MoS2 Formed on Mesoporous Graphene as a Highly Active Catalyst for Hydrogen Evolution

A highly active and stable electrocatalyst for hydrogen evolution is developed based on the in situ formation of MoS₂ nanoparticles on mesoporous graphene foams (MoS₂/MGF). Taking advantage of its high specific surface area and its interconnected conductive graphene skeleton, MGF provides a favorable microenvironment for the growth of highly dispersed MoS₂ nanoparticles while allowing rapid charge transfer kinetics. The MoS₂/MGF nanocomposites exhibit an excellent electrocatalytic activity for the hydrogen evolution reaction with a low overpotential and substantial apparent current densities. Such enhanced catalytic activity stems from the abundance of catalytic edge sites, the increase of electrochemically accessible surface area and the unique synergic effects between the MGF support and active catalyst. The electrode reactions are characterized by electrochemical impedance spectroscopy. A Tafel slope of ≈42 mV per decade is measured for a MoS₂/MGF modified electrode, suggesting the Volmer‐Heyrovsky mechanism of hydrogen evolution.     

A Bottom‐Up Approach to Build 3D Architectures from Nanosheets for Superior Lithium Storage

Two‐dimensional (2D) atomic layers such as graphene, and metal chalcogenides have recently attracted tremendous attention due to their unique properties and potential applications. Unfortunately, in most cases, the free‐standing nanosheets easily re‐stack due to their van der Waals forces, and lose the advantages of their separated atomic layer state. Here, a bottom‐up approach is developed to build three‐dimensional (3D) architectures by 2D nanosheets such as MoS₂ and graphene oxide nanosheets as building blocks, the thin nature of which can be well retained. After simply chemical reduction, the resulting 3D MoS₂‐graphene architectures possess high surface area, porous structure, thin walls and high electrical conductivity. Such unique features are favorable for the rapid diffusions of both lithium ions and electrons during lithium storage. As a consequence, MoS₂‐graphene electrodes exhibit high reversible capacity of ≈1200 mAh g^?1, with very good cycling performance. Moreover, such a simple and low‐cost assembly protocol can provide a new pathway for the large‐scale production of various functional 3D architectures for energy storage and conversions.     

Kinetic‐Oriented Construction of MoS2 Synergistic Interface to Boost pH‐Universal Hydrogen Evolution

As a prerequisite for a sustainable energy economy in the future, designing earth‐abundant MoS₂ catalysts with a comparable hydrogen evolution catalytic performance in both acidic and alkaline environments is still an urgent challenge. Decreasing the energy barriers could enhance the catalysts' activity but is not often a strategy for doing so. Here, the first kinetic‐oriented design of the MoS₂‐based heterostructure is presented for pH‐universal hydrogen evolution catalysis by optimizing the electronic structure based on the simultaneous modulation of the 3d‐band‐offsets of Ni, Co, and Mo near the interface. Benefiting from this desirable electronic structure, the obtained MoS₂/CoNi₂S₄ catalyst achieves an ultralow overpotential of 78 and 81 mV at 10 mA cm^?2, and turnover frequency as high as 2.7 and 1.7 s^?1 at the overpotential of 200 mV in alkaline and acidic media, respectively. The MoS₂/CoNi₂S₄ catalyst represents one of the best hydrogen evolution reaction performing ones among MoS₂‐based catalysts reported to date in both alkaline and acidic environments, and equally important is the remarkable long‐term stability with negligible activity loss after maintaining at 10 mA cm^?2 for 48 h in both acid and base. This work highlights the potential to deeply understand and rationally design highly efficient pH‐universal electrocatalysts for future energy storage and delivery.     

A Cake‐Style CoS2@MoS2/RGO Hybrid Catalyst for Efficient Hydrogen Evolution

A three‐tiered cake‐style composite is elaborately established, with the characteristic of a double‐deck of MoS₂ nanosheets and reduction of graphene oxide (RGO) sheets dotted with CoS₂ nanoparticles (CoS₂@MoS₂/RGO). Because of the prominent synergistic effect of graphene acting as conductive support, MoS₂ and CoS₂ providing abundant catalytically active sites, and the cake‐style structure promoting mechanical stability, the CoS₂@MoS₂/RGO exhibits a superior hydrogen evolution reaction activity with a small overpotential of 98 mV at cathodic current density of 10 mA cm^?2, and a small Tafel slope of 37.4 mV dec^?1, as well as excellent cycling stability. Density functional theory calculations reveal that the hydrogen adsorption free energy of CoS₂@MoS₂/RGO is close to zero.     

