A General Route to Prepare Low‐Ruthenium‐Content Bimetallic Electrocatalysts for pH‐Universal Hydrogen Evolution Reaction by Using Carbon Quantum Dots

A challenging but pressing task to design and synthesize novel, efficient, and robust pH‐universal hydrogen evolution reaction (HER) electrocatalysts for scalable and sustainable hydrogen production through electrochemical water splitting. Herein, we report a facile method to prepare an efficient and robust Ru‐M (M=Ni, Mn, Cu) bimetal nanoparticle and carbon quantum dot hybrid (RuM/CQDs) for pH‐universal HER. The RuNi/CQDs catalysts exhibit outstanding HER performance at all pH levels. The unexpected low overpotentials of 13, 58, and 18 mV shown by RuNi/CQDs allow a current density of 10 mA cm^?2 in 1 m KOH, 0.5 m H₂SO₄, and 1 m PBS, respectively, for Ru loading at 5.93 μgRu cm^?2. This performance is among the best catalytic activities reported for any platinum‐free electrocatalyst. Theoretical studies reveal that Ni doping results in a moderate weakening of the hydrogen bonding energy of nearby surface Ru atoms, which plays a critical role in improving the HER activity.     

Optimizing Electronic and Geometrical Structure of Vanadium Doped Cobalt Phosphides for Enhanced Electrocatalytic Hydrogen Evolution

Despite the expectation on transition-metal phosphides as precious-metal-free electrocatalysts, the reported performance of these materials still necessitates further improvement. Ingenious regulations of both geometric and electronic structure have been proposed as an effective approach to boost their electrocatalytic properties. In this regard, the self-supported V doped CoP nanowires on nickel foam are prepared to accommodate both optimized electronic structure and desired nanostructure, which enable large surface area, abundant active sites exposure, low charge transfer resistance, as well as favorable H* adsorption. As for the alkaline hydrogen evolution, it only requires a lower potential of 79 mV and 125 mV to drive 10 mA ⋅ cm⁻² and 100 mA ⋅ cm⁻² current with a Tafel slope of 47.41 mV ⋅ dec⁻¹, which prevails over commercial Pt/C catalysts. The catalyst also exhibits excellent durability to retain activity unchanged for more than 16 h. Such a simple and convenient strategy by electronic tuning and structure design provides a new avenue toward the exploration of efficient electrocatalysts.     

Boron-Induced Electronic-Structure Reformation of CoP Nanoparticles Drives Enhanced pH-Universal Hydrogen Evolution

Even though transition-metal phosphides (TMPs) have been developed as promising alternatives to Pt catalyst for the hydrogen evolution reaction (HER), further improvement of their performance requires fine regulation of the TMP sites related to their specific electronic structure. Herein, for the first time, boron (B)-modulated electrocatalytic characteristics in CoP anchored on the carbon nanotubes (B-CoP/CNT) with impressive HER activities over a wide pH range are reported. The HER performance surpasses commercial Pt/C in both neutral and alkaline media at large current density (>100 mA cm⁻²). A combined experimental and theoretical study identified that the B dopant could reform the local electronic configuration and atomic arrangement of bonded Co and adjacent P atoms, enhance the electrons’ delocalization capacity of Co atoms for high electrical conductivity, and optimize the free energy of H adsorption and H₂ desorption on the active sites for better HER kinetics.     

Single‐Shell Carbon‐Encapsulated Iron Nanoparticles: Synthesis and High Electrocatalytic Activity for Hydrogen Evolution Reaction

Efficient hydrogen evolution reaction (HER) through effective and inexpensive electrocatalysts is a valuable approach for clean and renewable energy systems. Here, single‐shell carbon‐encapsulated iron nanoparticles (SCEINs) decorated on single‐walled carbon nanotubes (SWNTs) are introduced as a novel highly active and durable non‐noble‐metal catalyst for the HER. This catalyst exhibits catalytic properties superior to previously studied nonprecious materials and comparable to those of platinum. The SCEIN/SWNT is synthesized by a novel fast and low‐cost aerosol chemical vapor deposition method in a one‐step synthesis. In SCEINs the single carbon layer does not prevent desired access of the reactants to the vicinity of the iron nanoparticles but protects the active metallic core from oxidation. This finding opens new avenues for utilizing active transition metals such as iron in a wide range of applications.     

