Polyoxomolybdate-derived MoS2/nitrogen-doped reduced graphene oxide hybrids for efficient hydrogen evolution

Integrating MoS₂ with carbon-based materials, especially graphene, is an effective strategy for preparing highly active non-noble-metal electrocatalysts in the hydrogen evolution reaction (HER). This work demonstrates a convenient hydrothermal method to fabricate molybdenum disulfide nanosheets/nitrogen-doped reduced graphene oxide (MoS₂/NGO) hybrids using polyoxomolybdate as the Mo precursor. Introducing more defects and expanding interlayer spacing of MoS₂ can be achieved through decreasing the pH value of the reactive system due to the existed high-nuclear polyoxometalate clusters. MoS₂/NGO hybrids prepared at low pH exhibit superior HER activity to those obtained at high pH. MoS₂/NGO-pH1.5 exhibits an ultralow overpotential of 81 mV at 10 mA cm⁻², a low Tafel slope of 60 mV·dec⁻¹ and good stability in alkaline electrolyte. Such excellent electrocatalytic activity is contributed by the abundant HER catalytic active sites, the increased electrochemically-accessible area and the synergetic effects between the active MoS₂ catalyst and NGO support.     

Ultrathin MoS2 nanosheets in situ grown on rich defective Ni0.96S as heterojunction bifunctional electrocatalysts for alkaline water electrolysis

Developing earth-abundant and highly active bifunctional electrocatalysts are critical to advance sustainable hydrogen production via alkaline water electrolysis but still challenging. Herein, heterojunction hybrid of ultrathin molybdenum disulfide (MoS₂) nanosheets and non-stoichiometric nickel sulfide (Ni_0.96S) is in situ prepared via a facile one-step hydrothermal strategy, followed by annealing at 400 °C for 1 h. Microstructural analysis shows that the hybrid is composed of intimate heterojunction interfaces between Ni_0.96S and MoS₂ with exposed active edges provided by ultrathin MoS₂ nanosheets and rich defects provided by non-stoichiometric Ni_0.96S nanocrystals. As expected, it is evaluated as bifunctional electrocatalysts to produce both hydrogen and oxygen via water electrolysis with a hydrogen evolution reaction (HER) overpotential of 104 mV at 10 mA cm⁻² and an oxygen evolution reaction (OER) overpotential of 266 mV at 20 mA cm⁻² under alkaline conditions, outperforming most current noble-metal-free electrocatalysts. This work provides a simple strategy toward the rational design of novel heterojunction electrocatalysts which would be a promising candidate for electrochemical overall water splitting.     

N-doped carbon wrapped CoFe alloy nanoparticles with MoS2 nanosheets as electrocatalyst for hydrogen and oxygen evolution reactions

Developing efficient and cost-effective transition metal-based electrocatalysts for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is crucial to generate clean and renewable hydrogen energy. The construction of hybrid catalysts with multiple active sites is an effective approach to promote catalytic performance. Herein, a molybdenum disulfide (MoS₂)-based hybrid with N-doped carbon wrapped CoFe alloy (MoS₂/CoFe@NC) was synthesized through a typical hydrothermal method. The MoS₂/CoFe@NC exhibits excellent electrocatalytic performance with overpotentials of 172 mV for HER and 337 mV for OER at 10 mA cm⁻², and long-term stability of 24-h electrolytic reaction in 1 M KOH solution. The chemical coupling between MoS₂ and CoFe@NC provides improved electronic structures and more accessible active sites. The CoFe@NC substrate accelerates the charge transfer to MoS₂ through a synergistic effect. This work demonstrates that the CoFe@NC is a promising substrate for depositing MoS₂ nanosheets (NSs) to achieve excellent catalytic performance for both HER and OER.     

