Functional Nanosheet Synthons by Covalent Modification of Transition-Metal Dichalcogenides

Presolski, Stanislav I.; Wang, Lu; Loo, Adeline Huiling; Ambrosi, Adriano; Lazar, Petr; Ranc, Václav; Otyepka, Michal; Zbořil, Radek; Tomanec, Ondřej; Ugolotti, Juri; Sofer, Zdeněk; Pumera, Martin

doi:10.1021/acs.chemmater.6b04171

Cited by 59 publications

(49 citation statements)

References 25 publications

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“…The most commonly used chemisorption strategy exploits chalcogen vacancy defects to coordinate nucleophiles in dative bonds, in particular thiols 112,259,[379][380][381][382][383][384][385][386][387][388] with dithiolane 389…”

Section: Functionalization Of Solution-processed Tmd Nanosheetsmentioning

confidence: 99%

Molecular chemistry approaches for tuning the properties of two-dimensional transition metal dichalcogenides

et al. 2018

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Two-dimensional (2D) semiconductors, such as ultrathin layers of transition metal dichalcogenides (TMDs), offer a unique combination of electronic, optical and mechanical properties, and hold potential to enable a host of new device applications spanning from flexible/wearable (opto)electronics to energy-harvesting and sensing technologies. A critical requirement for developing practical and reliable electronic devices based on semiconducting TMDs consists in achieving a full control over their charge-carrier polarity and doping. Inconveniently, such a challenging task cannot be accomplished by means of well-established doping techniques (e.g. ion implantation and diffusion), which unavoidably damage the 2D crystals resulting in degraded device performances. Nowadays, a number of alternatives are being investigated, including various (supra)molecular chemistry approaches relying on the combination of 2D semiconductors with electroactive donor/acceptor molecules. As yet, a large variety of molecular systems have been utilized for functionalizing 2D TMDs via both covalent and non-covalent interactions. Such research endeavours enabled not only the tuning of the charge-carrier doping but also the engineering of the optical, electronic, magnetic, thermal and sensing properties of semiconducting TMDs for specific device applications. Here, we will review the most enlightening recent advancements in experimental (supra)molecular chemistry methods for tailoring the properties of atomically-thin TMDs - in the form of substrate-supported or solution-dispersed nanosheets - and we will discuss the opportunities and the challenges towards the realization of novel hybrid materials and devices based on 2D semiconductors and molecular systems.

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Section: Functionalization Of Solution-processed Tmd Nanosheetsmentioning

confidence: 99%

Molecular chemistry approaches for tuning the properties of two-dimensional transition metal dichalcogenides

et al. 2018

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“…halide electrophiles (Figure 1a) or nucleophilic thiol reagents such as thiobarbituric acid. [18][19][20][39][40][41] Although 2H-MoS2 does not readily undergo these reactions, covalent functionalization of 2H-MoS2 has been reported using iodobenzene in the presence of a palladium catalyst. 41 The coverage of functional groups achieved after chemical exfoliation is limited to <25-30% per MoS2 unit, presumably due to the limited negative charge that can be held by the nanosheets after lithiation and exfoliation in water.…”

mentioning

confidence: 99%

Reductant-Activated, High-Coverage, Covalent Functionalization of 1T′-MoS₂

Yan

Cabán-Acevedo

Papadantonakis

et al. 2019

ACS Materials Lett.

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Recently developed covalent functionalization chemistry for MoS2 in the 1Tʹ phase enables the formation of covalent chalcogenide-carbon bonds from alkyl halides and aryl diazonium salts. However, the coverage of functional groups using this method has been limited by the negative charge stored in the exfoliated MoS2 sheets to <25-30% per MoS2 unit. We report herein a reductantactivated functionalization wherein one-electron metallocene reductants, such as nickelocene, octamethylnickelocene, and cobaltocene, are introduced during functionalization with methyl and propyl halides to tune the coverage of the alkyl groups. The reductant-activated functionalization yields functional group coverages up to 70%, ~ 1.5-2 times higher than the previous limit, and enables functionalization by weak electrophiles, such as 1-chloropropane, that are otherwise unreactive with chemically exfoliated MoS2. We also explored the dependence of coverage on the strength of the leaving group and the steric hindrance of the alkyl halide in the absence of reductants, and showed that functionalization was ineffective for chloride leaving groups and for secondary and tertiary alkyl iodides. These results demonstrate a substantial increase in coverage compared to functionalization without reductants, and may impact the performance of these materials in applications reliant on surface interactions. Furthermore, this method may be applicable to the covalent functionalization of similar layered materials and metal chalcogenides.