Nanosized Metal Phosphides Embedded in Nitrogen‐Doped Porous Carbon Nanofibers for Enhanced Hydrogen Evolution at All pH Values

Transition‐metal phosphides (TMPs) have emerged as promising catalyst candidates for the hydrogen evolution reaction (HER). Although numerous methods have been investigated to obtain TMPs, most rely on traditional synthetic methods that produce materials that are inherently deficient with respect to electrical conductivity. An electrospinning‐based reduction approach is presented, which generates nickel phosphide nanoparticles in N‐doped porous carbon nanofibers (Ni₂P@NPCNFs) in situ. Ni₂P nanoparticles are protected from irreversible fusion and aggregation in subsequent high‐temperature pyrolysis. The resistivity of Ni₂P@NPCNFs (5.34 Ω cm) is greatly decreased by 10⁴ times compared to Ni₂P (>10⁴ Ω cm) because N‐doped carbon NFs are incorporated. As an electrocatalyst for HER, Ni₂P@NPCNFs reveal remarkable performance compared to other previously reported catalysts in acidic media. Additionally, it offers excellent catalytic ability and durability in both neutral and basic media. Encouraged by the excellent electrocatalytic performance of Ni₂P@NPCNFs, a series of pea‐like M_xP@NPCNFs, including Fe₂P@NPCNFs, Co₂P@NPCNFs, and Cu₃P@NPCNFs, were synthesized by the same method. Detailed characterization suggests that the newly developed method could render combinations of ultrafine metal phosphides with porous carbon accessible; thereby, extending opportunities in electrocatalytic applications.     

Carbon Nanotubes Decorated with CoP Nanocrystals: A Highly Active Non‐Noble‐Metal Nanohybrid Electrocatalyst for Hydrogen Evolution

The development of effective and inexpensive hydrogen evolution reaction (HER) electrocatalysts for future renewable energy systems is highly desired. The strongly acidic conditions in proton exchange membranes create a need for acid‐stable HER catalysts. A nanohybrid that consists of carbon nanotubes decorated with CoP nanocrystals (CoP/CNT) was prepared by the low‐temperature phosphidation of a Co₃O₄/CNT precursor. As a novel non‐noble‐metal HER catalyst operating in acidic electrolytes, the nanohybrid exhibits an onset overpotential of as low as 40 mV, a Tafel slope of 54 mV dec^?1, an exchange current density of 0.13 mA cm^?2, and a Faradaic efficiency of nearly 100 %. This catalyst maintains its catalytic activity for at least 18 hours and only requires overpotentials of 70 and 122 mV to attain current densities of 2 and 10 mA cm^?2, respectively.     

Hierarchical Architectures Based on Ru Nanoparticles/Oxygen-Rich-Carbon Nanotubes for Efficient Hydrogen Evolution

Highly active and durable electrocatalysts are essential for producing hydrogen fuel through the hydrogen evolution reaction (HER). Here, a uniform deposition of Ru nanoparticles strongly interacting with oxygen-rich carbon nanotube architectures (Ru-OCNT) through ozonation and hydrothermal approaches has been designed. The hierarchical structure of Ru-OCNT is made by self-assembly of oxygen functionalities of OCNT. Ru nanoparticles interact strongly with OCNT at the Ru/OCNT interface to give excellent catalytic activity and stability of the Ru-OCNT, as further confirmed by density functional theory. Owing to the hierarchical structure and adjusted surface chemistry, Ru-OCNT has an overpotential of 34 mV at 10 mA cm⁻² with a Tafel slope of 27.8 mV dec⁻¹ in 1 M KOH, and an overpotential of 55 mV with Tafel slope of 33 mV dec⁻¹ in 0.5 M H₂SO₄. The smaller Tafel slope of Ru-OCNT than Ru-CNT and commercial Pt/C in both alkaline and acidic electrolytes indicates high catalytic activity and fast charge transfer kinetics. The as-proposed chemistry provides the rational design of hierarchically structured CNT/nanoparticle electrocatalysts for HER to produce hydrogen fuel.     