Hierarchical ZnS@C@MoS2 core-shell nanostructures as efficient hydrogen evolution electrocatalyst for alkaline water electrolysis

Low-cost and highly efficient electrocatalysts are critical to advance the hydrogen production industry via water electrolysis in alkaline media. Molybdenum disulfide (MoS₂) nanosheets as earth-abundant electrocatalyst became a star material due to its unique graphene-like layered structure favoring electron transfer for hydrogen evolution catalysis. However, its electrocatalytic activities greatly hindered by the poor conductivity and the fewer exposure of catalytically active edged sites. Herein, hierarchical ZnS@C@MoS₂ core-shell nanostructures were designed by using a bottom-up strategy combined with a simple selective etching. The coexistence of semiconductor ZnS and defective porous carbonaceous shell as the core not only enhanced the electrical conductivity, but also separated and loaded the exfoliated MoS₂ nanosheets which effectively proliferated the exposed catalytically active edge sites (Mo and S sites). Upon optimal conditions, hierarchical ZnS@C@MoS₂ core-shell nanostructures gave an overpotential of 118 mV at 10 mA/cm² with a Tafel slope value of 55.4 mV/dec and better cycling stability after 500 cycles during the alkaline HER process, superior to pristine MoS₂.     

Boosting electrochemical hydrogen evolution activity of MoS2 nanosheets via facile decoration of Au overlayer

--Owing to its unique physicochemical properties, two-dimensional (2D) layered MoS₂ has been proposed as a potential catalyst for efficient hydrogen evolution reaction (HER). However, their large-scale application is still hindered due to limited active sites, poor conductivity, and restacking during synthesis. Herein, we report a one-step hydrothermal route to grow MoS₂ nanosheets on molybdenum (Mo) foil substrate followed by Au decoration as an active cocatalyst to enhance the HER performance of MoS₂ nanosheets. A facile, quick, and controlled decoration of stable Au overlayer with different mass loadings was performed using a sputtering Au coating unit for different deposition times (10s, 30s, and 50s), thus paving the way for producing efficient and inexpensive HER electrocatalysts. Electrochemical studies of different Au–MoS₂/Mo hybrids demonstrate that the optimized Au–MoS₂/Mo-30s sample exhibits ultralow onset potential (52 ± 2 mV vs. RHE), small overpotentials of 136 ± 6 and 318 ± 3 mV (vs. RHE) at current densities of 10 and 100 mA cm^?2, a small Tafel slope (46.23 ± 6 mV/dec), along with an outstanding electrochemical stability over a couple of days. Presence of metallic 1T-phase of MoS₂, as well as the synergistic effect between MoS₂ and Au, result in enhanced electrical conductivity, high density of active sites, large electrochemically accessible surface area, and fast charge transfer at the catalyst-electrolyte interface for boosting HER activity of the hybrid catalyst.     

MoS2/NiFeS2 heterostructure as a highly efficient electrocatalyst for overall water splitting at high current densities

Searching for efficient, stable and low-cost nonprecious catalysts for oxygen and hydrogen evolution reactions (OER and HER) is highly desired in overall water splitting (OWS). Herein, presented is a nickel foam (NF)-supported MoS₂/NiFeS₂ heterostructure, as an efficient electrocatalyst for OER, HER and OWS. The MoS₂/NiFeS₂/NF catalyst achieves a 500 mA cm⁻² current density at a small overpotential of 303 mV for OER, and 228 mV for HER. Assembled as an electrolyzer for OWS, such a MoS₂/NiFeS₂/NF heterostructure catalyst shows a quite low cell voltage (≈1.79 V) at 500 mA cm⁻², which is among the best values of current non-noble metal electrocatalysts. Even at the extremely large current density of 1000 mA cm⁻², the MoS₂/NiFeS₂/NF catalyst presents low overpotentials of 314 and 253 mV for OER and HER, respectively. Furthermore, MoS₂/NiFeS₂/NF shows a ceaseless durability over 25 h with almost no change in the cell voltage. The superior catalytic activity and stability at large current densities (>500 mA cm⁻²) far exceed the benchmark RuO₂ and Pt/C catalysts. This work sheds a new light on the development of highly active and stable nonprecious electrocatalysts for industrial water electrolysis.     

1T/2H MoS2/MoO3 hybrid assembles with glycine as highly efficient and stable electrocatalyst for water splitting

Despite great efforts have been made during the past decade to improve the efficiency of hydrogen evolution reaction (HER) onto the MoS₂-based electrocatalysts via increasing the number of active sites, further improvements are crucial to avoid the detachment of 2D MoS₂ nanosheets from the substrate during the long-term water splitting under intense HER. In this study, we report on the formation of highly efficient and surprisingly stable layer composed of 2D nanoplatelets from the hybrid-type MoS₂ as a new prospective electrocatalyst for HER from acidic water solution. This layer was formed via one-pot hydrothermal synthesis in the solution containing ammonium heptamolybdate, thiourea and glycine (Gly). The products obtained were characterized by SEM, HRTEM, XRD, Raman, XPS, and potential cycling. Note that at the designed hybrid-type MoS₂/MoO₃-Gly nanoplatelets the HER rate can achieve a stable electrochemical performance for days with ~100 mA cm⁻² current density at −0.35 V potential vs RHE.     

