Solution‐Processed Two‐Dimensional MoS2 Nanosheets: Preparation,Hybridization, and Applications

As one member of the emerging class of ultrathin two‐dimensional (2D) transition‐metal dichalcogenide (TMD) nanomaterials, the ultra‐thin MoS₂ nanosheet has attracted increasing research interest as a result of its unique structure and fascinating properties. Solution‐phase methods are promising for the scalable production, functionalization, hybridization of MoS₂ nanosheets, thus enabling the widespread exploration of MoS₂‐based nanomaterials for various promising applications. In this Review, an overview of the recent progress of solution‐processed MoS₂ nanosheets is presented, with the emphasis on their synthetic strategies, functionalization, hybridization, properties, and applications. Finally, the challenges and opportunities in this research area will be proposed.     

First Report for Electrochemical Determination of Levodopa and Cabergoline: Application for Determination of Levodopa and Cabergoline in Human Serum,Urine and Pharmaceutical Formulations

The electrochemical oxidation of levodopa on the surface of a carbon paste electrode modified with graphene nanosheets, 1‐(4‐bromobenzyl)‐4‐ferrocenyl‐1H‐[1,2,3]‐triazole (1,4‐BBFT) and hydrophilic ionic liquid (n‐hexyl‐3‐methylimidazolium hexafluoro phosphate) as a binder is studied. It has been found that the oxidation of levodopa at the surface of a modified electrode occurs at a potential of about 210 mV less positive than that of an unmodified carbon paste electrode (CPE). The prepared modified electrode exhibits a very good resolution of the voltammetric peaks of levodopa and cabergoline. The electrode has been applied successfully for the determination of levodopa and cabergoline in some real samples.     

Single‐Step Exfoliation and Covalent Functionalization of MoS2 Nanosheets by an Organosulfur Reaction

A simple approach to exfoliate and functionalize MoS₂ in a single‐step is described, which combines the dispersion of MoS₂ in polybutadiene solution and ultrasonication processes. The great advantage of this process is that a colloidal stability of MoS₂ in nonpolar solvent is achieved by chemically bonding polybutadiene on the perimeter edge sites of MoS₂ sheets. In addition, elastomeric nanocomposite has been prepared with singular mechanical properties using functionalized MoS₂ as nanofiller in a polybutadiene matrix with a subsequent vulcanization reaction.     

Superior Performance of a MoS2‐RGO Composite and a Borocarbonitride in the Electrochemical Detection of Dopamine,Uric Acid and Adenine

A MoS₂‐RGO composite and borocarbonitride (BC₅N) have been used as electrodes to selectively detect dopamine and uric acid in the presence of ascorbic acid. Both the electrodes show excellent eletrocatalytic activity towards the detection of dopamine, the detection limits being 0.55 μM and 2.1 μM in the case of MoS₂‐RGO and BCN respectively. MoS₂‐RGO shows a linear range of current over the 1–110 μM concentrations of dopamine, while BCN shows over the 2.3–20 μM range. BCN also exhibits satisfactory performance in the oxidation of uric acid with a detection limit of 3.8 μM and the linear range from 4 to 40 μM. The MoS₂‐RGO has also been used to detect adenine as well.     

Covalent Assembly of MoS2 Nanosheets with SnS Nanodots as Linkages for Lithium/Sodium‐Ion Batteries

Weak van der Waals interactions between interlayers of two‐dimensional layered materials result in disabled across‐interlayer electron transfer and poor layered structural stability, seriously deteriorating their performance in energy applications. Herein, we propose a novel covalent assembly strategy for MoS₂ nanosheets to realize unique MoS₂/SnS hollow superassemblies (HSs) by using SnS nanodots as covalent linkages. The covalent assembly based on all‐inorganic and carbon‐free concept enables effective across‐interlayer electron transfer, facilitated ion diffusion kinetics, and outstanding mechanical stability, which are evidenced by experimental characterization, DFT calculations, and mechanical simulations. Consequently, the MoS₂/SnS HSs exhibit superb rate performance and long cycling stability in lithium‐ion batteries, representing the best comprehensive performance in carbon‐free MoS₂‐based anodes to date. Moreover, the MoS₂/SnS HSs also show excellent sodium storage performance in sodium‐ion batteries.     