Reduced Graphene Oxide‐Modified Carbon Nanotube/Polyimide Film Supported MoS2 Nanoparticles for Electrocatalytic Hydrogen Evolution

Efficient evolution of hydrogen through electrocatalysis at low overpotentials holds tremendous promise for clean energy. Herein, a highly active and stable MoS₂ electrocatalyst is supported on reduced graphene oxide‐modified carbon nanotube/polyimide (PI/CNT‐RGO) film for hydrogen evolution reaction (HER). The PI/CNT‐RGO film allows the intimate growth of MoS₂ nanoparticles on its surface. The nanosize and high dispersion of MoS₂ nanoparticles provide a vast amount of available edge sites and the coupling of RGO and MoS₂ enhances the electron transfer between the edge sites and the substrate, greatly improving the HER activity of PI/CNT‐RGO‐MoS₂ film. The MoS₂ with a smaller loading less than 0.04 mg cm^?2 on the PI/CNT‐RGO film exhibits excellent HER activities with a low overpotential of 0.09 V and large current densities, as well as good stability. The Tafel slope of 61 mV dec^?1 reveals the Volmer–Heyrovsky mechanism for HER. Thus, this work paves a potential pathway for designing efficient MoS₂‐based electrocatalysts for HER.     

Efficient and Stable Bifunctional Electrocatalysts Ni/NixMy (M = P,S) for Overall Water Splitting

Development of easy‐to‐make, highly active, and stable bifunctional electrocatalysts for water splitting is important for future renewable energy systems. Three‐dimension (3D) porous Ni/Ni₈P₃ and Ni/Ni₉S₈ electrodes are prepared by sequential treatment of commercial Ni‐foam with acid activation, followed by phosphorization or sulfurization. The resultant materials can act as self‐supported bifunctional electrocatalytic electrodes for direct water splitting with excellent activity toward oxygen evolution reaction and hydrogen evolution reaction in alkaline media. Stable performance can be maintained for at least 24 h, illustrating their versatile and practical nature for clean energy generation. Furthermore, an advanced water electrolyzer through exploiting Ni/Ni₈P₃ as both anode and cathode is fabricated, which requires a cell voltage of 1.61 V to deliver a 10 mA cm^?2 water splitting current density in 1.0 m KOH solution. This performance is significantly better than that of the noble metal benchmark—integrated Ni/IrO₂ and Ni/Pt–C electrodes. Therefore, these bifunctional electrodes have significant potential for realistic large‐scale production of hydrogen as a replacement clean fuel to polluting and limited fossil‐fuels.     

High‐Concentration Aqueous Dispersions of MoS2

Molybdenum disulfide (MoS₂) nanosheets have been attracting increasing research interests due to their unique material properties. However, the lack of a reliable large‐scale production method impedes their practical applications. Here a facile, efficient, and scalable method for the fabrication of high‐concentration aqueous dispersion of MoS₂ nanosheets using combined grinding and sonication is reported. The 26.7 ± 0.7 mg/mL concentration achieved is the highest concentration in an aqueous solution reported up to now. Grinding generates pure shear forces to detach the MoS₂ layers from the bulk materials. Subsequent sonication further breaks larger crystallites into smaller crystallites, which promotes the dispersion of MoS₂ nanosheets in ethanol/water solutions. The exfoliation process establishes a new paradigm in the top‐down fabrication of 2D nanosheets in aqueous solution. In the meantime, MoS₂‐based sensing film produced using this approach has successfully demonstrated the feasibility of a low‐cost and efficient NH₃ gas sensor using inkjet printing as a viable method.     

