Amorphous MoS2 nanosheets on MoO2 films/Mo foil as free-standing electrode for synergetic electrocatalytic hydrogen evolution reaction

A facile oxidation-sulfidation strategy is proposed to fabricate the vertically aligned amorphous MoS₂ nanosheets on MoO₂ films/Mo foil (MF) as free-standing electrode, which features as the integration of three merits (high conductivity, abundant exposures of active sites, and enhanced mass transfer) into one electrode for hydrogen evolution reaction (HER). Density functional theory (DFT) calculations reveal the strong interaction between MoS₂ and MoO₂, which can enhance the intrinsic conductivity with narrow bandgap, and decreases hydrogen adsorption free energy (ΔG_H1 = ~0.06 eV) to facilitate the HER process. Benefiting from the unique hierarchical structure with amorphous MoS₂ nanosheets on conductive MoO₂ films/MF to facilitate the electron/mass transfer by eliminate contact resistance, controllable number of stacking layers and size of MoS₂ slabs to expose more edge sites, the optimal MoS₂/MoO₂/MF exhibits outstanding activity with overpotential of 154 mV at the current density of 10 mA cm⁻², Tafel slope of 52.1 mV dec⁻¹, and robust stability. Furthermore, the intrinsic HER activity (vs. ECSA) on MoS₂/MoO₂/MF is significantly enhanced, which shows 4.5 and 18.6 times higher than those of MoS₂/MF and MoO₂/MF at overpotential of 200 mV, respectively.     

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.     

Heterostructure and phase engineering synergistically activated highly efficient alkaline hydrogen evolution in Mo2C/MoS2-rGO hybrids

Heterostructure and phase engineering are effective method to tune the electronic structure of MoS₂, which can activate and boost its intrinsic catalytic activity. Herein, the theoretical calculations reveal that the free energy of H1 adsorption (ΔG_H1) for Mo₂C (−0.65 eV) is lower than MoS₂ (2.05 eV), which is favorable for hydrogen adsorption. Inspired by the theoretical predictions, we develop a facile strategy to prepare nanostructured Mo₂C/MoS₂ dispersed on reduced graphene oxide (rGO) via a hydrothermal preparation and carburization reaction. Since the Mo₂C/MoS₂-rGO nanostructures with great deal of both MoS₂ and Mo₂C edges by heterostructure and phase engineering, which can induce massive active sites for HER on the surface of rGO, the intimate interfacial coupling effect between Mo₂C and MoS₂ can effectively improve the charge transfer rate. The Mo₂C/MoS₂-rGO catalyst exhibits exceptional HER properties, delivering a high turnover frequency (TOF) of 0.209 s⁻¹ at an overpotential of 200 mV in 0.1 M KOH. This work may open a new window for designing NPM electrocatalysts with highly efficient HER property based on earth-abundant materials.     

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.     

Defective-MoS2/rGO heterostructures with conductive 1T phase MoS2 for efficient hydrogen evolution reaction

As a two-dimensional material, molybdenum disulfide (MoS₂) exhibits great potential to replace metal platinum-based catalysts for hydrogen evolution reaction (HER). However, poor electrical conductivity and low intrinsic activity of MoS₂ limit its application in electrocatalysis. Herein, we prepare a defective-MoS₂/rGO heterostructures material containing 1T phase MoS₂ and evaluate its HER performance. The experimental results shown that defective-MoS₂/rGO heterostructures exhibits outstanding HER performance with a low overpotential at 154.77 mV affording the current density of 10 mA cm^?2 and small Tafel slope of 56.17 mV dec^?1. The unique HER performance of as-prepared catalyst can be attributed to the presence of 1T phase MoS₂, which has more active sites and higher intrinsic conductivity. While the defects of as-prepared catalyst fully expose the active sites and further improve catalytic activity. Furthermore, the interaction between MoS₂ and rGO heterostructures can accelerate electron transfer kinetics, and effectively ensure that the obtained catalyst displays excellent conductivity and structural stability, so the as-prepared catalyst also exhibits outstanding electrochemical cycling stability. This work provides a feasible and effective method for preparation of defective-MoS₂/rGO heterostructures, which also supplies a new strategy for designing of highly active and conductive catalysts for HER.     

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.     

Nano-pom-pom multiphasic MoS2 grown on carbonized wood as electrode for efficient hydrogen evolution in acidic and alkaline media

Molybdenum disulfide (MoS₂), attracts great attention in hydrogen evolution reaction (HER) field, however, low catalytic activity sites and poor conductivity still limit its further application. In this study, an efficient hydrogen evolution electrode with nano-pom-pom multiphasic MoS₂ uniformly grew on porous carbonized wood (NP MoS₂/CW) was developed. Interestingly, the nano-pom-pom are stacked from sheets of MoS₂. Fully exposed active edges of nano-pom-pom MoS₂ and high excellent electrical conductivity of carbonized wood enhance collectively electrocatalytic performance for HER. Specifically, the NP MoS₂/CW electrode requires an overpotential of 109.5 mV and 305 mV to achieve the current density of 10 mA cm⁻² and 400 mA cm⁻², respectively (0.5 M H₂SO₄). NP MoS₂/CW has excellent electrocatalytic performance and stability in acidic and alkaline media due to the perfect combination of NP MoS₂ unique nanostructure and the unique properties of CW. Therefore, the present work provides a promising strategy into the rational development and utilization of MoS₂ for the development of hydrogen evolution.     