Photoelectrochemical Detection of H2O2 Based on Flower‐Like CuInS2‐Graphene Hybrid

A novel photoelectrochemcial biosensing system was fabricated based on the composition of horseradish peroxidase (HRP), flower‐like CuInS₂ (CIS) and graphene on indium tin oxide (ITO) electrode for detecting H₂O₂. The graphene layer was used as highly conductive scaffolds for electron transport from the ITO electrode to CIS. Furthermore, the flower‐like CIS enhanced the multi‐reflection of light and provided matrixes for the adsorption of HRP. Utilizing one‐pot solvothermal method, we prepared flower‐like CIS‐graphene hybrid (GCIS). Electrochemical tests displayed advantage of graphene with better electron conductivity, and HRP/GCIS showed higher photoelectrochemical behavior.     

Nanomolar Determination of Methyldopa in the Presence of Large Amounts of Hydrochlorothiazide Using a Carbon Paste Electrode Modified with Graphene Oxide Nanosheets and 3‐(4′‐Amino‐3′‐hydroxy‐biphenyl‐4‐yl)‐acrylic Acid

A novel electrochemical sensor for sensitive detection of methyldopa at physiological pH was developed by the bulk modification of carbon paste electrode (CPE) with graphene oxide nanosheets and 3‐(4′‐amino‐3′‐hydroxy‐biphenyl‐4‐yl)‐acrylic acid (3,′AA). Applying square wave voltammetry (SWV), in phosphate buffer solution (PBS) of pH 7.0, the oxidation current increased linearly with two concentration intervals of methyldopa, one is 1.0×10^?8–1.0×10^?6 M and the other is 1.0×10^?6–4.5×10^?5 M. The detection limit (3σ) obtained by SWV was 9.0 nM. The modified electrode was successfully applied for simultaneous determination of methyldopa and hydrochlorothiazide. Finally, the proposed method was applied to the determination of methyldopa and hydrochlorothiazide in some real samples.     

Side‐Chain‐Directed Dispersion of MoS2 Nanosheets by V‐Shaped Polyaromatic Compounds

Bulk molybdenum disulfide (MoS₂) itself is virtually insoluble in common organic solvents because of the tight stacks of multiple MoS₂ nanosheets. Here we report that V‐shaped polyaromatic compounds with non‐ionic side chains can efficiently exfoliate and disperse the inorganic nanosheets. Simple grinding and sonication (less than total 1 h) of MoS₂ powder with the V‐shaped compounds gave rise to large MoS₂ nanosheets highly dispersed in NMP through efficient host‐guest S–π interactions. DLS and AFM analyses revealed that the lateral sizes (ca. 150–270 nm) and thicknesses (ca. 2–8 nm) of the products depend on the identity of the non‐ionic side chains on the V‐shaped dispersant.     

MoS_2纳米片及其增强环氧树脂基复合材料的制备与性能研究

以液相分散法为基础制备了MoS2纳米片悬浮液.对该悬浮液进行了吸光性能和荧光性能表征;结果显示悬浮液荧光信号明显增强;同时得到增加超声时间、降低离心转速、采用粒径较大的块状粉末和加入球磨工艺这些因素是可以提高悬浮液的吸光度的优化工艺条件.采用微区荧光测试测得了单个MoS2纳米片的荧光光谱,其主峰位置在652 nm,对应的带隙能量是1.9 e V;还对单个纳米片进行退火处理,其荧光信号在退火后有所增强.对MoS2纳米片进行了AFM和SEM表征显示大部分纳米片的平面尺寸在几百纳米,厚度约为几纳米.另外,将MoS2纳米片悬浮液与E51环氧树脂混合,制备了MoS2纳米片增强环氧树脂基复合材料.对该复合材料进行了荧光性能和拉伸性能测试.结果显示复合材料的荧光信号也明显增强;且经退火后,因为复合材料内部残余热应力的关系,该复合材料的荧光信号的峰值位置出现移动.同时,该复合材料的韧性也有提升.     

Selective Detection of Dopamine in the Presence of Uric Acid Using NiO Nanoparticles Decorated on Graphene Nanosheets Modified Screen‐printed Electrodes

A convenient, low cost, and sensitive electrochemical method, based on a disposable graphene nanosheets (GR) and NiO nanoparticles modified carbon screen printed electrode (NiO/GR/SPE), is described for the simultaneous determination of dopamine (DA) and uric acid (UA). The modified electrode exhibited good electrocatalytic properties toward the oxidation of DA and UA. A peak potential difference of 150 mV between DA and UA was large enough to determine DA and UA individually and simultaneously. The anodic peak currents of DA were found to be linear in the concentration range of 1.0–500.0 μM with the detection limit of 3.14×10^?7 M.     

