Solvothermal synthesis of oxygen-incorporated MoS2-x nanosheets with abundant undercoordinated Mo for efficient hydrogen evolution

Activating the inert basal planes of layered molybdenum disulfide (MoS₂) is critical to deliver its high hydrogen evolution reaction (HER) efficiency. Herein, oxygen-incorparated MoS_x with abundant undercoordinated Mo atoms is fabricated by a facile solvothermal procedure, which realizes synergistically structural and electronic regulations of MoS₂ inert basal planes. Experiment results reveal that oxygen incoparation can effectively modulate the electronic structure and further optimize the intrinsic conductivity, while the defect-rich structure with abundant undercoordinated Mo atoms increases the number of active sites. Moreover, the influence of solvothermal temperature on activity of MoS_2-x is also investigated. The achieved MoS_x electrocatalyst prepared at 220 °C exhibits a superior activity for HER with a low overpotential of 191 mV at 10 mA cm⁻², a small Tafel slope of 67 mV dec⁻¹, and an excellent stability due to the largest surface area and superior conductivity.     

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.     

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.     

Micrometer‒Scale biomass carbon tube matrix auxiliary MoS2 heterojunction for electrocatalytic hydrogen evolution

Electrocatalytic materials for hydrogen evolution reaction are crucial in water splitting. Developing low‒cost and highly active catalyst remains an enormous challenge. Herein, we reported a simple approach to synthesize a molybdenum disulfide/micrometer‒scale biomass carbon tube matrix (BCTM) which is derived from available and accessible plant wild celery. Molybdenum disulfide (MoS₂) nanosheet could be well dispersed on the BCTM to form porous structure, while the BCTM can enhance the conductivity of MoS₂ nanosheet. The synergistic effects between the MoS₂ nanosheet and BCTM contribute to high hydrogen evolution reaction activity. MoS₂/BCTM shows admirable catalytic ability with a low overpotential of 176 mV at 10 mA cm⁻², a small Tafel slope 51 mV·dec⁻¹, and outstanding stability over 2000 cycles under acidic conditions. This novel strategy provides a low‒cost route to synthesize excellent MoS₂‒based catalyst, which may widely apply in the fields of electrocatalysis and photocatalysis.     

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.     

Mesoporous nickel-sulfide/nickel/N-doped carbon as HER and OER bifunctional electrocatalyst for water electrolysis

The development of non-precious metal-based highly active bi-functional electrocatalysts for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is critical factor for making water electrolysis a viable process for large-scale industrial applications. In this study, bi-functional water splitting electrocatalysts in the form of nickel-sulfide/nickel nanoparticles integrated into a three-dimensional N-doped porous carbon matrix, are prepared using NaCl as a porous structure-forming template. Microstructures of the catalytic materials are characterized by scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy and N₂ adsorption-desorption analysis. The most active catalyst synthesized in this study exhibits a low HER overpotential of 70 mV at 10 mA cm⁻² and a low Tafel slope of 45 mV dec⁻¹. In OER, the optimized sample performs better than a state-of-the-art RuO₂ catalyst and produces an overpotential of 337 mV at 10 mA cm⁻², lower than that of RuO₂. The newly obtained materials are also used as HER/OER electrocatalysts in a specially assembled two-electrode water splitting cell. The cell demonstrates high activity and good stability in 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.     

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.     

Cobalt phosphide nanoparticles embedded in 3D N-doped porous carbon for efficient hydrogen and oxygen evolution reactions

An electrocatalyst based on a unique three-dimensional (3D) N-doped porous carbon sheet networks embedded with CoP₂ nanoparticles (CoP₂@3D-NPC) was synthesized by a facile pyrolysis process as well as an in-situ phosphatization method. The improved CoP₂@3D-NPC hybrid materials show excellent electrocatalytic activity toward HER and OER. This material provides a low overpotential of 126 mV at 10 mA cm⁻² in 0.5 M H₂SO₄ and 167 mV at 20 mA cm⁻² in 1.0 M KOH for HER with a small Tafel slope value of 59 mV dec⁻¹, respectively. Besides, it is also active for the OER under alkaline conditions. Such a prominent property of the CoP₂@3D-NPC electrocatalyst could be attributed to its excellent electrical conductivity of 3D carbon substrate, strong synergistic effect between CoP₂ nanoparticles and carbon nanosheet as well as extra active sites created by the N-doped structure.     

