Nitrogen‐Doped Porous Molybdenum Carbide and Phosphide Hybrids on a Carbon Matrix as Highly Effective Electrocatalysts for the Hydrogen Evolution Reaction

The efficient evolution of hydrogen through electrocatalysis is considered a promising approach to the production of clean hydrogen fuel. Platinum (Pt)‐based materials are regarded as the most active hydrogen evolution reaction (HER) catalysts. However, the low abundance and high cost of Pt hinders the large‐scale application of these catalysts. Active, inexpensive, and earth‐abundant electrocatalysts to replace Pt‐based materials would be highly beneficial to the production of cost‐effective hydrogen energy. Herein, a novel organoimido‐derivatized heteropolyoxometalate, Mo4‐CNP, is designed as a precursor for electrocatalysts of the HER. It is demonstrated that the carbon, nitrogen, and phosphorus sources derived from the Mo4‐CNP molecules lead to in situ confined carburization, phosphorization, and chemical doping on an atomic scale, thus forming nitrogen‐doped porous molybdenum carbide and phosphide hybrids, which exhibit remarkable electrocatalytic activity for the HER. Such an organically functionalized polyoxometalate‐assisted strategy described here provides a new perspective for the development of highly active non‐noble metal electrocatalysts for hydrogen evolution.     

Engineering Cobalt Phosphide (CoP) Thin Film Catalysts for Enhanced Hydrogen Evolution Activity on Silicon Photocathodes

Transition metal phosphide catalysts have recently emerged as active, earth abundant alternatives to precious metals for the hydrogen evolution reaction in acid. High performance, scalable catalysts are necessary for the successful implementation of photoelectrochemical water splitting devices, which have the potential to generate hydrogen in a sustainable manner. Herein, a general synthetic route is reported to produce transition metal phosphide thin films, which is used to fabricate cobalt phosphide (CoP) catalysts with high average turnover frequency (TOF_avg), 0.48 H₂ s^?1 and 1.0 H₂ s^?1 at 100 and 120 mV overpotential, respectively. Furthermore, it is shown that CoP thin films can be applied to silicon photoabsorbers to generate one of the most active precious metal‐free crystalline silicon photocathodes to date, achieving ?10 mA cm^?2 at +0.345 V vs. reversible hydrogen electrode. The synthesis route presented here provides a platform for both fundamental studies of well‐defined electrocatalysts and the fabrication of high‐performance photoelectrodes.     

Mesoporous MoO3–x Material as an Efficient Electrocatalyst for Hydrogen Evolution Reactions

A unique approach for the synthesis of nonstoichiometric, mesoporous molybdenum oxide (MoO_3–x) with nanosized crystalline walls by using a soft template (PEO‐b‐PS) synthesis method is introduced. The as‐synthesized mesoporous MoO_3–x is very active and stable (durability > 12 h) for the electrochemical hydrogen evolution reaction (HER) under both acidic and alkaline conditions. The intrinsic MoO₃ serves as an HER electrocatalyst without the assistance of carbon materials, noble metals, or MoS₂ materials. The results from transmission electron microscopy and N₂ sorption techniques show that the as‐synthesized mesoporous MoO_3–x has large accessible pores (20–40 nm), which are able to facilitate mass transport and charge transfer during HER. In terms of X‐ray diffraction, X‐ray photoelectron spectroscopy, temperature‐programmed oxidation, and diffusive reflectance UV–vis spectroscopy, the mesoporous MoO_3–x exhibits mixed oxidation states (Mo⁵⁺, Mo⁶⁺) and an oxygen‐deficient structure. The as‐synthesized MoO_3–x only requires a low overpotential (≈0.14 V) to achieve a 10 mA cm^?2 current density in 0.1 m KOH and the Tafel slope is as low as 56 mV dec^?1. Density functional theory calculations demonstrate a change of electronic structure and the possible reaction pathway of HER. Oxygen vacancies and mesoporosity serve as key factors for excellent performance.     

