrocatalysts for HER. It entails creating the interfaces of the electrocatalysts with suitable proportions of phosphide nanostructures. Zr-MOF/Ni2P@nickel foam (NF) electrodes with interface regulated by Ni2P nanostructures were successfully developed for high-efficient pH-universal HER electrocatalysts. The presence of Ni2P nanostructures with abundant active sites at the Zr-MOFs@NF interfaces boosted the electronic conductivity and local charge density of the hybrid electrocatalysts. This helped to improve their reaction kinetics and electrocatalytic activity. By optimizing the Ni2P amount, Zr-MOF/Ni2P@NF demonstrated impressive stability and superior HER activities, with a low overpotential of 149 mV (acidic electrolytes) and 143 mV (alkaline electrolytes) at 10 mA cm−2. The proven strategy in this work can be expanded to many types of MOF-based materials for wider practical applications.

Nitrided Rhodium Nanoclusters with Optimized Water Bonding and Splitting Effects for pH-Universal H2-Production.

The nitridation of noble metals-based catalysts to further enhance their hydrogen evolution reaction (HER) kinetics in neutral and alkaline conditions would be an effective strategy for developing high-performance wide pH HER catalysts. Herein, a facile molten urea method is employed to construct the nitrided Rh nanoclusters (RhxN) supported on N-doped carbon (RhxN-NC). The uniformly distributed RhxN clusters exhibited optimized water bonding and splitting effects, therefore resulting in excellent pH-universal HER performance. The optimized RhxN-NC catalyst only requires 8, 12, and 109mV overpotentials to reach the current density of 10mA cm-2 in 0.5M H2SO4, 1.0M KOH, and 1.0M PBS electrolytes, respectively. The spectroscopic characterizations and theoretical calculation further confirm the vital role of Rh-N moieties in RhxN clusters in improving the transfer of electrons and facilitating the generation of H2. This work not only provides a suitable nitridation method for noble metal species in mild conditions but also makes a breakthrough in synthesizing noble metal nitrides-based electrocatalysts to achieve an exceptional wide-pH HER performance and other catalysis.

Aluminum-incorporation activates vanadium carbide with electron-rich carbon sites for efficient pH-universal hydrogen evolution reaction

Vanadium carbide (VC) is the greatest potential hydrogen evolution reaction (HER) catalyst because of its platinum-like property and abundant earth reserves. However, it exhibits insufficient catalytic performance due to the unfavorable interaction of reaction intermediates with catalysts. In this work, using NH4VO3 as the main raw material, the flow ratio of CH4 to Ar was accurately controlled, and a non-transition metal Al-doped into VC (100) nano-flowers with carbon hybrids on nickel foams (Al-VC@C/NF) was prepared for the first time as a high-efficiency HER catalyst by chemical vapor carbonization. The overpotential of Al-VC@C/NF catalysts in 0.5 M H2SO4 and 1 M KOH at a current density of 10 mA cm−2 are only 58 mV and 97 mV, respectively, which are the best HER performance among non-noble metal vanadium carbide based catalysts. Simultaneously, Al-VC@C/NF exhibits small Tafel slope (45 mV dec-1 and 73 mV dec-1) and excellent stability in acidic and alkaline media. Theoretical calculations demonstrate that doped Al atoms can induce electron redistribution on the vanadium carbide surface to form electron-rich carbon sites, which significantly reduces the energy barrier during the HER process. This work provides a new tactic to modulate vanadium-based carbons as efficient HER catalysts through non-transition metal doping.

Interfacial synergistic effect of Ru nanoparticles embedded onto amorphous/crystalline WO3 nanorods on boosting the pH-universal hydrogen evolution reaction

The development of high-efficiency pH-universal electrocatalyst is of great significance for hydrogen evolution reaction (HER). In this work, a rod-like Ru/WO3-VO electrocatalyst was constructed for HER via a solid-phase reaction strategy. Due to the restriction of atomic migration at solid phase interface, plenty of oxygen vacancies (VO) and structure distortions were generated in amorphous/crystalline WO3 phase (WO3-VO). The optimized Ru/WO3-VO annealed at 450 °C with 2.2 wt% Ru achieves outstanding intrinsic activity with low overpotential and Tafel slope in a 0–14 pH range. A turnover frequency value 7.2 higher than that of commercial Pt/C is abtaind on Ru/WO3-VO at overpotential of 100 mV. Density functional theory calculations reveal that H* adsorption and desorption balanced by tuning the interface electronic structure contributes synergistic effect to the pH-universal HER activity of Ru/WO3-VO. The crystalline/amorphous semiconductor-metal heterointerface is crucial to designing and synthesizing electrocatalysts for optimal HER activity.

Site difference influence of anchored Ru in mesoporous carbon on electrocatalytic performance toward pH-universal hydrogen evolution reaction

Site difference influence of anchored Ru in mesoporous carbon on electrocatalytic performance toward pH-universal hydrogen evolution reaction