Supramolecular networks stabilise and functionalise black phosphorus

Korolkov, Vladimir V.; Timokhin, I. A.; Haubrichs, Rolf; Smith, Emily F.; Yang, Lixu; Yang, Sihai; Champness, Neil R.; Schröder, Martin; Beton, Peter H.

doi:10.1038/s41467-017-01797-6

Cited by 74 publications

(67 citation statements)

References 72 publications

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“…Whereas its outstanding physical and materials properties have been intensively investigated, its chemistry remains almost unexplored . Indeed, a first series of noncovalent functionalization protocols has been reported, mainly focused on improving the intrinsic instability of BP against water and oxygen . Beyond these approaches, the covalent functionalization of the interface is one of the most promising routes for fine‐tuning the chemical and physical properties of 2D nanomaterials .…”

Section: Figurementioning

confidence: 99%

Lattice Opening upon Bulk Reductive Covalent Functionalization of Black Phosphorus

et al. 2019

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The chemical bulk reductive covalent functionalization of thin-layerb lack phosphorus (BP) using BP intercalation compounds has been developed. Through effective reductive activation, covalent functionalization of the charged BP by reaction with organic alkylh alides is achieved. Functionalization was extensively demonstrated by means of several spectroscopic techniques and DFT calculations;t he products showed higher functionalization degrees than those obtained by neutral routes.Since 2014, two-dimensional (2D) black phosphorus (BP) has attracted tremendous attention throughout the scientific community due to its high p-type charge carrier mobility and its tunable direct band gap. [1][2][3][4][5][6][7][8][9] In contrast to graphene,B P exhibits amarked puckering of the sp 3 structure,constituting atwo-dimensional s-only system, involving one lone electron pair at each Pa tom. Whereas its outstanding physical and materials properties have been intensively investigated, its chemistry remains almost unexplored. [10][11][12] Indeed, af irst series of noncovalent functionalization protocols has been reported, mainly focused on improving the intrinsic instability of BP against water and oxygen. [13][14][15][16][17] Beyond these approaches,t he covalent functionalization of the interface is one of the most promising routes for fine-tuning the chemical and physical properties of 2D nanomaterials. [18,19] In this sense,only afew recent reports on single-flake chemistry with diazonium salts, [20] and wet-chemistry on previously exfoliated flakes with nucleophiles [21][22][23] or carbon-free radicals [24] have been reported so far.This is probably due to the intrinsic low degree of reactivity of neutral BP towards these reactions and the difficulties associated with overcoming the huge van der Waals energy stored within aBPcrystal, thus blocking the direct functionalization of BP.A long this front, ab ulk wetchemical derivatization sequence remains to be found. Moreover, an unambiguous determination of the covalent binding and its influence in the chemical structure of the P-layers is required to systematically explore the characteristics of BP reactivity.To address these challenges we took advantage of the well-known reductive graphene chemistry using graphite intercalation compounds (GICs). [18,[25][26][27] As af irst success in this direction, we have recently reported the preparation of BP intercalation compounds (BPICs) with alkali metals (K and Na). [28] This paves the way for the exploration of the reductive route using activated negatively charged BP-ite nanosheets and electrophiles (E) as covalent reaction partners.Herein, we provide the first real proof for covalent binding in BP with alkyl halides using abattery of characterization techniques.F urthermore,d ensity functional theory (DFT) calculations were carried out to rationalize our results, providing adeep understanding of the covalent derivatization of BP.This thorough study reveals for the first time the lattice opening in BP,absent in graphene,which is a...

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Section: Figurementioning

confidence: 99%

Lattice Opening upon Bulk Reductive Covalent Functionalization of Black Phosphorus

et al. 2019

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“…9 However, due to lone pairs pointing outwards from the surface, BP is highly reactive with oxygen, which makes its properties sensitive to ambient conditions. 10,11 The rapid oxidation of BP can be prevented by capping layers, 12,13 and thus the stability and performance for future applications depends on intrinsic defects such as point defects, line defects and impurities. The development of novel devices is mostly hindered by the lack of understanding of defects and defect creation.…”

Section: Introductionmentioning

confidence: 99%

Structure and properties of intrinsic and extrinsic defects in black phosphorus

Gaberle

Shluger

2018

Nanoscale

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“…In the context of stabilizing BP under ambient conditions, Korolkov et al successfully formed SAMNs stabilized by hydrogen bonds by solution deposition to passivate BP and inhibit oxidation under ambient conditions [68]. The molecules used were trimesic acid (TA) and melamine cyanurate (CA.M), which are known to form supramolecular networks on other 2D materials.…”

Section: Non-covalent Functionalization Of Hbn and Black Phosphorusmentioning

confidence: 99%

Chemical modification of 2D materials using molecules and assemblies of molecules

Daukiya

Seibel

Feyter

2019

Advances in Physics: X

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In this article, we discuss the recent progress on controlled structural modification of 2D materials by means of molecular functionalization, with a focus on scanning probe microscopy techniques for their characterization. For many practical applications of these novel materials, it is necessary to tune their electronic and optical properties, and molecule-based functionalization is a powerful approach to reach this. We discuss recent covalent and non-covalent approaches, for functionalization of graphene, transition metal dichalcogenides, black phosphorus, and hexagonal boron nitride. Nanostructuring approaches and their impact on 2D materials' properties are highlighted.

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Supramolecular networks stabilise and functionalise black phosphorus

Cited by 74 publications

References 72 publications

Lattice Opening upon Bulk Reductive Covalent Functionalization of Black Phosphorus

Lattice Opening upon Bulk Reductive Covalent Functionalization of Black Phosphorus

Structure and properties of intrinsic and extrinsic defects in black phosphorus

Chemical modification of 2D materials using molecules and assemblies of molecules

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