Synergistically Tuning Water and Hydrogen Binding Abilities Over Co4N by Cr Doping for Exceptional Alkaline Hydrogen Evolution Electrocatalysis

Searching for highly efficient and cost‐effective electrocatalysts toward the hydrogen evolution reaction (HER) in alkaline electrolyte is highly desirable for the development of alkaline water splitting, but still remains a significant challenge. Herein, the rational design of Cr‐doped Co₄N nanorod arrays grown on carbon cloth (Cr–Co₄N/CC) that can efficiently catalyze the HER in alkaline media is reported. It displays outstanding performance, with the exceptionally small overpotential of 21 mV to obtain the current density of 10 mA cm^?2 and good stability in 1.0 m KOH, which is even better than the commercial Pt/C electrocatalyst, and much lower than most of the reported transition metal nitride‐based and other non‐noble metal‐based electrocatalysts toward the alkaline HER. Density functional theory (DFT) calculations and experimental results reveal that the Cr atoms not only act as oxophilic sites for boosting water adsorption and dissociation, but also modulate the electronic structure of Co₄N to endow optimized hydrogen binding abilities on Co atoms, thereby leading to accelerating both the alkaline Volmer and Heyrovsky reaction kinetics. In addition, this strategy can be extended to other metals (such as Mo, Mn, and Fe) doped Co₄N electrocatalysts, thus may open up a new avenue for the rational design of highly efficient transition metal nitride‐based HER catalysts and beyond.     

Active Edge Sites Engineering in Nickel Cobalt Selenide Solid Solutions for Highly Efficient Hydrogen Evolution

An effective multifaceted strategy is demonstrated to increase active edge site concentration in Ni_0.33Co_0.67Se₂ solid solutions prepared by in situ selenization process of nickel cobalt precursor. The simultaneous control of surface, phase, and morphology result in as‐prepared ternary solid solution with extremely high electrochemically active surface area (C _dl = 197 mF cm^?2), suggesting significant exposure of active sites in this ternary compound. Coupled with metallic‐like electrical conductivity and lower free energy for atomic hydrogen adsorption in Ni_0.33Co_0.67Se₂, identified by temperature‐dependent conductivities and density functional theory calculations, the authors have achieved unprecedented fast hydrogen evolution kinetics, approaching that of Pt. Specifically, the Ni_0.33Co_0.67Se₂ solid solutions show a low overpotential of 65 mV at ?10 mV cm^?2, with onset potential of mere 18 mV, an impressive small Tafel slope of 35 mV dec^?1, and a large exchange current density of 184 µA cm^?2 in acidic electrolyte. Further, it is shown that the as‐prepared Ni_0.33Co_0.67Se₂ solid solution not only works very well in acidic electrolyte but also delivers exceptional hydrogen evolution reaction (HER) performance in alkaline media. The outstanding HER performance makes this solid solution a promising candidate for mass hydrogen production.     

Unsaturated Sulfur Edge Engineering of Strongly Coupled MoS2 Nanosheet–Carbon Macroporous Hybrid Catalyst for Enhanced Hydrogen Generation

The low hydrogen adsorption free energy and strong acid/alkaline resistance of layered MoS₂ render it an excellent pH‐universal electrocatalyst for hydrogen evolution reaction (HER). However, the catalytic activity is dominantly suppressed by its limited active‐edge‐site density. Herein, a new strategy is reported for making a class of strongly coupled MoS₂ nanosheet–carbon macroporous hybrid catalysts with engineered unsaturated sulfur edges for boosting HER catalysis by controlling the precursor decomposition and subsequent sodiation/desodiation. Both surface chemical state analysis and first‐principles calculations verify that the resultant catalysts exhibit a desirable valence‐electron state with high exposure of unsaturated sulfur edges and an optimized hydrogen adsorption free energy, significantly improving the intrinsic HER catalytic activity. Such an electrocatalyst exhibits superior and stable catalytic activity toward HER with small overpotentials of 136 mV in 0.5 m H₂SO₄ and 155 mV in 1 m KOH at 10 mA cm^?2, which is the best report for MoS₂–C hybrid electrocatalysts to date. This work paves a new avenue to improve the intrinsic catalytic activity of 2D materials for hydrogen generation.     

