Carbon Dots Strongly Immobilized onto Carbon Nanohorns as Non-Metal Heterostructure with High Electrocatalytic Activity towards Protons Reduction in Hydrogen Evolution Reaction

Highly performing, non-metal inexpensive electrocatalysts for the production of hydrogen via electrochemical water splitting are called for the replacement of current platinum-based ones. In order to speed up the electrocatalytic hydrogen evolution, abundant active sites but also efficient charge transfer is needed. In this context, 0D carbon dots (CDs) with large specific surface area, low cost, high conductivity, and rich functional groups emerge as promising non-metal electrocatalysts. Additionally, the use of conductive substrates provides an effective strategy to boost their electrocatalytic performance. Herein, the unique 3D superstructure of carbon nanohorns (CNHs), as well as without any metal content in their structure, is used to provide a conductive support of high porosity, large specific surface area, and good electrical conductivity, for the in situ growth and immobilization of CDs, via a simple hydrothermal method. The direct contact of CDs with the 3D conductive network of CNHs promotes charge transfer, accelerating hydrogen evolution. The all-carbon non-metal CDs/CNHs nanoensembleshows an onset potential close to the one of Pt/C, low charge transfer resistance, and excellent stability.     

Molybdenum Carbide‐Decorated Metallic Cobalt@Nitrogen‐Doped Carbon Polyhedrons for Enhanced Electrocatalytic Hydrogen Evolution

Electrocatalytic hydrogen evolution reaction (HER) based on water splitting holds great promise for clean energy technologies, in which the key issue is exploring cost‐effective materials to replace noble metal catalysts. Here, a sequential chemical etching and pyrolysis strategy are developed to prepare molybdenum carbide‐decorated metallic cobalt@nitrogen‐doped porous carbon polyhedrons (denoted as Mo/Co@N–C) hybrids for enhanced electrocatalytic hydrogen evolution. The obtained metallic Co nanoparticles are coated by N‐doped carbon thin layers while the formed molybdenum carbide nanoparticles are well‐dispersed in the whole Co@N–C frames. Benefiting from the additionally implanted molybdenum carbide active sites, the HER performance of Mo/Co@N–C hybrids is significantly promoted compared with the single Co@N–C that is derived from the pristine ZIF‐67 both in alkaline and acidic media. As a result, the as‐synthesized Mo/Co@N–C hybrids exhibit superior HER electrocatalytic activity, and only very low overpotentials of 157 and 187 mV are needed at 10 mA cm^?2 in 1 m KOH and 0.5 m H₂SO₄, respectively, opening a door for rational design and fabrication of novel low‐cost electrocatalysts with hierarchical structures toward electrochemical energy storage and conversion.     

In Situ Coupling of CoP Polyhedrons and Carbon Nanotubes as Highly Efficient Hydrogen Evolution Reaction Electrocatalyst

Hydrogen evolution reaction (HER) from water electrolysis is an attractive technique developed in recent years for cost‐effective clean energy. Although considerable efforts have been paid to create efficient catalysts for HER, the development of an affordable HER catalyst with superior performance under mild conditions is still highly desired. In this work, metal–organic frameworks (MOFs)‐templated strategy is proposed for in situ coupling of cobalt phosphide (CoP) polyhedrons nanoparticles and carbon nanotubes (CNTs). Due to the synergistic catalytic effect between CoP polyhedrons and CNTs, the as‐prepared CoP–CNTs hybrids show excellent HER performance. The resultant CoP–CNTs demonstrate excellent HER activity in 0.5 m H₂SO₄ with Tafel slope of 52 mV dec^?1, small onset overpotential of ≈64 mV, and a low overpotential of ≈139 mV at 10 mA cm^?2. Additionally, the catalyst also manifests superior durability in acid media. Considering the structure diversity of MOFs, the strategy presented here can be extended for synthesizing other well‐defined metal phosphides–CNTs hybrids, which may be used in the fields of catalysis, energy conversion and storage.     