In-situ synthesis of porous Ni2P nanosheets for efficient and stable hydrogen evolution reaction

The design and development of highly efficient and stable non-noble metal electrocatalysts for hydrogen evolution reaction (HER) have attracted increasing attention. However, some key issues related to large overpotential, high cost and poor stability at high current density still remains challenging. In this work, we report a facile in-situ integration strategy of porous Ni₂P nanosheet catalysts on 3D Ni foam framework (PNi₂P/NF) for efficient and stable HER in alkaline medium. The two-step method can creates high density of ultra-thin porous Ni₂P nanosheets firmly rooted into Ni foam substrate which can guarantee excellent electrical contacts, strong substrate adherence and large amount of active sites. Such a binder-free flexible HER cathode exhibits superior electrocatalytic performance with an overpotential of 134 mV at current density of 10 mA cm⁻². It also shows superior stability at higher current densities of 100 and 500 mA cm⁻² for at least 48 h and negligible performance degradation is observed.     

Ultrathin WS2 nanosheets vertically aligned on TiO2 nanobelts as efficient alkaline hydrogen evolution electrocatalyst

Highly efficient and durable non-noble metal-based hydrogen evolution electrocatalysts are critical to advance the production of hydrogen energy via alkaline water electrolysis. Herein, we prepared a novel TiO₂@WS₂ hybrid via a facile and scalable two-step hydrothermal strategy combined with selective etching. Benefited from acid-etched TiO₂ nanobelts with rough surface as substrate, ultrathin WS₂ nanosheets nucleated and vertically grew into few layers in the confined configuration with more exposed active edges. Furthermore, the partial incorporation of oxygen in WS₂ inherited from the remaining O–W bonds of tungsten precursor enhanced the electrical conductivity of the hybrid. Therefore, TiO₂@WS₂ hybrid was proved to be efficient and durable electrocatalyst for hydrogen evolution in alkaline medium. Upon optimal conditions, the hybrid only required a small onset overpotential of 95 mV and a low overpotential of 142 mV at 10 mA cm⁻², superior to pristine WS₂ and TiO₂. In addition, better cycling stability during the alkaline HER process was also obtained, indicating its capability in future practical application. The synthesis strategy presents a cost-effective approach to produce efficient WS₂-based HER electrocatalyst for electrochemical water splitting.     

Ru–MoS2@PPy hollow nanowire as an ultra-stable catalyst for alkaline hydrogen evolution reaction

Electrocatalytic hydrogen evolution reaction (HER) is one of the green and effective method to produce clean hydrogen energy. However, the development of non-Pt HER catalysts with excellent catalytic activity and long-term stability still remains a great challenge. Herein, a vertically aligned core-shell structure material with hollow polypyrrole (PPy) nanowire as a core and Ru-doped MoS₂ (Ru–MoS₂) nanosheets as a shell is firstly reported as a highly efficient and ultra-stable catalyst for HER in alkaline solutions. Results indicate that Ru–MoS₂@PPy catalyst demands a low overpotential of 37 mV at 10 mA cm^?2. In addition, the overpotential at 100 mA cm^?2 is 157 mV and it is almost unchanged after 40,000 cyclic voltammetry cycles. The existence of PPy core not only ensures the vertical growth of MoS₂ nanosheets to expose more edge sites, but also promotes the rapid transfer of electrons, contributing to the improvement of catalytic activity. More importantly, the strong interface interaction between MoS₂ and PPy prevents the collapse of the vertical structure of MoS₂ sheets in the electrocatalytic process and greatly enhances the stability of catalysts, which offers an effective strategy to design and synthesize the HER catalysts with superior catalytic stability.     

