Reaction with organic halides as a general method for the covalent functionalization of nanosheets of 2D chalcogenides and related materials

Manjunatha, S.; Rajesh, S.; Vishnoi, Pratap; Rao, C. N. R.

doi:10.1557/jmr.2017.224

Cited by 29 publications

(13 citation statements)

References 17 publications

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“…2. IR spectrum of WS 2 has a broad and less intense peaks which are in good agreement with IR data of bulk WS 2 reported earlier [56][57][58]. IR spectra of PNA and its WS 2 nanocomposites show peaks around 3400 cm −1 due to the imine N-H stretching vibrations [59].…”

Section: Ftir Studiessupporting

confidence: 89%

Synthesis, characterization and dielectric studies of poly(1-naphthylamine)–tungsten disulphide nanocomposites

Saidu

Thomas

2020

SN Appl. Sci.

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Here, novel poly(1-naphthylamine)-tungsten disulphide (PNA-WS 2 ) nanocomposites were synthesized through an in-situ chemical oxidative polymerization of 1-naphthylamine in the presence of ultrasonically dispersed WS 2 . The effect of WS 2 addition on the optoelectrical, morphological and thermal properties of PNA was studied by using different analytical tools. SEM images revealed that PNA aggregates are well supported on the dispersed WS 2 sheets. The formation of a fibrous network of PNA over the dispersed WS 2 layers evidenced from the TEM images has suggested larger surface area and better interfacial interaction between PNA and incorporated WS 2 layers . The thermal stability was improved upon the incorporation of WS 2 . Optical bandgap values of PNA-WS 2 nanocomposites were lower than that of bulk WS 2 and pristine PNA. Electrical and dielectric studies have confirmed an improvement in conductivity and dielectric properties with increasing WS 2 content, which was credited to the better charge transport between the polar backbone of PNA and charged surface of dispersed WS 2 due to enhanced interfacial area and electrostatic interactions between the components. A maximum AC conductivity of 4.4 × 10 -3 Sm −1 was displayed by nanocomposite containing 20% WS 2 loading and a further increase in WS 2 content showed a detrimental effect in electrical and dielectric properties. The present study has demonstrated that optical and dielectric properties of composites can be readily tuned by proper control of the composition and dispersion of WS 2 within the PNA matrix.

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Section: Ftir Studiessupporting

confidence: 89%

Synthesis, characterization and dielectric studies of poly(1-naphthylamine)–tungsten disulphide nanocomposites

Saidu

Thomas

2020

SN Appl. Sci.

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“…In contrast, the 1T phase has a tetragonal symmetry, with an octahedral metal coordination, as the layers are offset from each other. The conductivity of 2H is semiconducting, whereas 1T is metallic, in which the latter is recognized for its reactivity towards functionalization , as well as enhancing electrochemical properties . Moreover, both edge and basal sites are active in 1T-phase TMDs, further improving the electrocatalytic performance. , With good conductivity, fast electron-transfer kinetics, and increased catalytic sites, these 1T-TMDs are anticipated to promote the signal transduction of an electrochemical biosensor.…”

Section: Results and Discussionmentioning

confidence: 99%

1T-Phase Transition Metal Dichalcogenides (MoS₂, MoSe₂, WS₂, and WSe₂) with Fast Heterogeneous Electron Transfer: Application on Second-Generation Enzyme-Based Biosensor

Rohaizad¹,

Mayorga‐Martinez²,

Sofer

et al. 2017

ACS Appl. Mater. Interfaces

147

100

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Two-dimensional transition metal dichalcogenides (TMDs) have been in the spotlight for their intriguing properties, including a tunable band gap and fast heterogeneous electron-transfer (HET) rate. Understandably, they are especially attractive in the field of electrochemical biosensors. In this article, HET capabilities of various TMDs (MoS, MoSe, WS, and WSe) within group VI chemically exfoliated via t-BuLi intercalation are studied and these capabilities are used in the second generation electrochemical glucose biosensor. Strikingly, tungsten dichalcogenides (WS and WSe) exhibit superior HET properties compared to that of their molybdenum counterparts (MoS and MoSe). When incorporated into second generation glucose biosensors, WS and WSe generated a higher electrochemical responses than that of MoS and MoSe, following the same trend as expected. The commendable performance by WX is attributed to the dominance of 1T phase, revealed by characterization data. The developed and optimized 1T WX-based biosensor achieved analytical requirements of selectivity, wide linear ranges, as well as low limits of detection and quantification. The outstanding electrochemical performances of WS and WSe are to be recognized, adding on to the fact that they are not decorated with any metal nanoparticles. This is imperative to showcase the real potential of two-dimensional TMDs in electrochemical biosensors.

