Edge‐Terminated MoS2 Nanoassembled Electrocatalyst via In Situ Hybridization with 3D Carbon Network

Transition metal dichalcogenides, especially MoS₂, are considered as promising electrocatalysts for hydrogen evolution reaction (HER). Since the physicochemical properties of MoS₂ and electrode morphology are highly sensitive factor for HER performance, designed synthesis is highly pursued. Here, an in situ method to prepare a 3D carbon/MoS₂ hybrid catalyst, motivated by the graphene ribbon synthesis process, is reported. By rational design strategies, the hybrid electrocatalysts with cross‐connected porous structure are obtained, and they show a high HER activity even comparable to the state‐of‐the‐art MoS₂ catalyst without appreciable activity loss in long‐term operations. Based on various physicochemical techniques, it is demonstrated that the synthetic procedure can effectively guide the formation of active site and 3D structure with a distinctive feature; increased exposure of active sites by decreased domain size and intrinsically high activity through controlling the number of stacking layers. Moreover, the importance of structural properties of the MoS₂‐based catalysts is verified by controlled experiments, validating the effectiveness of the designed synthesis approach.     

Tuning of magnetic parameters in cobalt-polystyrene nanocomposites by reduction cycling

Cobalt nanoparticles were prepared by a reduction process inside polymer pores using CoSO₄·7H₂O and NaBH₄. A porous polymer network (sulphonated polystyrene) was chosen, as the template for the synthesis of elementary cobalt as high surface area cobalt nanoparticles are prone to oxidation. The preliminary studies reveal that the cobalt is first formed with an oxide protective layer outside and upon repeating the reduction cycles, inner pores of the polymers are opened which enhanced the yield of metallic cobalt. These high surface area cobalt nanoparticles embedded in a polymer are ideal for the synthesis of carbon nanotubes as cobalt can act as a catalyst for the nanotube synthesis. The concentration of cobalt can be tuned in this technique by repeating the cycling process.     

Cobalt Covalent Doping in MoS2 to Induce Bifunctionality of Overall Water Splitting

The layer‐structured MoS₂ is a typical hydrogen evolution reaction (HER) electrocatalyst but it possesses poor activity for the oxygen evolution reaction (OER). In this work, a cobalt covalent doping approach capable of inducing HER and OER bifunctionality into MoS₂ for efficient overall water splitting is reported. The results demonstrate that covalently doping cobalt into MoS₂ can lead to dramatically enhanced HER activity while simultaneously inducing remarkable OER activity. The catalyst with optimal cobalt doping density can readily achieve HER and OER onset potentials of ?0.02 and 1.45 V (vs reversible hydrogen electrode (RHE)) in 1.0 m KOH. Importantly, it can deliver high current densities of 10, 100, and 200 mA cm^?2 at low HER and OER overpotentials of 48, 132, 165 mV and 260, 350, 390 mV, respectively. The reported catalyst activation approach can be adapted for bifunctionalization of other transition metal dichalcogenides.     

Efficient Hydrogen Evolution Reaction Catalysis in Alkaline Media by All‐in‐One MoS2 with Multifunctional Active Sites

MoS₂ becomes an efficient and durable nonprecious‐metal electrocatalyst for the hydrogen evolution reaction (HER) when it contains multifunctional active sites for water splitting derived from 1T‐phase, defects, S vacancies, exposed Mo edges with expanded interlayer spacings. In contrast to previously reported MoS₂‐based catalysts targeting only a single or few of these characteristics, the all‐in‐one MoS₂ catalyst prepared herein features all of the above active site types. During synthesis, the intercalation of in situ generated NH₃ molecules into MoS₂ sheets affords ammoniated MoS₂ (A‐MoS₂) that predominantly comprises 1T‐MoS₂ and exhibits an expanded interlayer spacing. The subsequent reduction of A‐MoS₂ results in the removal of intercalated NH₃ and H₂S to form an all‐in‐one MoS₂ with multifunctional active sites mentioned above (R‐MoS₂) that exhibits electrocatalytic HER performance in alkaline media superior to those of all previously reported MoS₂‐based electrocatalysts. In particular, a hybrid MoS₂/nickel foam catalyst outperforms commercial Pt/C in the practically meaningful high‐current region (>25 mA cm^?2), demonstrating that R‐MoS₂‐based materials can potentially replace Pt catalysts in practical alkaline HER systems.     