Interfacial Structure of Water as a New Descriptor of the Hydrogen Evolution Reaction

Driven by the persisting poor understanding of the sluggish kinetics of the hydrogen evolution reaction (HER) on Pt in alkaline media, a direct correlation of the interfacial water structure and activity is still yet to be established. Herein, using Pt and Pt–Ni nanoparticles we first demonstrate a strong dependence of the proton donor structure on the HER activity and pH. The structure of the first layer changes from the proton acceptors to the donors with increasing pH. In the base, the reactivity of the interfacial water varied its structure, and the activation energies of water dissociation increased in the sequence: the dangling O−H bonds < the trihedrally coordinated water < the tetrahedrally coordinated water. Moreover, optimizing the adsorption of H and OH intermediates can re-orientate the interfacial water molecules with their H atoms pointing towards the electrode surface, thereby enhancing the kinetics of HER. Our results clarified the dynamic role of the water structure at the electrode–electrolyte interface during HER and the design of highly efficient HER catalysts.     

Graphitic C3N4 Decorated with CoP Co‐catalyst: Enhanced and Stable Photocatalytic H2 Evolution Activity from Water under Visible‐light Irradiation

In this work, graphitic C₃N₄ decorated with a CoP co‐catalyst (g‐C₃N₄/CoP) is reported for photocatalytic H₂ evolution reaction based on two‐step hydrothermal and phosphidation method. The structure of g‐C₃N₄/CoP is well confirmed by XRD, FTIR, TEM, XPS, and UV/Vis diffuse reflection spectra techniques. When the weight percentage of CoP loading is 3.4 wt % (g‐C₃N₄/CoP‐3.4 %), the highest H₂ evolution amount of 8.4×10² μmol g⁻¹ is obtained, which is 1.1×10³ times than that over pure g‐C₃N₄. This value also is comparable with that of g‐C₃N₄ loaded by the same amount of Pt. In cycling experiments, g‐C₃N₄/CoP‐3.4 % shows a stable photocatalytic activity. In addition, g‐C₃N₄/CoP‐3.4 % is an efficient photocatalyst for H₂ evolution under irradiation with natural solar light. Based on comparative photoluminescence emission spectra, photoelectrochemical I –t curves, EIS Nyquist plots, and polarization curves between g‐C₃N₄/CoP‐3.4 % and pure g‐C₃N₄, it is concluded that the presence of the CoP co‐catalyst accelerates the separation and transfer of photogenerated electrons of g‐C₃N₄, thus resulting in improved photocatalytic activity in the H₂ evolution reaction.     

Boron‐Dependency of Molybdenum Boride Electrocatalysts for the Hydrogen Evolution Reaction

Molybdenum‐based materials have been considered as alternative catalysts to noble metals, such as platinum, for the hydrogen evolution reaction (HER). We have synthesized four binary bulk molybdenum borides Mo₂B, α‐MoB, β‐MoB, and MoB₂ by arc‐melting. All four phases were tested for their electrocatalytic activity (linear sweep voltammetry) and stability (cyclic voltammetry) with respect to the HER in acidic conditions. Three of these phases were studied for their HER activity and by X‐ray photoelectron spectroscopy (XPS) for the first time; MoB₂ and β‐MoB show excellent activity in the same range as the recently reported α‐MoB and β‐Mo₂C phases, while the molybdenum richest phase Mo₂B show significantly lower HER activity, indicating a strong boron‐dependency of these borides for the HER. In addition, MoB₂ and β‐MoB show long‐term cycle stability in acidic solution.     

Phosphorus‐Doped Carbon Nitride Tubes with a Layered Micro‐nanostructure for Enhanced Visible‐Light Photocatalytic Hydrogen Evolution

Phosphorus‐doped hexagonal tubular carbon nitride (P‐TCN) with the layered stacking structure was obtained from a hexagonal rod‐like single crystal supramolecular precursor (monoclinic, C2/m). The production process of P‐TCN involves two steps: 1) the precursor was prepared by self‐assembly of melamine with cyanuric acid from in situ hydrolysis of melamine under phosphorous acid‐assisted hydrothermal conditions; 2) the pyrolysis was initiated at the center of precursor under heating, thus giving the hexagonal P‐TCN. The tubular structure favors the enhancement of light scattering and active sites. Meanwhile, the introduction of phosphorus leads to a narrow band gap and increased electric conductivity. Thus, the P‐TCN exhibited a high hydrogen evolution rate of 67 μmol h^?1 (0.1 g catalyst, λ >420 nm) in the presence of sacrificial agents, and an apparent quantum efficiency of 5.68 % at 420 nm, which is better than most of bulk g‐C₃N₄ reported.     