Engineering of molybdenum sulfide nanostructures towards efficient electrocatalytic hydrogen evolution

Water splitting is an appealing way of producing hydrogen fuel, which requires efficient and affordable electrode materials to make the overall process viable. In the last couple years, abundant transition metals (and their compounds and hybrids) attracted ever-growing attention as the alternatives of noble metals. Particularly the layered transition metal dichalcogenide (TMDs) are interesting with their stability and promising electrocatalytic performance for hydrogen evolution reaction (HER). However, the neat TMDs are often poor in terms of the abundance of catalytically active sites and electrical conductivity, which limit their application potential significantly. Herein, as a proof-of-concept, we report on the design of a high-performance electrocatalyst system formed by the decoration of ultrasmall molybdenum sulfide (MoS₂) nanosheets on carbon nanotubes (CNTs). The ultrasmall MoS₂ nanosheets provide distorted lattice, confined size and rich defects, which endows the resulting electrocatalysts (MoS₂/CNT) with abundant active sites. The CNTs, on the other hand, serve as the conductive net for ensuring electrocatalytic performance. As a result, the hybrid electrocatalyst exhibits excellent electrocatalytic performance for HER, achieving a large current density of 100 mA cm⁻² at overpotential of only 281 mV and a small Tafel slope of 43.6 mV dec⁻¹ along with a decent stability. Our results are of high interest for electrocatalyst technologists as well as hydrogen fuel researchers.     

Flower-like HEA/MoS2/MoP heterostructure based on interface engineering for efficient overall water splitting

The development of cheap, efficient, and active non-noble metal electrocatalysts for total hydrolysis of water (oxygen evolution reaction (OER) and hydrogen evolution reaction (HER)) is of great significance to promote the application of water splitting. Herein, a heterogeneous structured electrode based on FeAlCrMoV high-entropy alloy (HEA) was synthesized as a cost-effective electrocatalyst for hydrogen and oxygen evolution reactions in alkaline media. In combination of the interfacial synergistic effect and the high-entropy coordination environment, flower-like HEA/MoS₂/MoP exhibited the excellent HER and OER electrocatalytic performance. It showed a low overpotential of 230 mV at the current density of 10 mA cm⁻² for OER and 148 mV for HER in alkaline electrolyte, respectively. Furthermore, HEA/MoS₂/MoP as both anode and cathode also exhibited an overpotential of 1.60 V for overall water splitting. This work provides a new strategy for heterogeneous structure construction and overall water splitting based on high-entropy alloys.     

Self-standing and efficient bifunctional electrocatalyst for overall water splitting under alkaline media enabled by Mo1-xCoxS2 nanosheets anchored on carbon fiber paper

The layered MoS₂ nanostructures have been widely used in the electrochemical hydrogen evolution reaction (HER), but rarely applied in overall water splitting application for their ignorable oxygen evolution reaction (OER) activity. To address this issue, a novel self-standing and bifunctional electrocatalyst, consisting of Co-doped MoS₂ nanosheets anchored on carbon fiber paper, has been prepared via hydrothermal method. Taking advantage of conductive substrate of carbon fiber paper, sufficient-exposed active edges of MoS₂ sheets, and metallic character caused by Co-doping, our electrode exhibits high-efficient bifunctional activities for the overall water splitting in alkaline electrolyte (1 M KOH), which can produce a current density of 20 mA cm⁻² at an overpotential of 197 mV for HER and 235 mV for OER.     

Multi-shelled CoS2–MoS2 hollow spheres as efficient bifunctional electrocatalysts for overall water splitting

The exploration of highly efficient non-precious electrocatalysts is essential for water splitting devices. Herein, we synthesized CoS₂–MoS₂ multi-shelled hollow spheres (MSHSs) as efficient electrocatalysts both for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) using a Schiff base coordination polymer (CP). Co-CP solid spheres were converted to Co₃O₄ MSHSs by sintering in air. CoS₂–MoS₂ MSHSs were obtained by a solvothermal reaction of Co₃O₄ MSHSs and MoS₄²⁻ anions. CoS₂–MoS₂ MSHSs have a high specific surface area of 73.5 m²g^-1. Due to the synergistic effect between the CoS₂ and MoS₂, the electrode of CoS₂–MoS₂ MSHSs shows low overpotential of 109 mV with Tafel slope of 52.0 mV dec⁻¹ for HER, as well as a low overpotential of 288 mV with Tafel slope of 62.1 mV dec⁻¹ for OER at a current density of 10 mA cm⁻² in alkaline solution. The corresponding two-electrode system needs a potential of 1.61 V (vs. RHE) to obtain anodic current density of 10 mA cm⁻² for OER and maintains excellent stability for 10 h.     