Enhanced Electrocatalysis for Hydrogen Evolution Reactions from WS2 Nanoribbons

A facile route is developed to boost the electrocatalytic activity of WS₂ by chemically unzipping WS₂ nanotubes to form WS₂ nanoribbons (NRs) with increased edge content. Analysis indicates that the hydrogen evolution reaction activity is strongly associated with the number of exposed active edge sites. The formation of WS₂ NRs is an effective route for controlling the electrochemical properties of the 2D dichalcogenides, enabling their application in electrocatalysis.     

Doped‐MoSe2 Nanoflakes/3d Metal Oxide–Hydr(Oxy)Oxides Hybrid Catalysts for pH‐Universal Electrochemical Hydrogen Evolution Reaction

Clean hydrogen production is highly promising to meet future global energy demands. The design of earth‐abundant materials with both high activity for hydrogen evolution reaction (HER) and electrochemical stability in both acidic and alkaline environments is needed, in order to enable practical applications. Here, the authors report a non‐noble 3d metal Cl‐chemical doping of liquid phase exfoliated single‐/few‐layer flakes of MoSe₂ for creating MoSe₂/3d metal oxide–hydr(oxy)oxide hybrid HER‐catalysts. It is proposed that the electron‐transfer from MoSe₂ nanoflakes to metal cations and the chlorine complexation‐induced neutralization, as well as the in situ formation of metal oxide–hydr(oxy)oxides on the MoSe₂ nanoflakes' surface, tailor the proton affinity of the catalysts, increasing the number and HER‐kinetics of their active sites in both acidic and alkaline electrolytes. The electrochemical coupling between doped‐MoSe₂/metal oxide–hydr(oxy)oxide hybrids and single‐walled carbon nanotubes heterostructures further accelerates the HER process. Lastly, monolithic stacking of multiple heterostructures is reported as a facile electrode assembly strategy to achieve overpotential for a cathodic current density of 10 mA cm^?2 of 0.081 and 0.064 V in 0.5 m H₂SO₄ and 1 m KOH, respectively. This opens up new opportunities to address the current density versus overpotential requirements targeted in pH‐universal hydrogen production.     

Metal–Organic Framework Based Catalysts for Hydrogen Evolution

Highly efficient hydrogen evolution reactions (HERs) will determine the mass distributions of hydrogen‐powered clean technologies in the future. Metal–organic frameworks (MOFs) are emerging as a class of crystalline porous materials. Along with their derivatives, MOFs have recently been under intense study for their applications in various hydrogen production techniques. MOF‐based materials possess unique advantages, such as high specific surface area, crystalline porous structure, diverse and tunable chemical components, which offer attractive functionalities in catalyzing hydrogen evolution processes, by lowering reaction potentials, and speeding up reaction rates. Considering the rapid increase in research interest in hydrogen evolution in the last several years, this review aims to summarize recent advances in MOF‐associated hydrogen evolution research, including electrocatalytic, photocatalytic, and chemocatalytic HER. Particular attention is paid to the design and utilization of postsynthetic modification of MOFs, MOF‐supported catalysts, and MOF derivatives for highly efficient HER. The opportunities and challenges for MOF‐based materials in a hydrogen‐powered clean future are also discussed.     

Carbon‐Tailored Semimetal MoP as an Efficient Hydrogen Evolution Electrocatalyst in Both Alkaline and Acid Media

The electrolysis processes such as hydrogen evolution reaction (HER) require high efficient catalysts with robust surface stability. A high conductivity is also necessary to speed up the charge transport between the catalyst and the electrolyte. Recently, the observation of exceedingly high conductivity in the topological semimetal MoP, has provided a model catalyst to investigate the correlation between the electrical transport and the electrocatalytic activity for the HER. Thus, MoP is encapsulated in a Mo, P codoped carbon layer (MoP@C). This composite material exhibits outstanding HER performance, with an extremely low overpotential of 49 mV at a current density of 10 mA cm^?2 and a Tafel slope of 54 mV dec^?1 in an alkaline medium. In addition, electron transport analysis indicates that MoP exhibits high conductivity and mobility due to the existence of triple‐point fermions and a complex Fermi surface. Furthermore, the presence of P? C and Mo? C bonds at the interface between the carbon layer and the MoP particles modulates the band structure of MoP@C and facilitates fast electron transfer, accumulation, and subsequent delocalization, which are in turn responsible for the excellent HER activity.     