Prussian Blue‐Derived Iron Phosphide Nanoparticles in a Porous Graphene Aerogel as Efficient Electrocatalyst for Hydrogen Evolution Reaction

Tailoring of new hydrogen evolution reaction (HER) electrocatalyst with earth abundant elements is important for large scale water splitting and hydrogen production. In this work, we present a simple synthetic method for incorporating iron phosphide (FeP) particles into three‐dimensional (3D) porous graphene aerogel (GA) structure. The FeP formed in porous 3D GA (FeP/GA) is derived from electroactive Fe hexacyanoferrate (FeHCF). The advantage of incorporating FeP, in the porous 3D graphene network enables high accessibility for HER. As synthesized FeP/GA catalyst shows good electrocatalytic activity for HER in both acidic and alkaline solutions. The developed method can be useful for synthesizing metal hexacyanoferrate derived mono/bimetal phosphide catalyst in porous 3D graphene aerogels.     

Cobalt‐Embedded Nitrogen‐Rich Carbon Nanotubes Efficiently Catalyze Hydrogen Evolution Reaction at All pH Values

Despite being technically possible, splitting water to generate hydrogen is still practically unfeasible due mainly to the lack of sustainable and efficient catalysts for the half reactions involved. Herein we report the synthesis of cobalt‐embedded nitrogen‐rich carbon nanotubes (NRCNTs) that 1) can efficiently electrocatalyze the hydrogen evolution reaction (HER) with activities close to that of Pt and 2) function well under acidic, neutral or basic media alike, allowing them to be coupled with the best available oxygen‐evolving catalysts—which also play crucial roles in the overall water‐splitting reaction. The materials are synthesized by a simple, easily scalable synthetic route involving thermal treatment of Co²⁺‐embedded graphitic carbon nitride derived from inexpensive starting materials (dicyandiamide and CoCl₂). The materials’ efficient catalytic activity is mainly attributed to their nitrogen dopants and concomitant structural defects.     

钨掺杂的铁镍基层状氢氧化物用于电催化析氧和析氢反应

采用简便的一步水热合成法,在泡沫镍上原位生长微量W~(6+)掺入的Fe_(0.2)Ni(OH)_2双金属层状氢氧化物(LDH),以此来降低铁镍材料的过电势。通过场发射扫描电子显微镜(FESEM)、X射线衍射(XRD)、X射线光电子能谱(XPS)和拉曼光谱(Raman)等分析方法对材料形貌、组成、结构等进行表征,发现钨掺杂使催化剂材料的晶体结构和电子结构发生变化,W_(0.03)Fe_(0.2)Ni(OH)_2LDH表现出优异的电化学析氧(OER)和析氢(HER)性能。电化学测试表明该催化剂在25 mA·cm~(-2)电流密度下OER和HER过电势分别仅有271和208 mV,塔菲尔斜率分别为61和181 mV·dec~(-1)。此外,经过长达20 h计时电位稳定性测试后,材料的催化性能未见明显下降。     

Molybdenum Phosphosulfide: An Active,Acid‐Stable,Earth‐Abundant Catalyst for the Hydrogen Evolution Reaction

Introducing sulfur into the surface of molybdenum phosphide (MoP) produces a molybdenum phosphosulfide (MoP|S) catalyst with superb activity and stability for the hydrogen evolution reaction (HER) in acidic environments. The MoP|S catalyst reported herein exhibits one of the highest HER activities of any non‐noble‐metal electrocatalyst investigated in strong acid, while remaining perfectly stable in accelerated durability testing. Whereas mixed‐metal alloy catalysts are well‐known, MoP|S represents a more uncommon mixed‐anion catalyst where synergistic effects between sulfur and phosphorus produce a high‐surface‐area electrode that is more active than those based on either the pure sulfide or the pure phosphide. The extraordinarily high activity and stability of this catalyst open up avenues to replace platinum in technologies relevant to renewable energies, such as proton exchange membrane (PEM) electrolyzers and solar photoelectrochemical (PEC) water‐splitting cells.     