Bimetallic metal-organic framework derived electrocatalyst for efficient overall water splitting

The development of bifunctional catalysts that can be applied to both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is widely regarded as a key factor in the production of sustainable hydrogen fuel by electrochemical water splitting. In this work, we present a high-performance electrocatalyst based on nickel-cobalt metal-organic frameworks for overall water splitting. The as-obtained catalyst shows low overpotential to reaches the current density of 10 mA cm⁻² with 249 mV for OER and 143 mV for HER in alkaline media, respectively. More importantly, when the electrolyzer was assembled with the as-prepared catalyst as anode and cathode simultaneously, it demonstrates excellent activity just applies a potential of 1.68 V to achieve 10 mA cm⁻² current density for overall water splitting.     

N,P-co-doped carbon coupled with CoP as superior electrocatalysts for hydrogen evolution reaction and overall water splitting

To achieve high activity and stability for both hydrogen and oxygen evolution reactions through the non-precious-metal based electrocatalysts is still facing the great challenge. Herein, we demonstrate a facile strategy to prepare CoP nanoparticles (NPs) loaded on N, P dual-doped carbon (NPC) electrocatalysts with high concentration N and P dopants through a pyrolysis-deposition-phosphidation process. The great bifunctional electrocatalytic activity for both HER (the overpotential of 98 mV and 86 mV at 10 mA cm⁻² in both 0.5 M H₂SO₄ and 1 M KOH electrolytes, respectively) and OER (the overpotential of 300 mV at 10  mA cm⁻² in 1 M KOH electrolyte) were achieved. When CoP@NPC hybrid was used as two electrodes in the 1 M KOH electrolyte system for overall water splitting, the needed cell potential for achieving the current density of 10 mA cm⁻² is 1.6 V, and it also showed superior stability for HER and OER after 10 h’ test with almost negligible decay. Experimental results revealed that the P atoms in CoP were the active sites for HER and the CoP@NPC hybrid showed excellent bifunctional electrocatalytic properties due to the synergistic effects between the high catalytic activity of CoP NPs and NPC, in which the doping of N and P in carbon led to a stronger polarization between Co and P in CoP, promoting the charge transfer from Co to P in CoP, enhancing the catalytic activity of P sites and Co sites in CoP for HER and OER, respectively. Specifically, the improvements could result from the changed charge state, the increased active specific surface area, and the facilitated reaction kinetics by N, P co-doping and admixture. This work provides a high-efficient, low-cost and stable electrocatalyst for overall water splitting, and throws light on rational designing high performance electrocatalysts.     

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.     

Atomic-scale intercalation of amorphous MoS2 nanoparticles into N-doped carbon as a highly efficient electrocatalyst for hydrogen evolution reaction

The hydrogen evolution reaction (HER) properties of the catalysts are significantly dependent on their microscopic structure. Interfacial engineering at the atomic level is the main approach to design high performance of electrocatalysts. Herein, an interfacial modulation strategy is proposed to fabricate monolayer amorphous MoS₂ nanoparticles with an average of 3.5 nm in diameter stuck in multilayer N-doped carbon (MoS₂/NC), boosting a high HER activity. The amorphous MoS₂ could provide more edge active sites and NC layers endow the fast electron transfer. The XPS, Raman spectra and density functional theory (DFT) calculations reveal that the C–S bond in MoS₂/NC provides the fast electron transfer and decreases H binding energy. Benefiting the unique sandwiched structure, the MoS₂/NC boosts a low overpotential of 152.6 mV at a current density of 10 mA cm⁻², a small Tafel slope of 60.3 mV dec⁻¹, and outstanding long-term stability with 97.3% retention for over 24 h. This strategy provides a new opportunity and development of interfacial engineering for turning intrinsic catalytic activity for water splitting.     