Covalent Assembly of MoS2 Nanosheets with SnS Nanodots as Linkages for Lithium/Sodium-Ion Batteries

Weak van der Waals interactions between interlayers of two-dimensional layered materials result in disabled across-interlayer electron transfer and poor layered structural stability, seriously deteriorating their performance in energy applications. Herein, we propose a novel covalent assembly strategy for MoS₂ nanosheets to realize unique MoS₂/SnS hollow superassemblies (HSs) by using SnS nanodots as covalent linkages. The covalent assembly based on all-inorganic and carbon-free concept enables effective across-interlayer electron transfer, facilitated ion diffusion kinetics, and outstanding mechanical stability, which are evidenced by experimental characterization, DFT calculations, and mechanical simulations. Consequently, the MoS₂/SnS HSs exhibit superb rate performance and long cycling stability in lithium-ion batteries, representing the best comprehensive performance in carbon-free MoS₂-based anodes to date. Moreover, the MoS₂/SnS HSs also show excellent sodium storage performance in sodium-ion batteries.     

Electrochemical Sensor for Ultrasensitive Determination of Doxorubicin and Methotrexate Based on Cyclodextrin‐Graphene Hybrid Nanosheets

In this work, an electrochemical sensor based on a cyclodextrin‐graphene hybrid nanosheets modified glassy carbon electrode (CD‐GNs/GCE) was proposed for the ultrasensitive determination of doxorubicin and methotrexate. The peak currents of doxorubicin and methotrexate on the CD‐GNs/GCE increased 26.5 and 23.7 fold, respectively, compared to the results obtained on the bare GCE. Under optimized conditions, the linear response ranges for doxorubicin and methotrexate are 10 nM–0.2 µM and 0.1 µM–1.0 µM, with detection limits of 0.1 nM and 20 nM, respectively. The sensor showed the advantages of simple preparation, low cost, high sensitivity, good stability and reproducibility. These properties make the prepared sensor a promising tool for the determination of trace amounts of doxorubicin and methotrexate in biological, clinical and pharmaceutical fields.     

Application of a Carbon‐Paste Electrode Modified with 2,7‐Bis(ferrocenyl ethyl)fluoren‐9‐one and Carbon Nanotubes for Voltammetric Determination of Levodopa in the Presence of Uric Acid and Folic Acid

A carbon‐paste electrode modified with 2,7‐bis(ferrocenyl ethyl)fluoren‐9‐one and carbon nanotubes was used for the sensitive voltammetric determination of levodopa (LD). The electrochemical response characteristics of the modified electrode toward LD, uric acid (UA) and folic acid (FA) were investigated. The results showed an efficient catalytic activity of the electrode for the electrooxidation of LD, which leads to lowering its overpotential by more than 320 mV. The modified electrode exhibits an efficient electron mediating behavior together with well‐separated oxidation peaks for LD, UA and FA. Also, the modified electrode was used for determination of LD in some real samples.     

Synthesis of Highly Uniform Molybdenum–Glycerate Spheres and Their Conversion into Hierarchical MoS2 Hollow Nanospheres for Lithium‐Ion Batteries

Highly uniform Mo–glycerate solid spheres are synthesized for the first time through a solvothermal process. The size of these Mo–glycerate spheres can be easily controlled in the range of 400–1000 nm by varying the water content in the mixed solvent. As a precursor, these Mo–glycerate solid spheres can be converted into hierarchical MoS₂ hollow nanospheres through a subsequent sulfidation reaction. Owing to the unique ultrathin subunits and hollow interior, the as‐prepared MoS₂ hollow nanospheres exhibit appealing performance as the anode material for lithium‐ion batteries. Impressively, these hierarchical structures deliver a high capacity of about 1100 mAh g^?1 at 0.5 A g^?1 with good rate retention and long cycle life.     

Ultrasonic‐electrodeposition of Flower‐like Graphene Nanosheets in Ionic Liquid and Its Sensing for Ascorbic Acid

Choline chloride–based ionic liquid Ethaline were employed as the supporting electrolyte, graphene (GE) nanosheet was prepared with ultrasonic wave assisted electrodeposition for the first time. Scanning electron microscope results indicated that flower‐like GE nanosheets were obtained at the electrode surface. Energy dispersive X–ray spectroscopy, Fourier transform infrared spectra and Raman spectra were used to characterize the composition of the flower‐like GE nanosheets. Electrochemical methods showed that the flower‐like GE nanosheets based sensor exhibited high electrocatalytic activity for ascorbic acid (AA) oxidation and can be potentially used for the sensitive amperometric sensing of AA. Amperometric experiments showed that the sensor displayed broad linearity from 0.25 μM to 2.0 mM with a relative low detection limit of 0.1 μM (S/N = 3).     