Amorphous Molybdenum Sulfide/Carbon Nanotubes Hybrid Nanospheres Prepared by Ultrasonic Spray Pyrolysis for Electrocatalytic Hydrogen Evolution

Developing cost‐effective electrocatalysts with high activity and stability for hydrogen evolution reaction (HER) plays an important role in modern hydrogen economy. Amorphous molybdenum sulfide (MoS_x ) has recently emerged as one of the most promising alternatives to Pt‐based catalysts in HER, especially in acidic electrolytes. Here this study reports a simple ultrasonic spray pyrolysis method to synthesize hybrid HER catalysts composed of MoS_x firmly attached on entangled carbon nanotube nanospheres (MoS_x /CNTs). This synthetic process is fast, continuous, highly durable, and amenable to high‐volume production with high yields and exceptional quality. The MoS_x /CNTs hybrid catalyst prepared at 300 °C exhibits a low overpotential of 168 mV at the current density of 10 mA cm^?2 with a small Tafel slope of 36 mV dec^?1. Electrochemical measurements and X‐ray photoelectron spectroscopy analyses reveal that the CNT network not only promotes the charge transfer in corresponding HER process but also enhances the stability of the active sites in MoS_x . This work demonstrates that ultrasonic spray pyrolysis is a reliable and versatile approach for synthesizing amorphous MoS_x‐based HER catalysts.     

Stable Rhodium (IV) Oxide for Alkaline Hydrogen Evolution Reaction

Water electrolysis in alkaline electrolyte is an attractive way toward clean hydrogen energy via the hydrogen evolution reaction (HER), whereas the sluggish water dissociation impedes the following hydrogen evolution. Noble metal oxides possess promising capability for catalyzing water dissociation and hydrogen evolution; however, they are never utilized for the HER due to the instability under the reductive potential. Here it is shown that compressive strain can stabilize RhO₂ clusters and promote their catalytic activity. To this end, a strawberry-like structure with RhO₂ clusters embedded in the surface layer of Rh nanoparticles is engineered, in which the incompatibility between the oxide cluster and the metal substrate causes intensive compressive strain. As such, RhO₂ clusters remain stable at a reduction potential up to −0.3 V versus reversible hydrogen electrode and present an alkaline HER activity superior to commercial Pt/C.     

Confining Sub-Nanometer Pt Clusters in Hollow Mesoporous Carbon Spheres for Boosting Hydrogen Evolution Activity

Electrochemical water splitting is considered as a promising approach to produce clean and sustainable hydrogen fuel. As a new class of nanomaterials with high ratio of surface atoms and tunable composition and electronic structure, metal clusters are promising candidates as catalysts. Here, a new strategy is demonstrated to synthesize active and stable Pt-based electrocatalysts for hydrogen evolution by confining Pt clusters in hollow mesoporous carbon spheres (Pt₅/HMCS). Such a structure would effectively stabilize the Pt clusters during the ligand removal process, leading to remarkable electrocatalytic performance for hydrogen production in both acidic and alkaline solutions. Particularly, the optimal Pt₅/HMCS electrocatalyst exhibits 12 times the mass activity of Pt in commercial Pt/C catalyst with similar Pt loading. This study exemplifies a simple yet effective approach to improve the cost effectiveness of precious-metal-based catalysts with stabilized metal clusters.     

Hierarchical Nanorods of MoS2/MoP Heterojunction for Efficient Electrocatalytic Hydrogen Evolution Reaction

Hierarchical nanostructures with tailored component and architectures are attractive for energy‐related applications. Here, the delicate design and construction of hierarchical MoS₂/MoP (H‐MoS₂/MoP) nanorods for the hydrogen evolution reaction (HER) are demonstrated. This multiscale design rationally combines the compositional and structural advantages of MoS₂/MoP heterojunction into a hierarchical architecture, which can modulate electronic structure of S, remarkably facilitating the electrocatalytic HER. Benefitting from their unique architecture and electronic structure, the H‐MoS₂/MoP nanorods exhibit excellent performance for HER with ultralow overpotential of 92 mV at current density of 10 mA cm^?2 in 1 m KOH and high stability. This work not only provides an efficient approach to constructing hierarchical heterojunctions, but also a multiscale strategy for all‐round regulation of the electronic structure and hierarchical morphology of nanomaterials for energy‐related applications.     