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“…

biomedicine, [2,3] tribology, [4] photonics, [5] and electrocatalysis, [6] among others. [7] This progress has focused on the functionalization of mono-or few-layer nanosheets with lateral dimensions greater than 100 nm by combining chemical exfoliation, [8][9][10][11][12] micromechanical exfoliation, [13] or liquid exfoliation [14] with the reaction of functionalities. [7] This progress has focused on the functionalization of mono-or few-layer nanosheets with lateral dimensions greater than 100 nm by combining chemical exfoliation, [8][9][10][11][12] micromechanical exfoliation, [13] or liquid exfoliation [14] with the reaction of functionalities.

…”

mentioning

confidence: 99%

Simultaneous Fabrication and Functionalization of Nanoparticles of 2D Materials with Hybrid Optical Properties

Ibrahim

Irannejad

Wales

et al. 2018

Advanced Optical Materials

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biomedicine, [2,3] tribology, [4] photonics, [5] and electrocatalysis, [6] among others. Significant progress has been made recently in fabricating and functionalizing 2D nanosheets of transition metal dichalcogenides. [7] This progress has focused on the functionalization of mono-or few-layer nanosheets with lateral dimensions greater than 100 nm by combining chemical exfoliation, [8][9][10][11][12] micromechanical exfoliation, [13] or liquid exfoliation [14] with the reaction of functionalities. The formation and functionalization of smaller 2D nanoparticles or quantum dots, on the other hand, is still in its infancy.In what has been cited as the first direct evidence of covalent functionalization of a nanoscale transition metal dichalcogenide, Tuxen et al. produced MoS 2 monolayer nanoclusters in ultrahigh vacuum on a gold substrate and attached dibenzothiophene molecules to the clusters via controlled vapor exposure. [15,16] Beyond substrate-supported nanoclusters, the functionalization of nongraphene 2D nanoparticles suspended in solution was reported last year. Atkin et al. combined ultrasonication of WS 2 with microwave treatment in a citric acid-containing solution to produce monolayer WS 2 nanosheets ≈20-80 nm in diameter decorated with 2-5 nm carbon dots. [6] Jung et al. impinged BN flakes with super-heated nanoparticles then exposed them to water vapor to produce edge-hydroxylated BN quantum dots with 8 nm lateral size. [2] These techniques for fabricating and functionalizing 2D nanosheets and smaller nanoparticles are relatively slow (in some cases requiring several days), often require dangerous chemicals and elevated temperatures, and their demonstration has been material specific. In the case of functionalized 2D nanoparticles other than graphene, such as functionalized MoS 2 , WS 2 , and BN quantum dots, potentially exciting multifunctional optical properties have not been realized. The ability to produce a variety of hybrid 2D nanoparticles that possess the optical properties of both the host 2D material and functional groups would be extremely valuable for many of the aforementioned applications.We introduce a rapid femtosecond laser technique that simultaneously reduces the dimensions of flakes of 2D materials to a few nanometers and dissociates solvent molecules to bond with the edges of the freshly cleaved 2D sheets, in order to produce functionalized nanoparticles of 2D materials. Etha nol, a common and inexpensive solvent, is used to facilitate functionalization A general, rapid technique is introduced to simultaneously fabricate and functionalize nanoparticles of 2D materials. A femtosecond laser is used to irradiate flakes of 2D materials in an ethanol-containing solvent. The highly energetic laser pulses exfoliate and cleave the flakes into nanosheets with diameters of ≈3 nm and simultaneously dissociate the solvent molecules. The dissociated carbon and oxygen atoms bond with the freshly cleaved 2D nanoparticles to satisfy edge sites, resulting in the formation of hybrid 2D nanoparticles...

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Functional Nanosheet Synthons by Covalent Modification of Transition-Metal Dichalcogenides

Cited by 59 publications

References 25 publications

Molecular chemistry approaches for tuning the properties of two-dimensional transition metal dichalcogenides

Molecular chemistry approaches for tuning the properties of two-dimensional transition metal dichalcogenides

Reductant-Activated, High-Coverage, Covalent Functionalization of 1T′-MoS₂

Simultaneous Fabrication and Functionalization of Nanoparticles of 2D Materials with Hybrid Optical Properties

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Functional Nanosheet Synthons by Covalent Modification of Transition-Metal Dichalcogenides

Cited by 59 publications

References 25 publications

Molecular chemistry approaches for tuning the properties of two-dimensional transition metal dichalcogenides

Molecular chemistry approaches for tuning the properties of two-dimensional transition metal dichalcogenides

Reductant-Activated, High-Coverage, Covalent Functionalization of 1T′-MoS2

Simultaneous Fabrication and Functionalization of Nanoparticles of 2D Materials with Hybrid Optical Properties

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Reductant-Activated, High-Coverage, Covalent Functionalization of 1T′-MoS₂