Controlled Assembly of Porphyrin‐MoS2 Composite Nanosheets for Enhanced Photoelectrochemical Performance

As a promising non‐precious metal photoelectrochemical (PEC) catalyst, MoS₂ exhibits high electrocatalytic activity and stability, while the weak light absorption efficiency and low photoresponse current limit its practical application. Herein, a facile co‐assembly approach is proposed to construct porphyrin‐MoS₂ composite photoelectrocatalysts. The as‐prepared photoelectrocatalysts show a significantly enhanced photocurrent response as high as 16 μA cm^?2, which is about 2 times higher than that of bare MoS₂. Furthermore, the obtained porphyrin‐MoS₂ catalysts exhibit excellent durability when tested for 23000 s, thus providing a useful strategy for the design of highly efficient dye‐sensitized PEC catalysts.     

Electrochemical Behavior of Caffeic Acid Assayed with Gold Nanoparticles/Graphene Nanosheets Modified Glassy Carbon Electrode

A gold nanoparticle (AuNP) and graphene nanosheet (GN) modified glassy carbon electrode (GCE) is proposed as voltammetric sensor for caffeic acid assay. The sensor exhibits a surface‐confined and reversible process for oxidation of caffeic acid revealed by cyclic voltammetry. The results show more favorable electron transfer kinetics than the bare GCE. The linear response of the sensor is from 5×10^?7 to 5×10^?5 M with a detection limit of 5×10^?8 M (S/N=3). The AuNP/GN nanocomposite shows more favorable electrochemical activity and should be a kind of more robust and advanced functional material, which provides a promising platform for electrochemical sensors and biosensors. The method was successfully applied to detect caffeic acid in pharmaceutical tablets with satisfactory results.     

Ultrathin MoS2 Nanosheets Supported on N‐doped Carbon Nanoboxes with Enhanced Lithium Storage and Electrocatalytic Properties

Molybdenum disulfide (MoS₂) has received considerable interest for electrochemical energy storage and conversion. In this work, we have designed and synthesized a unique hybrid hollow structure by growing ultrathin MoS₂ nanosheets on N‐doped carbon shells (denoted as C@MoS₂ nanoboxes). The N‐doped carbon shells can greatly improve the conductivity of the hybrid structure and effectively prevent the aggregation of MoS₂ nanosheets. The ultrathin MoS₂ nanosheets could provide more active sites for electrochemical reactions. When evaluated as an anode material for lithium‐ion batteries, these C@MoS₂ nanoboxes show high specific capacity of around 1000 mAh g^?1, excellent cycling stability up to 200 cycles, and superior rate performance. Moreover, they also show enhanced electrocatalytic activity for the electrochemical hydrogen evolution.     

MnO2‐TiO2 Nanocomposite and 2‐(3,4‐Dihydroxyphenethyl) Isoindoline‐1,3‐Dione as an Electrochemical Platform for the Concurrent Determination of Cysteine,Tryptophan and Uric Acid

A novel modified carbon paste electrode (CPE) based on an MnO₂‐TiO₂ nanocomposite and 2‐(3,4 dihydroxyphenethyl) isoindoline‐1,3‐dione (DPID) as the modifier for the simultaneous analysis of cysteine (Cys), tryptophan (Trp) and uric acid (UA), as three key biochemicals present in human body. The MnO₂/TiO₂ nanocomposite was synthesized through a chemical co‐precipitation approach and the resulting electrode (MnO₂‐TiO₂/DPID/CPE) was used for studying the electrochemical oxidation of cysteine (Cys), tryptophan (Trp) and uric acid. As opposed to conventional CPEs, the oxidation peak potential of cysteine on MnO₂‐TiO₂/DPID/CPE had a 600.0 mV decrease in overpotential and could be observed at 30.0 mV, and the signals were linear from 0.025 to 200.0 μM, and a lower detection limit of 0.013 μM was reached. The MnO₂‐TiO₂/DPID/CPE was satisfactorily used for the concurrent analysis of Cys, Trp and UA in pharmaceutical and biological samples.     

Gold Nanoparticles‐β‐Cyclodextrin‐Chitosan‐Graphene Modified Glassy Carbon Electrode for Ultrasensitive Detection of Dopamine and Uric Acid

The nanocomposite (denoted as GR‐AuNPs‐CD‐CS) of graphene (GR), gold nanoparticles (AuNPs), chitosan (CS) and β‐cyclodextrin (β‐CD) was prepared to modify a glassy carbon electrode. The as‐modified electrode was explored for the ultrasensitive detection of dopamine (DA) and uric acid (UA). The modified electrode demonstrated linearly increased current response in the concentration range of 0.1–120 µm for DA and 0.05–70 µm for UA, with so far the best detection limit for DA and UA. Good stability and repeatability were further demonstrated for the as‐made sensor.