Hierarchical NiCo2S4 Nanowire Arrays Supported on Ni Foam: An Efficient and Durable Bifunctional Electrocatalyst for Oxygen and Hydrogen Evolution Reactions

A recent approach for solar‐to‐hydrogen generation has been water electrolysis using efficient, stable, and inexpensive bifunctional electrocatalysts within strong electrolytes. Herein, the direct growth of 1D NiCo₂S₄ nanowire (NW) arrays on a 3D Ni foam (NF) is described. This NiCo₂S₄ NW/NF array functions as an efficient bifunctional electrocatalyst for overall water splitting with excellent activity and stability. The 3D‐Ni foam facilitates the directional growth, exposing more active sites of the catalyst for electrochemical reactions at the electrode–electrolyte interface. The binder‐free, self‐made NiCo₂S₄ NW/NF electrode delivers a hydrogen production current density of 10 mA cm^–2 at an overpotential of 260 mV for the oxygen evolution reaction and at 210 mV (versus a reversible hydrogen electrode) for the hydrogen evolution reaction in 1 m KOH. This highly active and stable bifunctional electrocatalyst enables the preparation of an alkaline water electrolyzer that could deliver 10 mA cm^–2 under a cell voltage of 1.63 V. Because the nonprecious‐metal NiCo₂S₄ NW/NF foam‐based electrodes afford the vigorous and continuous evolution of both H₂ and O₂ at 1.68 V, generated using a solar panel, they appear to be promising water splitting devices for large‐scale solar‐to‐hydrogen generation.     

Self‐Assembly of Flexible Free‐Standing 3D Porous MoS2‐Reduced Graphene Oxide Structure for High‐Performance Lithium‐Ion Batteries

Flexible freestanding electrodes are highly desired to realize wearable/flexible batteries as required for the design and production of flexible electronic devices. Here, the excellent electrochemical performance and inherent flexibility of atomically thin 2D MoS₂ along with the self‐assembly properties of liquid crystalline graphene oxide (LCGO) dispersion are exploited to fabricate a porous anode for high‐performance lithium ion batteries. Flexible, free‐standing MoS₂–reduced graphene oxide (MG) film with a 3D porous structure is fabricated via a facile spontaneous self‐assembly process and subsequent freeze‐drying. This is the first report of a one‐pot self‐assembly, gelation, and subsequent reduction of MoS₂/LCGO composite to form a flexible, high performance electrode for charge storage. The gelation process occurs directly in the mixed dispersion of MoS₂ and LCGO nanosheets at a low temperature (70 °C) and normal atmosphere (1 atm). The MG film with 75 wt% of MoS₂ exhibits a high reversible capacity of 800 mAh g^?1 at a current density of 100 mA g^?1. It also demonstrates excellent rate capability, and excellent cycling stability with no capacity drop over 500 charge/discharge cycles at a current density of 400 mA g^?1.     

Bifunctional Porous NiFe/NiCo2O4/Ni Foam Electrodes with Triple Hierarchy and Double Synergies for Efficient Whole Cell Water Splitting

A 3D hierarchical porous catalyst architecture based on earth abundant metals Ni, Fe, and Co has been fabricated through a facile hydrothermal and electrodeposition method for efficient oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). The electrode is comprised of three levels of porous structures including the bottom supermacroporous Ni foam (≈500 μm) substrate, the intermediate layer of vertically aligned macroporous NiCo₂O₄ nanoflakes (≈500 nm), and the topmost NiFe(oxy)hydroxide mesoporous nanosheets (≈5 nm). This hierarchical architecture is binder‐free and beneficial for exposing catalytic active sites, enhancing mass transport and accelerating dissipation of gases generated during water electrolysis. Serving as an anode catalyst, the designed hierarchical electrode displays excellent OER catalytic activity with an overpotential of 340 mV to achieve a high current density of 1200 mA cm^?2. Serving as a cathode catalyst, the catalyst exhibits excellent performance toward HER with a moderate overpotential of 105 mV to deliver a current density of 10 mA cm^?2. Serving as both anode and cathode catalysts in a two‐electrode water electrolysis system, the designed electrode only requires a potential of 1.67 V to deliver a current density of 10 mA cm^?2 and exhibits excellent durability in prolonged bulk alkaline water electrolysis.     