K–La–MgO as heterogeneous catalyst for synthesis of 3-(2-hydroxyethyl)-1,3-oxazolidin-2-one from diethanol amine and carbon dioxide

Cost-effective valorization of carbon dioxide into bulk and specialty chemicals using catalysis will be attractive in the foreseeable future. 1,3-Oxazolidin-2-one derivatives are one of the important classes of heterocyclic compounds which have wide applications in pharmaceutical industries due to their biological activities such as antibacterial, antimicrobial, antiseptic. Various synthetic routes are employed to prepare these compounds which include phosgenation, oxidative carbonylation, etc., which make use of polluting chemicals and homogeneous catalysts. The heterogeneous catalytic processes to synthesize these derivatives are quite limited. Thus, developing a green route which is environmental friendly is highly desirable. The current work deals with development of a heterogeneous reusable catalyst and its application to synthesize 1,3-oxazolidin-2-one derivatives using carbon dioxide as a C1 source. The fact that no use of promoter or organic co-catalyst is made in the current process makes the synthesis route more favorable. Pure La–MgO and K–La–MgO with different K loading (1, 3, 5, and 7 wt%) synthesized by combustion route were screened for carbonylation of diethanol amine. 5% K–La–MgO was found to be the best catalyst. The catalyst was well characterized in virgin form and after use by various analytical techniques like TEM, SEM, XRD, CO₂ and NH₃-TPD, BET surface area analysis. With 5% K–La/MgO, 72% conversion of diethanol amine was achieved with 100% selectivity of the desired product at optimum conditions, i.e., 150 °C, 5 wt% K–La/MgO catalyst loading of 0.02 g/cm³ and 2.0 MPa CO₂ pressure. Reaction mechanism was proposed and kinetic model developed. The apparent activation energy was calculated as 18.76 kcal/mol. The catalyst was robust and recyclable. The process is clean and green.     

Highly Robust Non‐Noble Alkaline Hydrogen‐Evolving Electrocatalyst from Se‐Doped Molybdenum Disulfide Particles on Interwoven CoSe2 Nanowire Arrays

Developing efficient non‐noble and earth‐abundant hydrogen‐evolving electrocatalysts is highly desirable for improving the energy efficiency of water splitting in base. Molybdenum disulfide (MoS₂) is a promising candidate, but its catalytic activity is kinetically retarded in alkaline media due to the unfavorable water adsorption and dissociation feature. A heterogeneous electrocatalyst is reported that is constructed by selenium‐doped MoS₂ (Se‐MoS₂) particles on 3D interwoven cobalt diselenide (CoSe₂) nanowire arrays that drives the hydrogen evolution reaction (HER) with fast reaction kinetics in base. The resultant Se‐MoS₂/CoSe₂ hybrid exhibits an outstanding catalytic HER performance with extremely low overpotentials of 30 and 93 mV at 10 and 100 mA cm^–2 in base, respectively, which outperforms most of the inexpensive alkaline HER catalysts, and is among the best alkaline catalytic activity reported so far. Moreover, this hybrid catalyst shows exceptional catalytic performance with very low overpotentials of 84 and 95 mV at 10 mA cm^–2 in acidic and neutral electrolytes, respectively, implying robust pH universality of this hybrid catalyst. This work may provide new inspirations for the development of high‐performance MoS₂‐based HER electrocatalysts in unfavorable basic media for promising catalytic applications.     