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“…The nucleophilic reaction occurs because of electron transfer between the metallic 1T phase and the halide, resulting in forming the covalent C−S bond. Interestingly, semiconducting sheets of the stable 2H form have been functionalized by reaction with iodobenzenes in the presence of a Pd 0 catalyst . It has also been shown that other organic bromides and iodides including certain fluorophores react with the MoS 2 sheets forming C−S bonds.…”

Section: Methodsmentioning

confidence: 99%

Covalently Functionalized Nanoparticles of Semiconducting Metal Chalcogenides and Their Attributes

et al. 2017

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Covalent functionalization of the semiconducting chalcogenide nanoparticles ZnS, ZnSea nd CdS by reaction with organic halides, specifically iodobenzenes, has been demonstrated. DFT calculations have thrown light on the electronic structure of the functionalized chalcogenides. Chalcogenides with bonded phenyl groups exhibit al ong wavelength charge-transfer band as predicted by theory.F unctionalization has been carried out with fluorophores as well. Functionalization of semiconductingc halcogenide particles offers many possibilities for study of their properties and application.Chemical modificationo fn anomaterials by appropriate functional groups has become an active area of research in recent years. Functionalization enables us to tune physical andc hemical properties of the materials,t hereby making them more suitable for various applications.[1-5] Stability and solventd ispersibility of materials can also be enhanced by surface functionalization.I th as been shown recently that organic halides can be used to functionalize MoS 2 sheets.[3] Thus, the reaction of iodobenzenes with the metallic 1T form of MoS 2 functionalizes the surface forming CÀSb onds. The nucleophilic reaction occurs because of electron transfer betweent he metallic1 T phase and the halide,r esulting in forming the covalentC ÀS bond. Interestingly,s emiconducting sheets of the stable 2H form have been functionalized by reactionw ith iodobenzenes in the presence of aP d 0 catalyst. [6,7] It has also been shown that other organic bromides and iodides including certain fluorophores react with the MoS 2 sheets forming CÀSb onds. Encouraged by these results, we have explored whether covalent functionalization of nanoparticles of semiconducting metal chalcogenides such as ZnS and CdS can be carriedo ut by the reactionw ith organic halides such as iodobenzenes. We find that it is indeed possible to do so by the use of the Pd 0 catalyst. Such covalent functionalization resultsi nc harge-transfer between the sulfide and the benzene, giving rise to al ongwavelength absorption band. DFT calculations, carried out to understand the electronic structure and properties of the functionalized chalcogenides, predict the occurrence of ac hargetransfer band. We shall first examine functionalization of ZnS nanoparticles by iodobenzenes. ZnS nanoparticles of % 5-10 nm diameter ( Figure S1;S upporting Information), prepared by ap rocedure reported in the literature, [8] were reactedw ith iodobenzene, 4-iodoanisole or 4-iodonitrobenzene (Scheme 1) by heating in toluene under an itrogen atmosphere.T he solid products obtained show evidencef or covalentl inking of the phenyl group with ZnS.

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Reaction with organic halides as a general method for the covalent functionalization of nanosheets of 2D chalcogenides and related materials

Abstract: Abstract

Cited by 29 publications

References 17 publications

Synthesis, characterization and dielectric studies of poly(1-naphthylamine)–tungsten disulphide nanocomposites

Synthesis, characterization and dielectric studies of poly(1-naphthylamine)–tungsten disulphide nanocomposites

1T-Phase Transition Metal Dichalcogenides (MoS₂, MoSe₂, WS₂, and WSe₂) with Fast Heterogeneous Electron Transfer: Application on Second-Generation Enzyme-Based Biosensor

Covalently Functionalized Nanoparticles of Semiconducting Metal Chalcogenides and Their Attributes

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Reaction with organic halides as a general method for the covalent functionalization of nanosheets of 2D chalcogenides and related materials

Abstract: Abstract

Cited by 29 publications

References 17 publications

Synthesis, characterization and dielectric studies of poly(1-naphthylamine)–tungsten disulphide nanocomposites

Synthesis, characterization and dielectric studies of poly(1-naphthylamine)–tungsten disulphide nanocomposites

1T-Phase Transition Metal Dichalcogenides (MoS2, MoSe2, WS2, and WSe2) with Fast Heterogeneous Electron Transfer: Application on Second-Generation Enzyme-Based Biosensor

Covalently Functionalized Nanoparticles of Semiconducting Metal Chalcogenides and Their Attributes

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1T-Phase Transition Metal Dichalcogenides (MoS₂, MoSe₂, WS₂, and WSe₂) with Fast Heterogeneous Electron Transfer: Application on Second-Generation Enzyme-Based Biosensor