Graphene‐Like Carbon Nitride Nanosheets for Improved Photocatalytic Activities

“Graphitic” (g)‐C₃N₄ with a layered structure has the potential of forming graphene‐like nanosheets with unusual physicochemical properties due to weak van der Waals forces between layers. Herein is shown that g‐C₃N₄ nanosheets with a thickness of around 2 nm can be easily obtained by a simple top‐down strategy, namely, thermal oxidation etching of bulk g‐C₃N₄ in air. Compared to the bulk g‐C₃N₄, the highly anisotropic 2D‐nanosheets possess a high specific surface area of 306 m² g^?1, a larger bandgap (by 0.2 eV), improved electron transport ability along the in‐plane direction, and increased lifetime of photoexcited charge carriers because of the quantum confinement effect. As a consequence, the photocatalytic activities of g‐C₃N₄ nanosheets have been remarkably improved in terms of ?OH radical generation and photocatalytic hydrogen evolution.     

Hybrid 2D Dual‐Metal–Organic Frameworks for Enhanced Water Oxidation Catalysis

Metal–organic frameworks (MOFs) and MOF‐derived nanostructures are recently emerging as promising catalysts for electrocatalysis applications. Herein, 2D MOFs nanosheets decorated with Fe‐MOF nanoparticles are synthesized and evaluated as the catalysts for water oxidation catalysis in alkaline medium. A dramatic enhancement of the catalytic activity is demonstrated by introduction of electrochemically inert Fe‐MOF nanoparticles onto active 2D MOFs nanosheets. In the case of active Ni‐MOF nanosheets (Ni‐MOF@Fe‐MOF), the overpotential is 265 mV to reach a current density of 10 mA cm^?2 in 1 m KOH, which is lowered by ≈100 mV after hybridization due to the 2D nanosheet morphology and the synergistic effect between Ni active centers and Fe species. Similar performance improvement is also successfully demonstrated in the active NiCo‐MOF nanosheets. More importantly, the real catalytic active species in the hybrid Ni‐MOF@Fe‐MOF catalyst are unraveled. It is found that, NiO nanograins (≈5 nm) are formed in situ during oxygen evolution reaction (OER) process and act as OER active centers as well as building blocks of the porous nanosheet catalysts. These findings provide new insights into understanding MOF‐based catalysts for water oxidation catalysis, and also shed light on designing highly efficient MOF‐derived nanostructures for electrocatalysis.     

Controllable Thermochemical Generation of Active Defects in the Horizontal/Vertical MoS2 for Enhanced Hydrogen Evolution

As for 2D transition metal dichalcogenides, the creation of proper active defects concentrations is considered as the efficient strategy for improving hydrogen evolution performance. However, the synthesis methods of large-area MoS₂ catalysts with controllable active defects are limited, also for its working mechanism. Herein, thermochemical generation of active defects for MoS₂ catalysts has established by annealing sodium hypophosphite, in which the phosphine is spontaneously generated and chemically tailors the MoS₂ lattice. The defects formation is confirmed by the investigation of slightly-changed surface structure and unpaired electrons for the annealed samples. The hydrogen evolution reaction performances of horizontally/vertically grown MoS₂ films are improved by controlling reaction conditions, indicating the active defects could form in the basal plane and edges with retained crystal structure. The overpotential of MoS₂ samples converted from 10 nm Mo reduces from −520 to −265 mV with largely decreased Tafel slope. The electrochemical microreactor studies reveal the protons adsorption of active sites shows much more significant contribution, than interfacial charge transfer with the enhanced remarkable performance (−100 mV at 10 mA cm⁻²). This study presents the large-area synthesized strategy for MoS₂ based catalysts with controllable defects concentration and helps establish rational design principles for future MoS₂ family electrocatalysts.     

Dual Functionalization of Liquid‐Exfoliated Semiconducting 2H‐MoS2 with Lanthanide Complexes Bearing Magnetic and Luminescence Properties

Liquid exfoliated, atomically thin semiconducting transition metal dichalcogenides (TMDs), as inorganic equivalents of graphene, have attracted great interest due to their distinctive physical, optoelectronic, and chemical properties. Functionalization of 2D TMDs brings new prospects for applications in optoelectronics, quantum technologies, catalysis, and medicine. In this report, dual functionalization of 2D semiconducting 2H‐MoS₂ nanosheets through simultaneous incorporation of magnetic and luminescent properties is demonstrated. A facile method is proposed for tuning the properties of the TDM semiconductors and accessing multimodal platforms, consisting in covalent grafting of lanthanide complexes onto the surface of 2D TMDs. Dual functionalization of liquid‐exfoliated MoS₂ nanosheets is demonstrated simultaneously with both europium (III) and gadolinium (III) complexes to form a colloidally stable luminescent (with millisecond lifetimes) and paramagnetic MoS₂‐based nanohybrid material. This work is the first example of transition metal dichalcogenide nanosheets functionalized with preformed lanthanide complexes. These findings open new prospects for covalent functionalization of TMDs with molecular species bearing specific functionalities as a means to tune the optoelectronic properties of the semiconductors, in order to create advanced materials and devices with a wide range of functionalities.     