Three-dimensional ZnCo/MoS2–Co3S4/NF heterostructure supported on nickel foam as highly efficient catalyst for hydrogen evolution reaction

Exploring inexpensive and earth-abundant electrocatalysts for hydrogen evolution reactions is crucial in electrochemical sustainable chemistry field. In this work, a high-efficiency and inexpensive non-noble metal catalysts as alternatives to hydrogen evolution reaction (HER) was designed by one-step hydrothermal and two-step electrodeposition method. The as-prepared catalyst is composed of the synergistic MoS₂–Co₃S₄ layer decorated by ZnCo layered double hydroxides (ZnCo-LDH), which forms a multi-layer heterostructure (ZnCo/MoS₂–Co₃S₄/NF). The synthesized ZnCo/MoS₂–Co₃S₄/NF exhibits a small overpotential of 31 mV and a low Tafel plot of 53.13 mV dec^?1 at a current density of 10 mA cm^?2, which is close to the HER performance of the overpotential (26 mV) of Pt/C/NF. The synthesized ZnCo/MoS₂–Co₃S₄/NF also has good stability in alkaline solution. The excellent electrochemical performance of ZnCo/MoS₂–Co₃S₄/NF electrode originates from its abundant active sites and good electronic conductivity brought by the multilayer heterostructure. This work provides a simple and feasible way to design alkaline HER electrocatalysts by growing heterostructures on macroscopic substrates.     

Phosphorus-doping induced electronic modulation of CoS2–MoS2 hollow spheres on MoO2 film-Mo foil for synergistically boosting alkaline hydrogen evolution reaction

Combination of anionic doping and multicomponent synergism are effective approach to improve the performance of electrocatalysts toward hydrogen evolution reaction (HER) process. Herein, P-doped CoS₂–MoS₂ hollow spheres assembled by countless sheets on oxidized Mo foil (P–CoS₂/MoS₂/MoO₂) was synthesized by hydrothermal and phosphorization process. The unique hollow structure with countless sheets as wall endows more accessible active sites, fast electron/mass transport and high conductivity. P-doping could redistribute the local charge density and optimize the surface charge state to improve the intrinsic activity and accelerate reaction kinetics. The optimized P–CoS₂/MoS₂/MoO₂ exhibits an outstanding HER performance with an overpotential of 85 mV to reach 10 mA cm⁻², a small Tafel slope of 84.6 mV dec⁻¹, superior intrinsic HER activity and robust durability under alkaline solution. This work proposed a feasible strategy to build the hollow, heterostructured and binder-free electrode in renewable energy application.     

Phase controlled synthesis and the phase dependent photo-and electrocatalysis of CdS@CoMo2S4/MoS2 catalyst for HER

Herein we report a heterostructure with ultrathin nanosheets of Co-doped molybdenum sulfide on CdS nanorod array (donated as CdS@CoMo₂S₄/MoS₂) by hydrothermal synthesis. Firstly, elemental Co doping MoS₂ (CoMo₂S₄) delivers the double benefits of increased active sites and enhanced conductivity. Secondly, the structural characteristics maximally exposes the MoS₂ edges and enlarges interfacial contact area between the composite catalyst and electrolyte, as well as the efficient interfacial charge transfer. The ratio of CoMo₂S₄/MoS₂ in CdS@CoMo₂S₄/MoS₂ plays a crucial role for the enhanced photo-assistant electrocatalytic hydrogen evolution reaction (HER). We can tune the ratio of CoMo₂S₄/MoS₂ by controlling the preparation time or the ratio of precursor of Co/Mo. The catalyst with predominant MoS₂ phase shows superior photocatalytic HER performance with a high H₂ production rate of 46.60 μmol mg⁻¹ h⁻¹. Meanwhile, the catalyst with predominant CoMo₂S₄ phase exhibits not only relatively low overpotential of 172 mV at 10 mA cm⁻², which outperforms most values that have been reported on catalyst supported on ITO substrate, but also possesses H₂ production rate of 23.47 μmol mg⁻¹ h⁻¹. The superior photo-assistant electrocatalytic HER activity results from the synergistically structural and electronic modulations, as well as the proper energy band alignment between MoS₂ and CdS. This investigation could provide an approach to integrate the electro- and photocatalytic activities for HER, especially the photo responding behaviour at a bias potential which is meaningful to produce H₂ for actual application.     

