Interstitial Hydrogen Atom to Boost Intrinsic Catalytic Activity of Tungsten Oxide for Hydrogen Evolution Reaction

Tungsten oxide (WO₃) is an appealing electrocatalyst for the hydrogen evolution reaction (HER) owing to its cost-effectiveness and structural adjustability. However, the WO₃ electrocatalyst displays undesirable intrinsic activity for the HER, which originates from the strong hydrogen adsorption energy. Herein, for effective defect engineering, a hydrogen atom inserted into the interstitial lattice site of tungsten oxide (H_0.23WO₃) is proposed to enhance the catalytic activity by adjusting the surface electronic structure and weakening the hydrogen adsorption energy. Experimentally, the H_0.23WO₃ electrocatalyst is successfully prepared on reduced graphene oxide. It exhibits significantly improved electrocatalytic activity for HER, with a low overpotential of 33 mV to drive a current density of 10 mA cm⁻² and ultra-long catalytic stability at high-throughput hydrogen output (200 000 s, 90 mA cm⁻²) in acidic media. Theoretically, density functional theory calculations indicate that strong interactions between interstitial hydrogen and lattice oxygen lower the electron density distributions of the d-orbitals of the active tungsten (W) centers to weaken the adsorption of hydrogen intermediates on W-sites, thereby sufficiently promoting fast desorption from the catalyst surface. This work enriches defect engineering to modulate the electron structure and provides a new pathway for the rational design of efficient catalysts for HER.     

2D Cobalt Chalcogenide Heteronanostructures Enable Efficient Alkaline Hydrogen Evolution Reaction

The development of high-efficiency non-precious metal electrocatalysts for alkaline electrolyte hydrogen evolution reactions (HER) is of great significance in energy conversion to overcome the limited supply of fossil fuels and carbon emission. Here, a highly active electrocatalyst is presented for hydrogen production, consisting of 2D CoSe₂/Co₃S₄ heterostructured nanosheets along Co₃O₄ nanofibers. The different reaction rate between the ion exchange reaction and redox reaction leads to the heterogeneous volume swelling, promoting the growth of 2D structure. The 2D/1D heteronanostructures enable the improved the electrochemical active area, the number of active sites, and more favorable H binding energy compared to individual cobalt chalcogenides. The roles of the different composition of the heterojunction are investigated, and the electrocatalysts based on the CoSe₂/Co₃S₄@Co₃O₄ exhibited an overpotential as low as 165 mV for 10 mA cm⁻² and 393 mV for 200 mA cm⁻² in 1 m KOH electrolyte. The as-prepared electrocatalysts remained active after 55 h operation without any significant decrease, indicating the excellent long-term operation stability of the electrode. The Faradaic efficiency of hydrogen production is close to 100% at different voltages. This work provides a new design strategy toward Co-based catalysts for efficient alkaline HER.     

Twinned Tungsten Carbonitride Nanocrystals Boost Hydrogen Evolution Activity and Stability

Synergistic integration of two active metal‐based compounds can lead to much higher electrocatalytic activity than either of the two individually, due to the interfacial effects. Herein, a proof‐of‐concept strategy is creatively developed for the successful fabrication of twinned tungsten carbonitride (WCN) nanocrystals, where W₂C and WN are chemically bonded at the molecule level. High‐angle annular dark‐field scanning transmission electron microscopy (HAADF‐STEM) and X‐ray absorption fine structure (XAFS) spectroscopy analyses demonstrate that the intergrowth of W₂C and WN in the WCN nanocrystals produces abundant N–W–C interfaces, leading to a significant enhancement in catalytic activity and stability for hydrogen evolution reaction (HER). Indeed, it shows 14.2 times higher and 140 mV lower in the respective turn‐over frequency (TOF) and overpotential at 10 mA cm^?2 compared to W₂C alone. To complement the experimental observation, the theoretical calculations demonstrate that the WCN endows more favorable hydrogen evolution reaction than the single W₂C or WN crystals due to abundant interfaces, beneficial electronic states, lower work function, and more active W sites at the N–W–C interfaces.     