Cobalt‐Bridged Ionic Liquid Polymer on a Carbon Nanotube for Enhanced Oxygen Evolution Reaction Activity

By taking inspiration from the catalytic properties of single‐site catalysts and the enhancement of performance through ionic liquids on metal catalysts, we exploited a scalable way to place single cobalt ions on a carbon‐nanotube surface bridged by polymerized ionic liquid. Single dispersed cobalt ions coordinated by ionic liquid are used as heterogeneous catalysts for the oxygen evolution reaction (OER). Performance data reveals high activity and stable operation without chemical instability.     

Self‐Supported FeP‐CoMoP Hierarchical Nanostructures for Efficient Hydrogen Evolution

Fabricating highly efficient electrocatalysts for electrochemical hydrogen generation is a top priority to relief the global energy crisis and environmental contamination. Herein, a rational synthetic strategy is developed for constructing well‐defined FeP?CoMoP hierarchical nanostructures (HNSs). In general terms, the self‐supported Co nanorods (NRs) are grown on conductive carbon cloth and directly serve as a self‐sacrificing template. After solvothermal treatment, Co NRs are converted into well‐ordered Co?Mo nanotubes (NTs). Subsequently, the small‐sized Fe oxyhydroxide nanorods arrays are hydrothermally grown on the surface of Co?Mo NTs to form Fe?Co?Mo HNSs, which are then converted into FeP?CoMoP HNSs through a facile phosphorization treatment. FeP?CoMoP HNSs display high activity for hydrogen evolution reaction (HER) with an ultralow cathodic overpotential of 33 mV at 10 mA cm^?2 and a Tafel slope of 51 mV dec^?1. Moreover, FeP?CoMoP HNSs also possess an excellent electrochemical durability in alkaline media. First‐principles density functional theory (DFT) calculations demonstrate that the remarkable HER activitiy of FeP?CoMoP HNSs originates from the synergistic effect between FeP and CoMoP.     

Synergistically Interactive Pyridinic‐N–MoP Sites: Identified Active Centers for Enhanced Hydrogen Evolution in Alkaline Solution

For electrocatalysts for the hydrogen evolution reaction (HER), encapsulating transition metal phosphides (TMPs) into nitrogen‐doped carbon materials has been known as an effective strategy to elevate the activity and stability. Yet still, it remains unclear how the TMPs work synergistically with the N‐doped support, and which N configuration (pyridinic N, pyrrolic N, or graphitic N) contributes predominantly to the synergy. Here we present a HER electrocatalyst (denoted as MoP@NCHSs) comprising MoP nanoparticles encapsulated in N‐doped carbon hollow spheres, which displays excellent activity and stability for HER in alkaline media. Results of experimental investigations and theoretical calculations indicate that the synergy between MoP and the pyridinic N can most effectively promote the HER in alkaline media.     

Phase‐Junction Electrocatalysts towards Enhanced Hydrogen Evolution Reaction in Alkaline Media

To ensure sustainable hydrogen production by water electrolysis, robust, earth‐abundant, and high‐efficient electrocatalysts are required. Constructing a hybrid system could lead to further improvement in electrocatalytic activity. Interface engineering in composite catalysts is thus critical to determine the performance, and the phase‐junction interface should improve the catalytic activity. Here, we show that nickel diphosphide phase junction (c‐NiP₂/m‐NiP₂) is an effective electrocatalyst for hydrogen production in alkaline media. The overpotential (at 10 mA cm^?2) for NiP₂‐650 (c/m) in alkaline media could be significantly reduced by 26 % and 96 % compared with c‐NiP₂ and m‐NiP₂, respectively. The enhancement of catalytic activity should be attributed to the strong water dissociation ability and the rearrangement of electrons around the phase junction, which markedly improved the Volmer step and benefited the reduction process of adsorbed protons.