Amorphous Molybdenum Sulfide/Carbon Nanotubes Hybrid Nanospheres Prepared by Ultrasonic Spray Pyrolysis for Electrocatalytic Hydrogen Evolution

Developing cost‐effective electrocatalysts with high activity and stability for hydrogen evolution reaction (HER) plays an important role in modern hydrogen economy. Amorphous molybdenum sulfide (MoS_x ) has recently emerged as one of the most promising alternatives to Pt‐based catalysts in HER, especially in acidic electrolytes. Here this study reports a simple ultrasonic spray pyrolysis method to synthesize hybrid HER catalysts composed of MoS_x firmly attached on entangled carbon nanotube nanospheres (MoS_x /CNTs). This synthetic process is fast, continuous, highly durable, and amenable to high‐volume production with high yields and exceptional quality. The MoS_x /CNTs hybrid catalyst prepared at 300 °C exhibits a low overpotential of 168 mV at the current density of 10 mA cm^?2 with a small Tafel slope of 36 mV dec^?1. Electrochemical measurements and X‐ray photoelectron spectroscopy analyses reveal that the CNT network not only promotes the charge transfer in corresponding HER process but also enhances the stability of the active sites in MoS_x . This work demonstrates that ultrasonic spray pyrolysis is a reliable and versatile approach for synthesizing amorphous MoS_x‐based HER catalysts.     

Computational investigations of Cu-embedded MoS<Subscript>2</Subscript> sheet for CO oxidation catalysis

Elevated amount of CO levels in the atmosphere poses serious health and environmental hazards. Oxidation of CO using suitable catalysts is one of the methods to control it. By means of DFT calculations, single Cu atom doped in S vacancy of MoS₂ nanosheet is studied for CO oxidation catalysis. Cu atom is strongly confined at the S-defective site of the MoS₂ sheet, possessing high energy barrier for the diffusion to its neighboring sites. Adsorption energy, charge transfer and orbital hybridization of CO and O₂ molecules adsorbed Cu-doped MoS₂ sheet reveal that O₂ is relatively more strongly adsorbed than CO. High adsorption energy of O₂ (??2.115 eV) and large charge transfer between O₂ and Cu–MoS₂ sheet (0.493e), compared to CO, make O₂ adsorption more favorable, which extenuates CO poisoning and hence helps in the efficient CO oxidation process. The complete oxidation of CO takes place in two steps: \( {\text{CO}} + {\text{O}}_{2} \to {\text{OOCO}} \) with activation energy of 0.201 eV, succeeded by \( {\text{OOCO}} + {\text{CO}} \to 2{\text{CO}}_{2} \) without any energy barrier. Our results show that the basal plane of MoS₂ sheet gets activated by embedding it with Cu metal, which can catalyze CO oxidation reaction effectively and without poisoning issues. The high activity, stability and low cost features can possibly encourage fabricating MoS₂-based catalysts for CO oxidation reaction.     

Electrochemically Exfoliated High‐Quality 2H‐MoS2 for Multiflake Thin Film Flexible Biosensors

2D molybdenum disulfide (MoS₂) gives a new inspiration for the field of nanoelectronics, photovoltaics, and sensorics. However, the most common processing technology, e.g., liquid‐phase based scalable exfoliation used for device fabrication, leads to the number of shortcomings that impede their large area production and integration. Major challenges are associated with the small size and low concentration of MoS₂ flakes, as well as insufficient control over their physical properties, e.g., internal heterogeneity of the metallic and semiconducting phases. Here it is demonstrated that large semiconducting MoS₂ sheets (with dimensions up to 50 µm) can be obtained by a facile cathodic exfoliation approach in nonaqueous electrolyte. The synthetic process avoids surface oxidation thus preserving the MoS₂ sheets with intact crystalline structure. It is further demonstrated at the proof‐of‐concept level, a solution‐processed large area (60 × 60 µm) flexible Ebola biosensor, based on a MoS₂ thin film (6 µm thickness) fabricated via restacking of the multiple flakes on the polyimide substrate. The experimental results reveal a low detection limit (in femtomolar–picomolar range) of the fabricated sensor devices. The presented exfoliation method opens up new opportunities for fabrication of large arrays of multifunctional biomedical devices based on novel 2D materials.     