Interface engineering of the NiCo2O4@MoS2/TM heterostructure to realize the efficient alkaline oxygen evolution reaction

Electrochemical water splitting is considered as a promising strategy for the efficient hydrogen production, yet it is hindered by the sluggish oxygen evolution reaction (OER). Herein, heterostructure OER catalyst is fabricated by combining MoS₂ nanosheets with NiCo₂O₄ hollow sphere on Ti mesh. Benefiting from the heterogeneous nanointerface between NiCo₂O₄ and MoS₂, this electrocatalyst demonstrates excellent OER activity in basic environment with overpotentials of 313 and 380 mV achieving 10 and 100 mA cm⁻². The superb catalytic performance stems from hollow the nanostructure and interfacial engineering strategy that enhance intrinsic activity and provide faster charge transfer. Hence, this work provides a feasible path for exploiting the high-efficient catalysts.     

One-step potentiostatic electrodeposition of Ni–Se–Mo film on Ni foam for alkaline hydrogen evolution reaction

Exploring efficient, abundant, low-cost and stable materials for hydrogen evolution reaction (HER) is highly desired but still a challenging task. Herein, Ni–Se–Mo electrocatalysts supported on nickel foam (NF) substrate were synthesized by a facile one-step electrodeposition method. The Ni–Se–Mo film presents high electrocatalytic activity and stability toward HER, with a low overpotential of 101 mV to afford a current density of 10 mA cm⁻² in 1.0 M KOH medium. Such excellent HER performance of Ni–Se–Mo film induced by the synergistic effects from Mo-doped Ni–Se film leads to the fast electron transfer. This work provides the validity of interface engineering strategy in preparing highly efficient transition metal chalcogenides based HER electrocatalysts.     

Ni3S2-MoSx nanorods grown on Ni foam as high-efficient electrocatalysts for overall water splitting

In order to solve the problem of large overpotential in water electrolysis for hydrogen production, transition metal sulfides are promising bifunctional electrocatalysts for hydrogen evolution reaction/oxygen evolution reaction that can significantly reduce overpotential. In this work, Ni₃S₂ and amorphous MoS_x nanorods directly grown on Ni foam (Ni₃S₂-MoS_x/NF) were prepared via one-step solvothermal process, which were used as a high-efficient electrocatalyst for overall water splitting. The Ni₃S₂-MoS_x/NF composite exhibits very low overpotentials of 65 and 312 mV to reach 10 mA cm⁻² and 50 mA cm⁻² in 1.0 M KOH for HER and OER, respectively. Besides, it exhibits a low Tafel slope (81 mV dec⁻¹ for HER, 103 mV dec⁻¹ for OER), high exchange current density (1.51 mA cm⁻² for HER, 0.26 mA cm⁻² for OER), and remarkable long-term cycle stability. This work provides new perspective for further the development of highly effective non-noble-metal materials in the energy field.     

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.     

Three-dimensional interconnected MoS2 nanosheets on industrial 316L stainless steel mesh as an efficient hydrogen evolution electrode

The development of inexpensive and competent electrocatalysts for high-efficiency hydrogen evolution reaction (HER) has been greatly significant to realize hydrogen production in large scale. In this paper, we selected the inexpensive and commercially accessible stainless steel as the conductive substrate for loading MoS₂ as a cathode for efficient HER under alkaline condition. Interconnected MoS₂ nanosheets were grown uniformly on 316-type stainless steel meshes with different mesh numbers via a facile hydrothermal way. And the optimized MoS₂/stainless steel electrocatalysts exhibited superior electrocatalytic performance for HER with a low overpotential of 160 mV at 10 mA cm⁻² and a small Tafel slope of 61 mV dec⁻¹ in 1 M KOH. Systematic study of the electrochemical properties was performed on the MoS₂/stainless steel electrocatalysts in comparison with the commonly used carbon cloth to better comprehend the origin of the superior HER performance as well as stability. By collaborative optimization of MoS₂ nanosheets and the cheap stainless steel substrate, the interconnected MoS₂ nanosheets on stainless steel provide an alternative strategy for the development of efficient and robust HER catalysts in strong alkaline environment.     