KOH碱化处理对Fe3N纳米颗粒电催化制氢性能影响

采用KOH溶液在通电条件下对Fe₃N纳米颗粒表面改性的方法, 探究了碱化处理对Fe₃N纳米颗粒电催化性能的影响。采用XRD、TEM、EDX、XPS、拉曼光谱和傅立叶变换红外光谱对碱化前后的Fe₃N样品进行形貌和成分的表征, 采用时间电流曲线、LSV曲线、Tafel斜率、交流阻抗法和CV曲线对碱化前后的Fe₃N样品进行电催化制氢(HER)性能的分析。结果表明, 用KOH处理的Fe₃N样品, 平均晶粒尺寸由(80±10) nm缩小为(70±10) nm, 形状由破碎的链状结构变为椭圆形结构, 物相由ε-Fe₃N相部分转变为α-Fe₂O₃相; 尺寸、形貌和成分的改变, 使得碱化后的样品有更多的电催化活性位点暴露。由电流密度为10 mA/cm²的过电位0.429 V降为0.204 V, Tafel斜率由103 mV/dec降为95 mV/dec。过电势降低, 交流阻抗变小, 电化学活性面积增大, 表明KOH碱化处理后的样品电催化制氢的能力得到大大提高。     

Interface Metal Oxides Regulating Electronic State around Nickel Species for Efficient Alkaline Hydrogen Electrocatalysis

Heterogeneous electrocatalysis typically depends on the surface electronic states of active sites. Modulating the surface charge state of an electrocatalysts can be employed to improve performance. Among all the investigated materials, nickel (Ni)-based catalysts are the only non-noble-metal-based alternatives for both hydrogen oxidation and evolution reactions (HOR and HER) in alkaline electrolyte, while their activities should be further improved because of the unfavorable hydrogen adsorption behavior. Hereto, Ni with exceptional HOR electrocatalytic performance by changing the d-band center by metal oxides interface coupling formed in situ is endowed. The resultant MoO₂ coupled Ni heterostructures exhibit an apparent HOR activity, even approaching to that of commercial 20% Pt/C benchmark, but with better long-term stability in alkaline electrolyte. An exceptional HER performance is also achieved by the Ni-MoO₂ heterostructures. The experiment results are rationalized by the theoretical calculations, which indicate that coupling MoO₂ with Ni results in the downshift of d-band center of Ni, and thus weakens hydrogen adsorption and benefits for hydroxyl adsorption. This concept is further proved by other metal oxides (e.g., CeO₂, V₂O₃, WO₃, Cr₂O₃)-formed Ni-based heterostructures to engineer efficient hydrogen electrocatalysts.     

Closest Packing Polymorphism Interfaced Metastable Transition Metal for Efficient Hydrogen Evolution

Metastable materials are promising because of their catalytic properties, high-energy structure, and unique electronic environment. However, the unstable nature inherited from the metastability hinders further performance improvement and practical applications of these materials. Herein, this limitation is successfully addressed by constructing an in situ polymorphism interface (inf) between the metastable hexagonal-close-packed (hcp) phase and its stable counterpart (face-centered cubic, fcc) in cobalt–nickel (CoNi) alloy. Calculations reveal that the interfacial synergism derived from the hcp and fcc phases lowers the formation energy and enhances stability. Consequently, the optimized CoNi-inf exhibits an exceptionally low potential of 72 mV at 10 mA cm⁻² and a Tafel slope of 57 mV dec⁻¹ for the hydrogen evolution reaction (HER) in 1.0 m KOH. Furthermore, it is superior to most state-of-the-art non-noble-metal-based HER catalysts. No noticeable activity decay or structural changes are observed even over 14 h of catalysis. The computational simulation further rationalizes that the interface of CoNi-inf with a suitable d-band center provides uniform sites for hydrogen adsorption, leading to a distinguished HER catalytic activity. This work, therefore, presents a new route for designing metastable catalysts for potential energy conversion.     

Ultrathin Transition Metal Dichalcogenide/3d Metal Hydroxide Hybridized Nanosheets to Enhance Hydrogen Evolution Activity

The vast majority of the reported hydrogen evolution reaction (HER) electrocatalysts perform poorly under alkaline conditions due to the sluggish water dissociation kinetics. Herein, a hybridization catalyst construction concept is presented to dramatically enhance the alkaline HER activities of catalysts based on 2D transition metal dichalcogenides (TMDs) (MoS₂ and WS₂). A series of ultrathin 2D‐hybrids are synthesized via facile controllable growth of 3d metal (Ni, Co, Fe, Mn) hydroxides on the monolayer 2D‐TMD nanosheets. The resultant Ni(OH)₂ and Co(OH)₂ hybridized ultrathin MoS₂ and WS₂ nanosheet catalysts exhibit significantly enhanced alkaline HER activity and stability compared to their bare counterparts. The 2D‐MoS₂/Co(OH)₂ hybrid achieves an extremely low overpotential of ≈128 mV at 10 mA cm^?2 in 1 m KOH. The combined theoretical and experimental studies confirm that the formation of the heterostructured boundaries by suitable hybridization of the TMD and 3d metal hydroxides is responsible for the improved alkaline HER activities because of the enhanced water dissociation step and lowers the corresponding kinetic energy barrier by the hybridized 3d metal hydroxides.     