Scalable and controllable synthesis of 2D high-proportion 1T-phase MoS2

Two-dimensional molybdenum disulfide (2D MoS₂) is considered as a promising candidate for many applications due to its unique structure and properties. However, the controllable synthesis of large-scale and high-quality 2D 1T-phase MoS₂ is still a challenge. Herein, we present the scalable and controllable synthesis of 2D MoS₂ from 2H to 1T@2H phase by using K₂SO₄ salt as a simultaneous high-temperature sulfur source and template. The as-synthesized 1T@2H-2D MoS₂ exhibits a high yield and can be easily assembled into freestanding electrode with high specific capacitance of 434 F/g at a scan rate of 1 mV/s in LiClO₄ ethylene carbonate/dimethyl carbonate (EC/DMC). Moreover, various single-crystal 2D transition metal sulfides (WS₂, PbS, MnS and Ni₉S₈) and 2D S-doped carbon can be synthesized using this method. We believe that this study may provide a new sight for scalable and controllable synthesis of other 2D materials beyond 2D MoS₂.

     

Molecular Nanowire Bonding to Epitaxial Single‐Layer MoS2 by an On‐Surface Ullmann Coupling Reaction

Lateral heterostructures consisting of 2D transition metal dichalcogenides (TMDCs) directly interfaced with molecular networks or nanowires can be used to construct new hybrid materials with interesting electronic and spintronic properties. However, chemical methods for selective and controllable bond formation between 2D materials and organic molecular networks need to be developed. As a demonstration of a self‐assembled organic nanowire‐TMDC system, a method to link and interconnect epitaxial single‐layer MoS₂ flakes with organic molecules is demonstrated. Whereas pristine epitaxial single‐layer MoS₂ has no affinity for molecular attachment, it is found that single‐layer MoS₂ will selectively bind the organic molecule 2,8‐dibromodibenzothiophene (DBDBT) in a surface‐assisted Ullmann coupling reaction when the MoS₂ has been activated by pre‐exposing it to hydrogen. Atom‐resolved scanning tunneling microscopy (STM) imaging is used to analyze the bonding of the nanowires, and thereby it is revealed that selective bonding takes place on a specific S atom at the corner site between the two types of zig‐zag edges available in a hexagonal single layer MoS₂ sheet. The method reported here successfully combining synthesis of epitaxial TMDCs and Ullmann coupling reactions on surfaces may open up new synthesis routes for 2D organic‐TMDC hybrid materials.     

Layer Thinning and Etching of Mechanically Exfoliated MoS2 Nanosheets by Thermal Annealing in Air

A simple thermal annealing method for layer thinning and etching of mechanically exfoliated MoS₂ nanosheets in air is reported. Using this method, single‐layer (1L) MoS₂ nanosheets are achieved after the thinning of MoS₂ nanosheets from double‐layer (2L) to quadri‐layer (4L) at 330 °C. The as‐prepared 1L MoS₂ nanosheet shows comparable optical and electrical properties with the mechanically exfoliated, pristine one. In addition, for the first time, the MoS₂ mesh with high‐density of triangular pits is also fabricated at 330 °C, which might arise from the anisotropic etching of the active MoS₂ edge sites. As a result of thermal annealing in air, the thinning of MoS₂ nanosheet is possible due to its oxidation to form MoO₃. Importantly, the MoO₃ fragments on the top of thinned MoS₂ layer induces the hole injection, resulting in the p‐type channel in fabricated field‐effect transistors.     

纳米MoS2的合成及其在重油深度转化中的应用

MoS_2是在催化剂领域、光化学领域以及润滑油领域都广受关注的材料。因其良好的加氢活性,通常在石油化工领域中作为加氢过程的催化剂活性组分。介绍了纳米MoS_2的插层剥离法、气相化学沉积法、前驱物分解法、水热合成法等多种合成方法,列举了不同方法合成MoS_2产品在形貌、大小、比表面积等方面的特点,并针对重油转化所需催化剂的特性对不同合成方法的优缺点进行了对比。最后简单介绍了意大利ENI公司以非负载MoS_2作为催化剂在浆态床加氢工业应用的实例。     