Vertically Aligned WS2 Nanosheets for Water Splitting

Vertically aligned WS₂ (VAWS₂) nanosheet films are prepared using a lithium based anodization electrolyte to fabricate WO₃ films followed by sulfurization. The VAWS₂ synthesized here is self‐organized as a conformal structure to expose active edge sites for water splitting. These vertically aligned nanosheets are composed of exfoliated WS₂ to provide abundant active edges for catalytic reactions. Hydrogen evolution activity of the VAWS₂ is demonstrated to show high catalytic current, low onset overpotential and small Tafel slope. By certain measures, this VAWS₂ nanosheet film outperforms some of the state‐of‐the‐art hydrogen evolution reaction (HER) catalysts, which opens up a new pathway to simply and scalably fabricate high‐performance water electrolysis catalysts.     

MoS2/Si Heterojunction with Vertically Standing Layered Structure for Ultrafast,High‐Detectivity,Self‐Driven Visible–Near Infrared Photodetectors

As an interesting layered material, molybdenum disulfide (MoS₂) has been extensively studied in recent years due to its exciting properties. However, the applications of MoS₂ in optoelectronic devices are impeded by the lack of high‐quality p–n junction, low light absorption for mono‐/multilayers, and the difficulty for large‐scale monolayer growth. Here, it is demonstrated that MoS₂ films with vertically standing layered structure can be deposited on silicon substrate with a scalable sputtering method, forming the heterojunction‐type photodetectors. Molecular layers of the MoS₂ films are perpendicular to the substrate, offering high‐speed paths for the separation and transportation of photo‐generated carriers. Owing to the strong light absorption of the relatively thick MoS₂ film and the unique vertically standing layered structure, MoS₂/Si heterojunction photodetectors with unprecedented performance are actualized. The self‐driven MoS₂/Si heterojunction photodetector is sensitive to a broadband wavelength from visible light to near‐infrared light, showing an extremely high detectivity up to ≈10¹³ Jones (Jones = cm Hz^1/2 W^?1), and an ultrafast response speed of ≈3 μs. The performance is significantly better than the photodetectors based on mono‐/multilayer MoS₂ nanosheets. Additionally, the MoS₂/Si photodetectors exhibit excellent stability in air for a month. This work unveils the great potential of MoS₂/Si heterojunction for optoelectronic applications.     

Cobalt–Cobalt Phosphide Nanoparticles@Nitrogen‐Phosphorus Doped Carbon/Graphene Derived from Cobalt Ions Adsorbed Saccharomycete Yeasts as an Efficient,Stable, and Large‐Current‐Density Electrode for Hydrogen Evolution Reactions

Development of electrocatalysts for hydrogen evolution reaction (HER) with low overpotential and robust stability remains as one of the most serious challenges for energy conversion. Herein, a serviceable and highly active HER electrocatalyst with multilevel porous structure (Co‐Co₂P nanoparticles@N, P doped carbon/reduced graphene oxides (Co‐Co₂P@NPC/rGO)) is synthesized by Saccharomycete cells as template to adsorb metal ions and graphene nanosheets as separating agent to prevent aggregation, which is composed of Co‐Co₂P nanoparticles with size of ≈104.7 nm embedded into carbonized Saccharomycete cells. The Saccharomycete cells provide not only carbon source to produce carbon shells, but also phosphorus source to prepare metal phosphides. In order to realize the practicability and permanent stability, the binderless and 3D electrodes composed of obtained Co‐Co₂P@NPC/rGO powder are constructed, which possess a low overpotential of 61.5 mV (achieve 10 mA cm^?2) and the high current density with extraordinary catalytic stability (1000 mA cm^?2 for 20 h) in 0.5 m H₂SO₄. The preparation process is appropriate for synthesizing various metal or metal phosphide@carbon electrocatalysts. This work may provide a biological template method for rational design and fabrication of various metals or metal compounds@carbon 3D electrodes with promising applications in energy conversion and storage.     