非贵金属/碳氮复合材料电催化析氧反应的研究进展

析氧反应(OER)是一种复杂的四电子转移反应,其动力学缓慢、所需能量高,制约了电解水制氢等新型能源技术的发展.近年来,非贵金属复合材料因其优异的催化活性以及相比于贵金属基催化剂的成本优势而受到广泛关注.本文概述了这一研究领域的最新进展,首先简要介绍析氧反应的机理以及材料催化性能的评价方法,重点关注非贵金属/碳氮复合材料...     

Adsorbed p-Aminothiophenol Molecules on Platinum Nanoparticles Improve Electrocatalytic Hydrogen Evolution

Electrocatalytic hydrogen evolution is an important approach to produce clean energy, and many electrocatalysts (e.g., platinum) are developed for hydrogen production. However, the electrocatalytic efficiency of commonly used metal catalysts needs to be improved to compensate their high cost. Herein, the electrocatalytic efficiency of platinum nanoparticles (PtNPs) in hydrogen evolution is largely improved via simple surface adsorption of sub-monolayer p-aminothiophenol (PATP) molecules. The overpotential goes down to 86.1 mV, which is 50.2 mV lower than that on naked PtNPs. This catalytic activity is even better than that of 20 wt.% Pt/C, despite the much smaller active surface area of PATP-adsorbed PtNPs than Pt/C. It is theoretically and experimentally confirmed that the improved electrocatalytic activity in hydrogen evolution can be attributed to the change in electronic structure of PtNPs induced by surface adsorption of PATP molecules. More importantly, this strategy can also be used to improve the electrocatalytic activity of palladium, gold, and silver nanoparticles. Therefore, this work provides a simple, convenient, and versatile method for improving the electrocatalytic activity of metal nanocatalysts. This surface adsorption strategy may also be used for improving the efficiency of many other nanocatalysts in many reactions.     

Ultrafine Dual‐Phased Carbide Nanocrystals Confined in Porous Nitrogen‐Doped Carbon Dodecahedrons for Efficient Hydrogen Evolution Reaction

Designing novel non‐noble electrocatalysts with controlled structures and composition remains a great challenge for efficient hydrogen evolution reaction (HER). Herein, a rational synthesis of ultrafine carbide nanocrystals confined in porous nitrogen‐doped carbon dodecahedrons (PNCDs) by annealing functional zeolitic imidazolate framework (ZIF‐8) with molybdate or tungstate is reported. By controlling the substitution amount of MO₄ units (M = Mo or W) in the ZIF‐8 framework, dual‐phase carbide nanocrystals confined in PNCDs (denoted as MC‐M₂C/PNCDs) can be obtained, which exhibit superior activity toward the HER to the single‐phased MC/PNCDs and M₂C/PNCDs. The evenly distributed ultrafine nanocrystals favor the exposure of active sites. PNCDs as the support facilitate charge transfer and protect the nanocrystals from aggregation during the HER process. Moreover, the strong coupling interactions between MC and M₂C provide beneficial sites for both water dissociation and hydrogen desorption. This work highlights a new feasible strategy to explore efficient electrocatalysts via engineering on nanostructure and composition.     

Flexible Honeycombed Nanoporous/Glassy Hybrid for Efficient Electrocatalytic Hydrogen Generation

Hydrogen evolution reaction (HER) in alkaline media urgently requires electrocatalysts concurrently possessing excellent activity, flexible free‐standing capability, and low cost. A honeycombed nanoporous/glassy sandwich structure fabricated through dealloying metallic glass (MG) is reported. This free‐standing hybrid shows outstanding HER performance with a very small overpotential of 37 mV at 10 mA cm^?2 and a low Tafel slope of 30 mV dec^?1 in alkaline media, outperforming commercial Pt/C. By alloying 3 at% Pt into the MG precursor, a honeycombed Pt₇₅Ni₂₅ solid solution nanoporous structure, with fertile active sites and large contact areas for efficient HER, is created on the dealloyed MG surface. Meanwhile, the surface compressive lattice‐strain effect is also introduced by substituting the Pt lattice sites with the smaller Ni atoms, which can effectively reduce the hydrogen adsorption energy and thus improve the hydrogen evolution. Moreover, the outstanding stability and flexibility stemming from the ductile MG matrix also make the hybrid suitable for practical electrode application. This work not only offers a reliable strategy to develop cost‐effective and flexible multicomponent catalysts with low Pt usage for efficient HER, but also sheds light on understanding the alloying effects of the catalytic process.     