Tube- and ball-like amorphous MoS2 prepared by a solvothermal method

Amorphous MoS₂ was synthesized solvothermally in pyridine at 190 °C. XRD pattern indicated that the amorphous MoS₂ was made up of single layer and layer stacking had not taken place. TEM images showed that tube- and ball-like morphologies existed in the amorphous MoS₂. Electron diffraction did not reveal any crystal ordering in the tube and ball, which indicated that the tube and ball were completely amorphous. The influences of reaction conditions on the formation of these morphologies were also discussed. It was proposed that the formation of the tube- and ball-like structures might be energy-favorable for the single layer of MoS₂ under the synthesis conditions.     

Synthesis of Few‐Layer MoS2 Nanosheet‐Coated TiO2 Nanobelt Heterostructures for Enhanced Photocatalytic Activities

MoS₂ nanosheet‐coated TiO₂ nanobelt heterostructures—referred to as TiO₂@MoS₂—with a 3D hierarchical configuration are prepared via a hydrothermal reaction. The TiO₂ nanobelts used as a synthetic template inhibit the growth of MoS₂ crystals along the c‐axis, resulting in a few‐layer MoS₂ nanosheet coating on the TiO₂ nanobelts. The as‐prepared TiO₂@MoS₂ heterostructure shows a high photocatalytic hydrogen production even without the Pt co‐catalyst. Importantly, the TiO₂@MoS₂ heterostructure with 50 wt% of MoS₂ exhibits the highest hydrogen production rate of 1.6 mmol h^?1g^?1. Moreover, such a heterostructure possesses a strong adsorption ability towards organic dyes and shows high performance in photocatalytic degradation of the dye molecules.     

A Critical Review on Enhancement of Photocatalytic Hydrogen Production by Molybdenum Disulfide: From Growth to Interfacial Activities

Ultrathin 2D molybdenum disulfide (MoS₂), which is the flagship of 2D transition‐metal dichalcogenide nanomaterials, has drawn much attention in the last few years. 2D MoS₂ has been banked as an alternative to platinum for highly active hydrogen evolution reaction because of its low cost, high surface‐to‐volume ratio, and abundant active sites. However, when MoS₂ is used directly as a photocatalyst, contrary to public expectation, it still performs poorly due to lateral size, high recombination ratio of excitons, and low optical cross section. Besides, simply compositing MoS₂ as a cocatalyst with other semiconductors cannot satisfy the practical application, which stimulates the pursual of a comprehensive insight into recent advances in synthesis, properties, and enhanced hydrogen production of MoS₂. Therefore, in this Review, emphasis is given to synthetic methods, phase transitions, tunable optical properties, and interfacial engineering of 2D MoS₂. Abundant ways of band edge tuning, structural modification, and phase transition are addressed, which can generate the neoteric photocatalytic systems. Finally, the main challenges and opportunities with respect to MoS₂ being a cocatalyst and coherent light–matter interaction of MoS₂ in photocatalytic systems are proposed.     

Effect of Adventitious Carbon on Pit Formation of Monolayer MoS2

Forming pits on molybdenum disulfide (MoS₂) monolayers is desirable for (opto)electrical, catalytic, and biological applications. Thermal oxidation is a potentially scalable method to generate pits on monolayer MoS₂, and pits are assumed to preferentially form around undercoordinated sites, such as sulfur vacancies. However, studies on thermal oxidation of MoS₂ monolayers have not considered the effect of adventitious carbon (C) that is ubiquitous and interacts with oxygen at elevated temperatures. Herein, the effect of adventitious C on the pit formation on MoS₂ monolayers during thermal oxidation is studied. The in situ environmental transmission electron microscopy measurements herein show that pit formation is preferentially initiated at the interface between adventitious C nanoparticles and MoS₂, rather than only sulfur vacancies. Density functional theory (DFT) calculations reveal that the C/MoS₂ interface favors the sequential adsorption of oxygen atoms with facile kinetics. These results illustrate the important role of adventitious C on pit formation on monolayer MoS₂.     