Mo-chelate strategy for synthesizing ultrasmall Mo2C nanoparticles embedded in carbon nanosheets for efficient hydrogen evolution

Production of hydrogen from electrochemical water splitting has been regarded as one of the most economic and sustainable techniques for green fuel production. It is significant and challengeable to develop highly efficient and low cost noble metal-free electrocatalysts. Presently, molybdenum-based electrocatalysts were regarded as potential alternatives for the hydrogen evolution reaction (HER). Here, the well-dispersed and ultrasmall Mo₂C nanoparticles (NPs) anchored on 2D carbon nanosheets were synthesized by designing chelate precursor and following pyrolysis, which was proved to be an effective approach for preparing carbon-loaded Mo₂C NPs. The as-obtained Mo₂C/C material exhibits an outstanding activity and stability in hydrogen evolution reaction (HER). It needs an overpotential of 147 mV to drive 10 mA cm⁻² and Tafel slope is 64.2 mV dec⁻¹ in alkaline medium, implying that Mo₂C/C material will be a potential noble metal-free electrocatalyst for HER. The design of Mo-chelate precursor is a feasible route to synthesize ultrafine Mo₂C and it can provide a reference for synthesizing other nanoparticles and hindering particle coalescence at high preparation temperature.     

MoS2-supported on free-standing TiO2-nanotubes for efficient hydrogen evolution reaction

The electrochemical production of hydrogen is a promising and flexible approach towards the conversion of intermittent renewable energy sources into clean chemical fuel. However, low-cost, efficient, and durable electrocatalysts are yet to be developed to attain economies of scale in hydrogen generation. In this study, we fabricated highly ordered free-standing TiO₂ nanotube arrays (TiO₂-NTs), by simply anodizing Ti foils. The tube length, diameter, wall thickness, and surface structure of the TiO₂-NTs can be controlled by adjusting the anodization conditions. Subsequently, we synthesized and supported MoS₂ layers on free-standing TiO₂-NTs as an active material for the hydrogen evolution reaction (HER), using a slow evaporation method. The layers of MoS₂ uniformly disperse on the entire surface of the TiO₂-NTs composite. The electrochemical test shows that the MoS₂-supported free-standing (MoS₂/TiO₂-NTs) system exhibits excellent HER performance in acidic media with a low overpotential at 10 mA cm⁻² (170 mV), as well as small Tafel slope (70 mV decade⁻¹). Also, the MoS₂/TiO₂-NTs displays superior durability for HER after 5000 continuous potential cycles between −0.4 and + 0.2 (V vs. RHE). Our results demonstrate the potential application of MoS₂/TiO₂-NTs composite for cost-effective electrochemical production of hydrogen.     

Zinc oxide functionalized molybdenum disulfide heterostructures as efficient electrocatalysts for hydrogen evolution reaction

Technology urges to replace the state-of-the-art catalysts such as platinum with low cost, earth abundant and durable electrocatalysts for efficient hydrogen evolution (HER) reaction which is going to become the major sustainable production of energy in future. Herein, we present the heterostructure based MoS₂.ZnO (MZO) heterostructures for successful electrochemical water splitting process. For HER, the prepared MoS₂.ZnO nanocomposites show the over potential as low as 239 mV at cathodic current density 10 mAcm⁻² with an exchange current density of 3.2 μAcm⁻². A Tafel slope of about 62 mV per decade suggested to have the Volmer-Heyrovsky mechanism for the HER process with MoS₂.ZnO nanocomposite as the catalyst. The small Tafel slope indicates a promising electrocatalyst for HER in practical application. The strong interface formation at the MoS₂.ZnO heterostructure facilitates higher catalytic activity and excellent cycling stability. The heterostructure formation based on semiconductor two dimensional (2D) transition metal dichalcogenides (TMDC) open up new avenues for effective manipulation of HER catalysts.