Tunably fabricated nanotremella-like Bi2S3/MoS2: An excellent and highly stable electrocatalyst for alkaline hydrogen evolution reaction

Reasonable design of efficient and stable catalysts with low cost and abundant natural reserves is vital for electrocatalytic water splitting. Herein, novel nanotremella-like Bi₂S₃/MoS₂ composites with different mass ratios between Bi₂S₃ and MoS₂ have been successfully prepared through a hydrothermal approach and further applied to hydrogen evolution reaction (HER) in 1.0 M KOH electrolyte for the first time. When the mass ratio of Bi₂S₃ and MoS₂ is 5:5, as-prepared nanotremella-like Bi₂S₃/MoS₂ (marked as BMS-5) manifests favorable HER catalytic activity with overpotential of 124 mV at current density of 10 mA cm⁻² and relatively low Tafel slope of 123 mV dec⁻¹. Moreover, it exhibits an extraordinary durability for uninterrupted hydrogen generation. The enhanced HER performances are ascribed to the synergistic effects between Bi₂S₃ and MoS₂, giving rise to large electrocatalytic active area and fast HER kinetics. The results pave a new path to design and construct excellent Bi₂S₃/MoS₂ nanomaterials for electrocatalytic hydrogen generation.     

Synthesis of binder-free fluffy anemone-like MoS2 for electrocatalytic hydrogen evolution: A Mott-schottky study

Highly active anemone-like MoS₂ catalyst was vertically and directly deposited on fluorine-doped tin oxide (FTO) substrate via a straightforward facile hydrothermal method with excellent adhesion and appreciable stability for hydrogen evolution reaction (HER). MoS₂ catalyst with unique morphology full of active edge sites and surface areas was fabricated by varying synthesis time and specific concentration of precursors. Structural characteristics were investigated by X-ray diffraction pattern (XRD), and Raman spectroscopy. Field emission scanning electron microscopy (FESEM) images show the variation of morphology during synthesis time as a very important factor in the preparation process. It also reveals the lamellar structure of anemone-like MoS₂ with an average thickness of ~19 nm. Electrochemical tests including linear sweep voltammetry and electrochemical impedance spectroscopy were carried out. These tests suggest a high electrocatalytic activity for MoS₂/FTO electrode toward HER with a charge transfer resistance (R_ct) about 24 Ω, a Tafel slope of ~87 mV dec⁻¹, and an exchange current density of 0.063 mA cm⁻² for the optimum sample synthesized at 20 h during hydrothermal process. The catalytic activity of the samples for HER was carefully investigated and proposed in detailed discussions according to the Mott-Schottky equation for the first time. Based on Mott-Schottky analysis, the obtained samples are n-type semiconductors and the density of carriers (N_D) of samples was calculated. N_D of the optimum sample (sample B) obtained (2.23 ± 0.055) × 10¹⁷. Fabricated samples have good stability proved by repeating LSV test for 1000 cycles. This work optimizes the catalytic activity of the bare MoS₂ with a cost-effective, easy, and binder-free method. It is a promising base for future works on MoS₂ catalysts.     

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.     

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.     

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.     

Nanostructural Co–MoS2/NiCoS supported on reduced Graphene oxide as a high activity electrocatalyst for hydrogen evolution in alkaline media

There are many tremendous challenges to enhance the hydrogen evolution reaction (HER) activity of MoS₂. In this study, nanoflower-like Co–MoS₂/NiCoS structure supported on reduced Graphene Oxide (rGO) was rationally developed via a simple hydrothermal route, where the synergistic regulations of both interface structural and electronic conductivity were successfully presented by using controllable interface engineering and Co metal ions doped into MoS₂ nanosheets. Ascribed to the 3D flower-like nanostructure with massive active sites, the interface coupling effect between MoS₂ and Ni–Co–S phase, and Co-doped MoS₂ can modulate its surface electronic density. The optimal Co–MoS₂/NiCoS/rGO hybrid exhibits excellent HER activity in 1.0 M KOH, with a small overpotential (η₁₀, 84 mV) at 10 mA cm^?2 and a low Tafel slope (46 mV dec^?1), accompanied by good stability. This work provides an effective route to produce other electrocatalysts based on interface structure and electronic conductivity engineering for HER in the future.     

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.     

Preparation of ultrathin molybdenum disulfide dispersed on graphene via cobalt doping: A bifunctional catalyst for hydrogen and oxygen evolution reaction

The development of highly active and low-cost catalysts for hydrogen evolution reaction (HER) is significant for the development of clean and renewable energy research. Owing to the low H adsorption free energy, molybdenum disulfide (MoS₂) is regarded as a promising candidate for HER, but it shows low activity for oxygen evolution reaction (OER). Herein, graphene-supported cobalt-doped ultrathin molybdenum disulfide (Co–MoS₂/rGO) was synthesized via a one-pot hydrothermal method. The obtained hybrids modified electrode exhibits a high HER catalytic activity with a low overpotential of 147 mV at the current density of 10 mA cm⁻², a small Tafel slope of 49.5 mV dec⁻¹, as well as good electrochemical stability in acidic electrolyte. Meanwhile, the catalyst shows remarkable OER activity with a low overpotential of 347 mV at 10 mA cm⁻². The superior activity is ascribed not only to the high conductivity originated from the reduced graphene, but also to the synergistic effect between MoS₂ and cobalt.