In Situ Electrochemical Activation of Atomic Layer Deposition Coated MoS2 Basal Planes for Efficient Hydrogen Evolution Reaction

Molybdenum disulfide (MoS₂), which is composed of active edge sites and a catalytically inert basal plane, is a promising catalyst to replace the state‐of‐the‐art Pt for electrochemically catalyzing hydrogen evolution reaction (HER). Because the basal plane consists of the majority of the MoS₂ bulk materials, activation of basal plane sites is an important challenge to further enhance HER performance. Here, an in situ electrochemical activation process of the MoS₂ basal planes by using the atomic layer deposition (ALD) technique to improve the HER performance of commercial bulk MoS₂ is first demonstrated. The ALD technique is used to form islands of titanium dioxide (TiO₂) on the surface of the MoS₂ basal plane. The coated TiO₂ on the MoS₂ surface (ALD(TiO₂)‐MoS₂) is then leached out using an in situ electrochemical activation method, producing highly localized surface distortions on the MoS₂ basal plane. The MoS₂ catalysts with activated basal plane surfaces (ALD(Act.)‐MoS₂) have dramatically enhanced HER kinetics, resulting from more favorable hydrogen‐binding.     

Infrared Proximity Sensors Based on Photo-Induced Tunneling in van der Waals Integration

Infrared (IR) detectors based on photo-induced tunneling in van der Waals heterostructures (vdWHs) of graphene/h-BN/graphene or MoS₂/h-BN/graphene exhibit extremely low dark currents owing to a large electron barrier. However, a lack of tunneling barrier materials except for h-BN for 2D vdWHs limits their further enhancement. In this study, a broadband detection is reported with high sensitivity and fast photoresponse of IR proximity sensor by a vdW integration (2D-3D) of graphene or MoS₂, with NiO/Ni as the IR absorber and hole selective transport layer/counter electrode. The low Schottky barrier height of the reported junctions suppresses dark current with a high detectivity ≈ 10¹⁴ Jones and generates a photocurrent by transporting photo-excited carriers through a low hole barrier at a wide wavelength. Two types of integrated IR proximity sensor applications are developed: a passive sensor (MoS₂/NiO/Ni) for the near-IR (NIR) range and an active sensor (Gr/NiO/Ni) for the mid-IR (MIR) range. The former shows a broadband photoresponse to reflect the NIR, while the latter absorbs human body irradiation (2–16 µm wavelength) with a fast photoresponse of 3.5 s (rise time) and 1.8 s (fall time). The fabricated sensors utilize low power, broadband detection, high sensitivity, fast photoresponse, and large-scale area at room temperature.     

MoSx@NiO Composite Nanostructures: An Advanced Nonprecious Catalyst for Hydrogen Evolution Reaction in Alkaline Media

The design of the earth‐abundant, nonprecious, efficient, and stable electrocatalysts for efficient hydrogen evolution reaction (HER) in alkaline media is a hot research topic in the field of renewable energies. A heterostructured system composed of MoS_x deposited on NiO nanostructures (MoS_x@NiO) as a robust catalyst for water splitting is proposed here. NiO nanosponges are applied as cocatalyst for MoS₂ in alkaline media. Both NiO and MoS₂@NiO composites are prepared by a hydrothermal method. The NiO nanostructures exhibit sponge‐like morphology and are completely covered by the sheet‐like MoS₂. The NiO and MoS₂ exhibit cubic and hexagonal phases, respectively. In the MoS_x@NiO composite, the HER experiment in 1 m KOH electrolyte results in a low overpotential (406 mV) to produce 10 mA cm^?2 current density. The Tafel slope for that case is 43 mV per decade, which is the lowest ever achieved for MoS₂‐based electrocatalyst in alkaline media. The catalyst is highly stable for at least 13 h, with no decrease in the current density. This simple, cost‐effective, and environmentally friendly methodology can pave the way for exploitation of MoS_x@NiO composite catalysts not only for water splitting, but also for other applications such as lithium ion batteries, and fuel cells.