Monolithic Nickel Catalyst Featured with High-Density Crystalline Steps for Stable Hydrogen Evolution at Large Current Density

Producing hydrogen via electrochemical water splitting with minimum environmental harm can help resolve the energy crisis in a sustainable way. Here, this work fabricates the pure nickel nanopyramid arrays (NNAs) with dense high-index crystalline steps as the cata electrode via a screw dislocation-dominated growth kinetic for long-term durable and large current density hydrogen evolution reaction. Such a monolithic NNAs electrode offers an ultralow overpotential of 469 mV at a current density of 5000 mA cm⁻² in 1.0 m KOH electrolyte and shows a high stability up to 7000 h at a current density of 1000 mA cm⁻², which outperforms the reported catas and even the commercial platinum cata for long-term services under high current densities. Its unique structure can substantially stabilize the high-density surface crystalline steps on the catalytic electrode, which significantly elevates the catalytic activity and durability of nickel in an alkaline medium. In a typical commercial hydrogen gas generator, the total energy conversion rate of NNAs reaches 84.5% of that of a commercial Pt/Ti cata during a 60-day test of hydrogen production. This work approach can provide insights into the development of industry-compatible long-term durable, and high-performance non-noble metal catas for various applications.     

Interface Modulation of MoS2/Metal Oxide Heterostructures for Efficient Hydrogen Evolution Electrocatalysis

Developing efficient earth‐abundant MoS₂ based hydrogen evolution reaction (HER) electrocatalysts is important but challenging due to the sluggish kinetics in alkaline media. Herein, a strategy to fabricate a high‐performance MoS₂ based HER electrocatalyst by modulating interface electronic structure via metal oxides is developed. All the heterostructure catalysts present significant improvement of HER electrocatalytic activities, demonstrating a positive role of metal oxides decoration in promoting the rate‐limited water dissociation step for the HER mechanism in alkaline media. The as‐obtained MoS₂/Ni₂O₃H catalyst exhibits a low overpotential of 84 mV at 10 mA cm^?2 and small charge‐transfer resistance of 1.5 Ω in 1 m KOH solution. The current density (217 mA cm^?2) at the overpotential of 200 mV is about 2 and 24 times higher than that of commercial Pt/C and bare MoS₂, respectively. Additionally, these MoS₂/metal oxides heterostructure catalysts show outstanding long‐term stability under a harsh chronopotentiometry test. Theoretical calculations reveal the varied sensitivity of 3d‐band in different transition oxides, in which Ni‐3d of Ni₂O₃H is evidently activated to achieve fast electron transfer for HER as the electron‐depletion center. Both electronic properties and energetic reaction trends confirm the high electroactivity of MoS₂/Ni₂O₃H in the adsorption and dissociation of H₂O for highly efficient HER in alkaline media.     

Synergistic Interlayer and Defect Engineering in VS2 Nanosheets toward Efficient Electrocatalytic Hydrogen Evolution Reaction

A simple one‐pot solvothermal method is reported to synthesize VS₂ nanosheets featuring rich defects and an expanded (001) interlayer spacing as large as 1.00 nm, which is a ≈74% expansion as relative to that (0.575 nm) of the pristine counterpart. The interlayer‐expanded VS₂ nanosheets show extraordinary kinetic metrics for electrocatalytic hydrogen evolution reaction (HER), exhibiting a low overpotential of 43 mV at a geometric current density of 10 mA cm^?2, a small Tafel slope of 36 mV dec^?1, and long‐term stability of 60 h without any current fading. The performance is much better than that of the pristine VS₂ with a normal interlayer spacing, and even comparable to that of the commercial Pt/C electrocatalyst. The outstanding electrocatalytic activity is attributed to the expanded interlayer distance and the generated rich defects. Increased numbers of exposed active sites and modified electronic structures are achieved, resulting in an optimal free energy of hydrogen adsorption (?G_H) from density functional theory calculations. This work opens up a new door for developing transition‐metal dichalcogenide nanosheets as high active HER electrocatalysts by interlayer and defect engineering.