Synthesis of Hierarchical 4H/fcc Ru Nanotubes for Highly Efficient Hydrogen Evolution in Alkaline Media

Hierarchical metal nanostructures containing 1D nanobuilding blocks have stimulated great interest due to their abundant active sites for catalysis. Herein, hierarchical 4H/face‐centered cubic (fcc) Ru nanotubes (NTs) are synthesized by a hard template‐mediated method, in which 4H/fcc Au nanowires (NWs) serve as sacrificial templates which are then etched by copper ions (Cu²⁺) in dimethylformamide. The obtained hierarchical 4H/fcc Ru NTs contain ultrathin Ru shells (5–9 atomic layers) and tiny Ru nanorods with length of 4.2 ± 1.1 nm and diameter of 2.2 ± 0.5 nm vertically decorated on the surface of Ru shells. As an electrocatalyst for the hydrogen evolution reaction in alkaline media, the hierarchical 4H/fcc Ru NTs exhibit excellent electrocatalytic performance, which is better than 4H/fcc Au‐Ru NWs, commercial Pt/C, Ru/C, and most of the reported electrocatalysts.     

Interfacial Engineering of Polycrystalline Pt5P2 Nanocrystals and Amorphous Nickel Phosphate Nanorods for Electrocatalytic Alkaline Hydrogen Evolution

Electrocatalytic hydrogen evolution reaction (HER) in alkaline media is important for hydrogen economy but suffers from sluggish reaction kinetics due to a large water dissociation energy barrier. Herein, Pt₅P₂ nanocrystals anchoring on amorphous nickel phosphate nanorods as a high-performance interfacial electrocatalyst system (Pt₅P₂ NCs/a-NiPi) for the alkaline HER are demonstrated. At the unique polycrystalline/amorphous interface with abundant defects, strong electronic interaction, and optimized intermediate adsorption strength, water dissociation is accelerated over abundant oxophilic Ni sites of amorphous NiPi, while hydride coupling is promoted on the adjacent electron-rich Pt sites of Pt₅P₂. Meanwhile, the ultra-small-sized Pt₅P₂ nanocrystals and amorphous NiPi nanorods maximize the density of interfacial active sites for the Volmer–Tafel reaction. Pt₅P₂ NCs/a-NiPi exhibits small overpotentials of merely 9 and 41 mV at −10 and −100 mA cm⁻² in 1 M KOH, respectively. Notably, Pt₅P₂ NCs/a-NiPi exhibits an unprecedentedly high mass activity (MA) of 14.9 mA µg_Pt⁻¹ at an overpotential of 70 mV, which is 80 times higher than that of Pt/C and represents the highest MA of reported Pt-based electrocatalysts for the alkaline HER. This work demonstrates a phosphorization and interfacing strategy for promoting Pt utilization and in-depth mechanistic insights for the alkaline HER.     

Highly Robust Non‐Noble Alkaline Hydrogen‐Evolving Electrocatalyst from Se‐Doped Molybdenum Disulfide Particles on Interwoven CoSe2 Nanowire Arrays

Developing efficient non‐noble and earth‐abundant hydrogen‐evolving electrocatalysts is highly desirable for improving the energy efficiency of water splitting in base. Molybdenum disulfide (MoS₂) is a promising candidate, but its catalytic activity is kinetically retarded in alkaline media due to the unfavorable water adsorption and dissociation feature. A heterogeneous electrocatalyst is reported that is constructed by selenium‐doped MoS₂ (Se‐MoS₂) particles on 3D interwoven cobalt diselenide (CoSe₂) nanowire arrays that drives the hydrogen evolution reaction (HER) with fast reaction kinetics in base. The resultant Se‐MoS₂/CoSe₂ hybrid exhibits an outstanding catalytic HER performance with extremely low overpotentials of 30 and 93 mV at 10 and 100 mA cm^–2 in base, respectively, which outperforms most of the inexpensive alkaline HER catalysts, and is among the best alkaline catalytic activity reported so far. Moreover, this hybrid catalyst shows exceptional catalytic performance with very low overpotentials of 84 and 95 mV at 10 mA cm^–2 in acidic and neutral electrolytes, respectively, implying robust pH universality of this hybrid catalyst. This work may provide new inspirations for the development of high‐performance MoS₂‐based HER electrocatalysts in unfavorable basic media for promising catalytic applications.     