Implanting Isolated Ru Atoms into Edge‐Rich Carbon Matrix for Efficient Electrocatalytic Hydrogen Evolution

Although the maximized dispersion of metal atoms has been realized in the single‐atom catalysts, further improving the intrinsic activity of the catalysts is of vital importance. Here, the decoration of isolated Ru atoms into an edge‐rich carbon matrix is reported for the electrocatalytic hydrogen evolution reaction. The developed catalyst displays high catalytic performance with low overpotentials of 63 and 102 mV for achieving the current densities of 10 and 50 mA cm^?2, respectively. Its mass activity is about 9.6 times higher than that of the commercial Pt/C‐20% catalyst at an overpotential of 100 mV. Experimental results and density functional theory calculations suggest that the edges in the carbon matrix enhance the local electric field at the Ru site and accelerate the reaction kinetics for the hydrogen evolution. The present work may provide insights into electrocatalytic behavior and guide the design of advanced electrocatalysts.     

Ruthenium Oxide Nanosheets for Enhanced Oxygen Evolution Catalysis in Acidic Medium

The fabrication of highly active and robust hexagonal ruthenium oxide nanosheets for the electrocatalytic oxygen evolution reaction (OER) in an acidic environment is reported. The ruthenate nanosheets exhibit the best OER activity of all solution‐processed acid medium electrocatalysts reported to date, reaching 10 mA cm^?2 at an overpotential of only ≈255 mV. The nanosheets also demonstrate robustness under harsh oxidizing conditions. Theoretical calculations give insights into the OER mechanism and reveal that the edges are the origin of the high OER activity of the nanosheets. Moreover, the post OER analyses indicate, apart from coarsening, no observable change in the morphology of the nanosheets or oxidation states of ruthenium during the electrocatalytic process. Therefore, the present investigation suggests that ruthenate nanosheets are a promising acid medium OER catalyst with application potential in proton exchange membrane electrolyzers and beyond.     

Ruthenium‐Based Single‐Atom Alloy with High Electrocatalytic Activity for Hydrogen Evolution

Highly efficient and stable catalysts for the hydrogen evolution reaction, especially in alkaline conditions are crucial for the practical demands of electrochemical water splitting. Here, the synthesis of a novel RuAu single‐atom alloy (SAA) by laser ablation in liquid is reported. The SAA exhibits a high stability and a low overpotential, 24 mV@10 mA cm^?2, which is much lower than that of a Pt/C catalyst (46 mV) in alkaline media. Moreover, the turnover frequency of RuAu SAA is three times that of Pt/C catalyst. Density functional theory computation indicates the excellent catalytic activity of RuAu SAAs originates from the relay catalysis of Ru and Au active sites. This work opens a new avenue toward high‐performance SAAs via fast quenching of immiscible metals.     

Rational Design of Graphene‐Supported Single Atom Catalysts for Hydrogen Evolution Reaction

The proper choice of nonprecious transition metals as single atom catalysts (SACs) remains unclear for designing highly efficient electrocatalysts for hydrogen evolution reaction (HER). Herein, reported is an activity correlation with catalysts, electronic structure, in order to clarify the origin of reactivity for a series of transition metals supported on nitrogen‐doped graphene as SACs for HER by a combination of density functional theory calculations and electrochemical measurements. Only few of the transition metals (e.g., Co, Cr, Fe, Rh, and V) as SACs show good catalytic activity toward HER as their Gibbs free energies are varied between the range of –0.20 to 0.30 eV but among which Co‐SAC exhibits the highest electrochemical activity at 0.13 eV. Electronic structure studies show that the energy states of active valence d_z² orbitals and their resulting antibonding state determine the catalytic activity for HER. The fact that the antibonding state orbital is neither completely empty nor fully filled in the case of Co‐SAC is the main reason for its ideal hydrogen adsorption energy. Moreover, the electrochemical measurement shows that Co‐SAC exhibits a superior hydrogen evolution activity over Ni‐SAC and W‐SAC, confirming the theoretical calculation. This systematic study gives a fundamental understanding about the design of highly efficient SACs for HER.     