Ti-MOFs基复合材料的制备及其光电催化性能研究

以钛酸异丙酯为节点,2-氨基对苯二甲酸为连接体,构建具有多孔结构的钛基金属有机骨架(Ti-MOFs),即NH₂-MIL-125(Ti),通过原位沉积法将花状多级结构的二硫化钼(MoS₂)负载至Ti-MOFs表面,制备了具有多活性位点的光电催化剂MoS₂/Ti-MOFs,并考察了MoS₂负载量对Ti-MOFs光电催化性能的影响。扫描电子显微镜、红外光谱仪、X射线光子能谱等用于表征材料的形貌、结构及组成,电化学工作站用于研究材料的光电化学性能。此外,使用MoS₂/Ti-MOFs作为光电催化剂对模拟有机污染物2,4,6-三氯苯酚(2,4,6-TCP)进行降解,通过测试模拟污染物的降解效率,评估了合成的催化剂的光电催化活性。研究结果表明,MoS₂可有效负载于Ti-MOFs表面,且MoS₂负载量为20wt.%时,合成的催化剂(MoS₂/Ti-MOFs-80)的光电催化性能最优。MoS₂/Ti-MOFs-80在可见光照射下的光电流密度达到了0.290 mA/cm²。在可见光下照射6 h后,MoS₂/Ti-MOFs-80对2,4,6-TCP的去除效率达到了82.59%,且模拟污染物循环降解实验证实了MoS₂/Ti-MOFs-80具有良好的光电催化稳定性。     

Tunable Fabrication of Molybdenum Disulfide Quantum Dots for Intracellular MicroRNA Detection and Multiphoton Bioimaging

Molybdenum disulfide (MoS₂) quantum dots (QDs) (size <10 nm) possess attractive new properties due to the quantum confinement and edge effects as graphene QDs. However, the synthesis and application of MoS₂ QDs has not been investigated in great detail. Here, a facile and efficient approach for synthesis of controllable‐size MoS₂ QDs with excellent photoluminescence (PL) by using a sulfuric acid‐assisted ultrasonic route is developed for this investigation. Various MoS₂ structures including monolayer MoS₂ flake, nanoporous MoS₂, and MoS₂ QDs can be yielded by simply controlling the ultrasonic durations. Comprehensive microscopic and spectroscopic tools demonstrate that the MoS₂ QDs have uniform lateral size and possess excellent excitation‐independent blue PL. The as‐generated MoS₂ QDs show high quantum yield of 9.65%, long fluorescence lifetime of 4.66 ns, and good fluorescent stability over broad pH values from 4 to 10. Given the good intrinsic optical properties and large surface area combined with excellent physiological stability and biocompatibility, a MoS₂ QDs‐based intracellular microRNA imaging analysis system is successfully constructed. Importantly, the MoS₂ QDs show good performance as multiphoton bioimaging labeling. The proposed synthesis strategy paves a new way for facile and efficient preparing MoS₂ QDs with tunable‐size for biomedical imaging and optoelectronic devices application.     

Sustainable Fuel Production from Ambient Moisture via Ferroelectrically Driven MoS2 Nanosheets

Unlike traditional water splitting in an aqueous medium, direct decomposition of atmospheric water is a promising way to simultaneously dehumidify the living space and generate power. Here, a tailored superhygroscopic hydrogel, a catalyst, and a solar cell are integrated into a humidity digester that can break down ambient moisture into hydrogen and oxygen, creating an efficient electrochemical cell. The function of the hydrogel is to harvest moisture from ambient humidity and transfer the collected water to the catalyst. Barium titanate and vertical 2D MoS₂ nanosheets are integrated as the catalyst: the negatively polarized cathode can enhance the electron transport and attract H⁺ to the MoS₂ surface for water reduction, while water oxidation takes place at the positively polarized anode. By employing this mechanism, it is possible to maintain the relative humidity in a medium-sized room at <60% without any additional energy input, and a stable current of 12.5 mA cm⁻² is generated by the humidity digester when exposed to ambient light.