Structure Engineering of MoS2 via Simultaneous Oxygen and Phosphorus Incorporation for Improved Hydrogen Evolution

Oxygen and phosphorus dual‐doped MoS₂ nanosheets (O,P‐MoS₂) with porous structure and continuous conductive network are fabricated using a one‐pot NaH₂PO₂‐assisted hydrothermal approach. By simply changing the precursor solution, the chemical composition and resulting structure can be effectively controlled to obtain desired properties toward the hydrogen evolution reaction (HER). Thanks to the beneficial structure and strong synergistic effects between the incorporated oxygen and phosphorus, the optimal O,P‐MoS₂ exhibit superior electrocatalytic performances compared with those of oxygen single‐doped MoS₂ nanosheets (O‐MoS₂). Specifically, a low HER onset overpotential of 150 mV with a small Tafel slope of 53 mV dec^?1, excellent conductivity, and long‐term durability are achieved by the structural engineering of MoS₂ via O and P co‐doping, making it an efficient HER electrocatalyst for water electrocatalysis. This work provides an alternative strategy to manipulate transition metal dichalcogenides as advanced materials for electrocatalytic and related energy applications.     

纳米晶碳化钨薄膜的析氢催化性能

采用等离子体增强化学气相沉积法制备了具有纳米结构的碳化钨薄膜, 采用XRD、EDS、SEM方法表征了薄膜的表面形貌、化学组成和物相结构. 这种碳化钨纳米晶薄膜具有巨大的电化学比表面积、很好的电催化活性和电化学稳定性. 通过测试和计算表明, 几何面积为1cm²碳化钨薄膜/泡沫镍电极、碳化钨薄膜/镍电极的电化学比表面积分别为83.21和64.13cm2; 该薄膜电极材料的a值为0.422～0.452V, 接近低超电势材料; 析氢交换电流密度为4.02～4.22×10^-4A/cm²; 当超电势为263mV时, 其析氢反应的活化能为45.62～45.77kJ/mol.     

Achieving Efficient Alkaline Hydrogen Evolution Reaction over a Ni5P4 Catalyst Incorporating Single-Atomic Ru Sites

Developing efficient electrocatalysts for alkaline water electrolysis is central to substantial progress of alkaline hydrogen production. Herein, a Ni₅P₄ electrocatalyst incorporating single-atom Ru (Ni₅P₄-Ru) is synthesized through the filling of Ru³⁺ species into the metal vacancies of nickel hydroxides and subsequent phosphorization treatment. Electron paramagnetic resonance spectroscopy, X-ray-based measurements, and electron microscopy observations confirm the strong interaction between the nickel-vacancy defect and Ru cation, resulting in more than 3.83 wt% single-atom Ru incorporation in the obtained Ni₅P₄-Ru. The Ni₅P₄-Ru as an alkaline hydrogen evolution reaction catalyst achieves low onset potential of 17 mV and an overpotential of 54 mV at a current density of 10 mA cm^-2 together with a small Tafel slope of 52.0 mV decade^-1 and long-term stability. Further spectroscopy analyses combined with density functional theory calculations reveal that the doped Ru sites can cause localized structure polarization, which brings the low energy barrier for water dissociation on Ru site and the optimized hydrogen adsorption free energy on the interstitial site, well rationalizing the experimental reactivity.     

Topological Engineering of Pt-Group-Metal-Based Chiral Crystals toward High-Efficiency Hydrogen Evolution Catalysts

It has been demonstrated that topological nontrivial surface states can favor heterogeneous catalysis processes such as the hydrogen evolution reaction (HER), but a further decrease in mass loading and an increase in activity are still highly challenging. The observation of massless chiral fermions associated with large topological charge and long Fermi arc (FA) surface states inspires the investigation of their relationship with the charge transfer and adsorption process in the HER. In this study, it is found that the HER efficiency of Pt-group metals can be boosted significantly by introducing topological order. A giant nontrivial topological energy window and a long topological surface FA are expected at the surface when forming chiral crystals in the space group of P2₁3 (#198). This makes the nontrivial topological features resistant to a large change in the applied overpotential. As HER catalysts, PtAl and PtGa chiral crystals show turnover frequencies as high as 5.6 and 17.1 s⁻¹ and an overpotential as low as 14 and 13.3 mV at a current density of 10 mA cm⁻². These crystals outperform those of commercial Pt and nanostructured catalysts. This work opens a new avenue for the development of high-efficiency catalysts with the strategy of topological engineering of excellent transitional catalytic materials.     

