Covalent Reactions on Chemical Vapor Deposition Grown Graphene Studied by Surface‐Enhanced Raman Spectroscopy

Kovaříček, Petr; Bastl, Zdeněk; Valeš, Václav; Kalbáč, Martin

doi:10.1002/chem.201504689

Cited by 33 publications

(49 citation statements)

References 50 publications

(84 reference statements)

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“…3d) that were also calculated for θ ≈3%. This is in full agreement with recent surface-enhanced Raman scattering studies on functionalized chemical vapour deposition graphene, where a slight fingerprint for chemically modified graphene with a DOF of ∼0.5% leads to comparably weak Raman interbands in the D- and G-mode area46. Thus, we can conclude that the approach towards the maximal possible DOF of 12.5% (based on the ratio of K/C=1:8) is accompanied by clustering of addends and by the formation nonaltered sp 2 nano domains394041.…”

Section: Discussionsupporting

confidence: 91%

RETRACTED ARTICLE: Precise determination of graphene functionalization by in situ Raman spectroscopy

et al. 2017

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The verification of a successful covalent functionalization of graphene and related carbon allotropes can easily be carried out by Raman spectroscopy. Nevertheless, the unequivocal assignment and resolution of individual lattice modes associated with the covalent binding of addends was elusive up to now. Here we present an in situ Raman study of a controlled functionalization of potassium intercalated graphite, revealing several new bands appearing in the D-region of the spectrum. The evolution of these bands with increasing degree of functionalization from low to moderate levels provides a basis for the deconvolution of the different components towards quantifying the extent of functionalization. By complementary DFT calculations we were able to identify the vibrational changes in the close proximity of the addend bearing lattice carbon atoms and to assign them to specific Raman modes. The experimental in situ observation of the developing functionalization along with the reoxidation of the intercalated graphite represents an important step towards an improved understanding of the chemistry of graphene.

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Section: Discussionsupporting

confidence: 91%

RETRACTED ARTICLE: Precise determination of graphene functionalization by in situ Raman spectroscopy

et al. 2017

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“…Indeed, the black phosphorus does not burn down in the elemental fluorine. In analogy to chemistry of fluorinated graphene, a possible introduction of other functional groups via fluorine replacement could be possible, involving reactions with Grignard reagents, thiols, or other nucleophilic reagents …”

Section: Resultsmentioning

confidence: 99%

Fluorination of Black Phosphorus—Will Black Phosphorus Burn Down in the Elemental Fluorine?

Plutnar

Šturala

Mazánek

et al. 2018

Adv Funct Materials

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Black phosphorus (BP) represents a promising tunable bandgap alternative to graphene and other 2D materials in the field of semiconductors. However, its reactivity toward covalent modification of its surface (as a key to its bandgap adjustment) is scarcely reported. Here a method of covalent modification of BP involving reaction with fluorine is reported. Other allotropes of phosphorus are known to react violently with fluorine resulting in its complete burning down and formation of gaseous phosphorus pentafluoride. The results of our fluorination experiments conducted in analogy to the procedures used for fluorination of graphene indicate a successful binding of fluorine to BP. This route of modification of BP opens new possible ways toward covalent modification of the surface of this promising material.

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“…Among them, chemical functionalization offers the broadest variety of possibilities . Although several approaches for covalent grafting have been reported, only recently has the advancement towards specific applications revealed the need for spatially resolved methods that would provide patterned surface functionalization on the 2D material, aiming at sophisticated sensor arrays or device mass production . This non‐trivial task has been approached from several directions, using for instance photolithography, dip‐pen lithography or various writing techniques .…”

Section: Methodsmentioning

confidence: 99%

Spatially Resolved Covalent Functionalization Patterns on Graphene

et al. 2018

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Spatially resolved functionalization of 2D materials is highly demanded but very challenging to achieve.T he chemical patterning is typically tackled by preventing contact between the reagent and material, which brings various accompanying challenges.P hotochemical transformation on the other hand inherently provides remote high spatiotemporal resolution using the cleanest reagent-a photon. Herein, we combine two competing reactions on ag raphene substrate to create functionalization patterns on amicrometer scale via the Mitsunobu reaction. The mild reaction conditions allow introduction of covalently dynamic linkages,w hichc an serve as reversible labels for surface-or graphene-enhanced Raman spectroscopyc haracterization of the patterns prepared. The proposed methodology thus provides ap athwayf or local introduction of arbitrary functional groups on graphene.Graphene holds ap rominent position among two-dimensional (2D) materials owing to its unique properties, [1][2][3] which can be further tuned for particular applications [4][5][6] by several methods.Among them, chemical functionalization offers the broadest variety of possibilities. [7][8][9] Although several approaches for covalent grafting have been reported, [10][11][12][13][14][15] only recently has the advancement towards specific applications revealed the need for spatially resolved methods that would provide patterned surface functionalization on the 2D material, [16][17][18] aiming at sophisticated sensor arrays or device mass production. [19] This non-trivial task has been approached from several directions,u sing for instance photolithography, [20] dip-pen lithography [21][22][23] or various writing techniques. [24][25][26] Using covalent modification for spatially resolved functionalization typically relies on preventing contact of the reagents with graphene,t hus implying the use of ar esist mask [27] or controlled deposition [28,29] at the nanoscale,w hich either adds more steps (with concomitant contamination [30] ) or severely limits the processing speed, respectively.P hotochemical reactions represent au nique alternative to the abovementioned two approaches [31] because photochemistry responds to illumination patterns without the need for aresist or spatially confined reagent deposition.Thec ritical challenge for the surface functionalization of the 2D materials is unambiguous characterization of the reaction products facing the detection and resolution limits of many methods due to the strict monolayer nature of the materials. [32] Ty pical methods such as Raman spectroscopy [33][34][35] and X-ray photoelectron spectroscopy [36] (XPS) provide only limited insight into the actual chemistry taking place at the surface,anissue which has been tackled recently by the use of surface-and graphene-enhanced Raman spectroscopy (SERS and GERS,r espectively) [14,37] and also by other methods. [38,39] Application of SERS/GERS allows direct assignment of characteristic vibrational modes to particular species and thus provides solid evidence for species...

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Covalent Reactions on Chemical Vapor Deposition Grown Graphene Studied by Surface‐Enhanced Raman Spectroscopy

Cited by 33 publications

References 50 publications

RETRACTED ARTICLE: Precise determination of graphene functionalization by in situ Raman spectroscopy

RETRACTED ARTICLE: Precise determination of graphene functionalization by in situ Raman spectroscopy

Fluorination of Black Phosphorus—Will Black Phosphorus Burn Down in the Elemental Fluorine?

Spatially Resolved Covalent Functionalization Patterns on Graphene

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