Nickel–Copper Alloy Encapsulated in Graphitic Carbon Shells as Electrocatalysts for Hydrogen Evolution Reaction

Searching for cost‐effective and high‐performance electrocatalysts for hydrogen production is of paramount importance. Herein, nickel‐copper (NiCu) alloy nanoparticles are encapsulated into graphitic shells via an ambient‐pressure chemical vapor deposition process. The resulting carbon‐encapsulated NiCu (denoted as NiCu@C) composite possesses a well‐defined core–shell structure with tunable thicknesses of the shells and is examined as electrocatalysts for the hydrogen evolution reaction (HER) in acidic, neutral, and alkaline solutions. Electrochemical measurements indicate that the activity of the NiCu@C highly depends on the thickness of the shell. Single‐layered graphene encapsulated NiCu nanoparticles show remarkable HER activity and durability. To obtain a current density of 10 mA cm^?2, overpotentials of 48, 164, and 74 mV are needed in electrolyte solutions with pH = 0, 7, and 14, respectively. Such low overpotentials render the composite as one of the most active nonprecious electrocatalysts. Accelerated durability tests demonstrate that the NiCu@C catalysts exhibit excellent stability. Density function theory calculations are conducted to investigate the electronic structures of the NiCu@C. It is found that the representative Ni₄₃Cu₁₂@C₂₄₀ model shows an ideal adsorption energy of hydrogen (?0.03 eV), manifesting its high HER activity.     

Electronic Structure Engineering of LiCoO2 toward Enhanced Oxygen Electrocatalysis

Developing low‐cost and efficient electrocatalysts for the oxygen evolution reaction and oxygen reduction reaction is of critical significance to the practical application of some emerging energy storage and conversion devices (e.g., metal–air batteries, water electrolyzers, and fuel cells). Lithium cobalt oxide is a promising nonprecious metal‐based electrocatalyst for oxygen electrocatalysis; its activity, however, is still far from the requirements of practical applications. Here, a new LiCoO₂‐based electrocatalyst with nanosheet morphology is developed by a combination of Mg doping and shear force‐assisted exfoliation strategies toward enhanced oxygen reduction and evolution reaction kinetics. It is demonstrated that the coupling effect of Mg doping and the exfoliation can effectively modulate the electronic structure of LiCoO₂, in which Co³⁺ can be partially oxidized to Co⁴⁺ and the Co–O covalency can be enhanced, which is closely associated with the improvement of intrinsic activity. Meanwhile, the unique nanosheet morphology also helps to expose more active Co species. This work offers new insights into deploying the electronic structure engineering strategy for the development of efficient and durable catalysts for energy applications.     

Self‐Limited on‐Site Conversion of MoO3 Nanodots into Vertically Aligned Ultrasmall Monolayer MoS2 for Efficient Hydrogen Evolution

MoS₂ has emerged as a promising alternative electrocatalyst for the hydrogen evolution reaction (HER) due to high intrinsic per‐site activity on its edge sites and S‐vacancies. However, a significant challenge is the limited density of such sites. Reducing the size and layer number of MoS₂ and vertically aligning them would be an effective way to enrich and expose such sites for HER. Herein, a facile self‐limited on‐site conversion strategy for synthesizing monolayer MoS₂ in a couple of nanometers which are highly dispersed and vertically aligned on 3D porous carbon sheets is reported. It is discovered that the preformation of well‐dispersed MoO₃ nanodots in 1–2 nm as limited source is the key for the fabrication of such an ultrasmall MoS₂ monolayer. As indicated by X‐ray photoelectron spectroscopy and electron spin resonance data, these ultrasmall MoS₂ monolayers are rich in accessible S‐edge sites and vacancies and the smaller MoS₂ monolayers the more such sites they have, leading to enhanced electrocatalytic activity with a low overpotential of 126 mV at 10 mA cm^?2 and 140 mV at 100 mA mg^?1 for HER. This state‐of‐the‐art performance for MoS₂ electrocatalysts enables the present strategy as a new avenue for exploring well‐dispersed ultrasmall nanomaterials as efficient catalysts.