水分解制氢的光触媒陶瓷材料研究进展

利用自然光能使水分解制氢是解决能源短缺和环境污染的最好办法，光触媒材料可将光能转变为化学能，其应用前景十分广阔。详细叙述了光触媒催化作用的原理、光解媒材料的近期研究成果，并提出了光触媒材料今后主要应解决的关键问题。     

Coupling PtNi Ultrathin Nanowires with MXenes for Boosting Electrocatalytic Hydrogen Evolution in Both Acidic and Alkaline Solutions

Developing an efficient electrocatalyst for the hydrogen evolution reaction (HER) working in both acidic and alkaline solutions is highly desirable, but still remains challenging. Here, Pt_xNi ultrathin nanowires (NWs) with tunable compositions (x = 1.42, 3.21, 5.67) are in situ grown on MXenes (Ti₃C₂ nanosheets), serving as electrocatalysts toward HER. Such Pt_xNi@Ti₃C₂ electrocatalysts exhibit excellent HER performance in both acidic and alkaline solutions, with the Pt_3.21Ni@Ti₃C₂ being the best one. Specifically, Pt_3.21Ni@Ti₃C₂ achieves record‐breaking performance in terms of lowest overpotential (18.55 mV) and smallest Tafel slope (13.37 mV dec^?1) for HER in acidic media to date. Theory calculations and X‐ray photoelectron spectroscopy analyses demonstrate that the coupling of MXenes with the NWs not only approaches the Gibbs free energy for hydrogen adsorption close to zero through the electron transfer between them in acidic media, but also provides additional active sites for water dissociation in alkaline solution, both of them being beneficial to the HER performance.     

Surface Oxidation of AuNi Heterodimers to Achieve High Activities toward Hydrogen/Oxygen Evolution and Oxygen Reduction Reactions

Although much attention has been paid to the exploration of highly active electrocatalysts, especially catalysts for hydrogen evolution reaction (HER), oxygen evolution reaction (OER) and oxygen reduction reaction (ORR), the development of multifunctional catalysts remains a challenge. Here, we utilize AuNi heterodimers as the starting materials to achieve high activities toward HER, OER and ORR. The HER and ORR activities in an alkali environment are similar to those of Pt catalysts, and the OER activity is very high and better than that of commercial IrO₂. Both the experimental and calculated results suggest that the surface oxidation under oxidative conditions is the main reason for the different activities. The NiO/Ni interface which exists in the as‐synthesized heterodimers contributes to high HER activity, the Ni(OH)₂‐Ni‐Au interface and the surface Ni(OH)₂ obtained in electrochemical conditons gives rise to promising ORR and OER activities, respectively. As a comparison, a Au@Ni core‐shell structure is also synthesized and examined. The core‐shell structure shows lower activities for HER and OER than the heterodimers, and reduces O₂ selectively to H₂O₂. The work here allows for the development of a method to design multifunctional catalysts via the partial oxidation of a metal surface to create different active centers.     

Surface Engineering for Extremely Enhanced Charge Separation and Photocatalytic Hydrogen Evolution on g‐C3N4

Reinforcing the carrier separation is the key issue to maximize the photocatalytic hydrogen evolution (PHE) efficiency of graphitic carbon nitride (g‐C₃N₄). By a surface engineering of gradual doping of graphited carbon rings within g‐C₃N₄, suitable energy band structures and built‐in electric fields are established. Photoinduced electrons and holes are impelled into diverse directions, leading to a 21‐fold improvement in the PHE rate.     

光催化分解水制氢体系助催化剂研究进展

煤、石油、天然气等不可再生能源的消耗导致环境污染日益严重,开发和使用清洁的可再生能源迫在眉睫。利用太阳能光催化分解水制氢被认为是解决化石能源紧缺和环境污染问题的有效途径之一。光催化分解水制氢体系非常复杂,助催化剂是影响催化剂光催化效率的一个关键因素,它的引入可以有效提高催化剂的光催化活性和氢气产生速率,因此,开发廉价高效的助催化剂已逐渐成为本领域的研究热点。本文结合光催化分解水制氢原理,简要介绍了助催化剂的作用,对近年来光催化分解水产氢助催化剂的种类和研究内容进行了总结,分析和讨论了几类重要助催化剂的特点及作用机理,并对助催化剂的发展进行了展望,以期为新型高效光催化制氢材料的设计提供参考。