A feasible and environmentally friendly method to simultaneously synthesize MoS2 quantum dots and pore-rich monolayer MoS2 for hydrogen evolution reaction

MoS₂ has been one of a widely researched hydrogen evolution reaction (HER) catalyst materials in recent years. However, the basal plane of MoS₂ is considered to be inactive to hinder its further development. Herein, a new mass-scalable and facile intercalation method for the fabrication of multiple products, including pore-rich monolayer MoS₂ (PR MoS₂) and MoS₂ quantum dots (MoS₂ QDs), has been developed via the gas phase etching of bulk MoS₂ in an acetone vapor atmosphere. The obtained monolayer MoS₂ QDs with a narrow lateral size distribution (average size: 2.5 nm) present excitation-independent photoluminescence emission. Furthermore, the PR MoS₂ shows a significantly enhanced HER electrocatalytic activity and good stability in 0.5 M H₂SO₄ solution with a small overpotential of 241 mV at a current density of 10 mA cm⁻². These results demonstrate that the as-prepared PR MoS₂ is very promising for the application in HER.     

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.     

Synthesis and electrocatalytic activity of Ni0.85Se/MoS2 for hydrogen evolution reaction

Recently, the replacement of expensive platinum-based catalytic materials with non-precious metal materials to electrolyze water for hydrogen separation has attracted much attention. In this work, Ni_0.85Se, MoS₂ and their composite Ni_0.85Se/MoS₂ with different mole ratios are prepared successfully, as electrocatalysts to catalyze the hydrogen evolution reaction (HER) in water splitting. The result shows that MoS₂/Ni_0.85Se with a molar ratio of Mo/Ni = 30 (denoted as M30) has the best catalytic performance towards HER, with the lowest overpotential of 118 mV at 10 mA cm⁻², smallest Tafel slope of 49 mV·dec⁻¹ among all the synthesized materials. Long-term electrochemical testing shows that M30 has good stability for HER over at least 30 h. These results maybe due to the large electrochemical active surface area and high conductivity. This work shows that transition metal selenides and sulfides can form effective electrocatalyst for HER.     

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.     

High throughput preparation of Ni–Mo alloy thin films as efficient bifunctional electrocatalysts for water splitting

The synthesis of cost-effective and high-performance electrocatalysts for water splitting is the main challenge in electrochemical hydrogen production. In this study, we adopted a high throughput method to prepare bi-metallic catalysts for oxygen/hydrogen evolution reactions (OER/HER). A series of Ni–Mo alloy electrocatalysts with tunable compositions were prepared by a simple co-sputtering method. Due to the synergistic effect between Ni and Mo, the intrinsic electrocatalytic activity of the Ni–Mo alloy electrocatalysts is improved, resulting in excellent HER and OER performances. The Ni₉₀Mo₁₀ electrocatalyst shows the best HER performance, with an extremely low overpotential of 58 mV at 10 mA cm^?2, while the Ni₄₀Mo₆₀ electrocatalyst shows an overpotential of 258 mV at 10 mA cm^?2 in OER. More significantly, the assembled Ni₄₀Mo₆₀//Ni₉₀Mo₁₀ electrolyzer only needs a cell voltage of 1.57 V to reach 10 mA cm^?2 for overall water splitting.     

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.     

Ultrathin-layered MoS2 hollow nanospheres decorating Ni3S2 nanowires as high effective self-supporting electrode for hydrogen evolution reaction

High-activity and cost-effective transition metal sulfides (TMSs) have attracted tremendous attention as promising catalysts for hydrogen evolution reaction (HER). However, a significant challenge is the simultaneous construction of abundant electrochemical active sites and the fast electronic transmission path to boost a high-efficient HER. Herein, we demonstrate a facile one-step hydrothermal preparation of MoS₂ hollow nanospheres decorating Ni₃S₂ nanowires supported on Ni foam (NF), without any other additional template, surfactant or annealing. In this three-dimensional (3D) heterostructure, the ultrathin-layered MoS₂ hollow nanospheres contribute to the promotion of the total surface area and the electrochemical active sites. Meanwhile, the Ni₃S₂ nanowires are beneficial to the high electrical conductivity. Consequently, the optimized MoS₂/Ni₃S₂/NF-200-24 electrocatalyst presents an extremely superior HER activity to that of individual MoS₂/NF and Ni₃S₂/NF. The HER overpotentials are 85 mV at 10 mA cm⁻² and 189 mV at 100 mA cm⁻², which are also comparable with the state-of-the-art 20% Pt/C/NF electrode at both low and high current.