Effect of graphene flake size on functionalisation: quantifying reaction extent and imaging locus with single Pt atom tags

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Autori principali: Rubio Carrero, Noelia, Au, Heather, Coulter, Gabriel, GUETAZ, Laure, GEBEL, Gérard, Mattevi, Cecilia, Shaffer, Milo
Natura: Recurso digital
Pubblicazione: Zenodo 2021
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author Rubio Carrero, Noelia
Au, Heather
Coulter, Gabriel
GUETAZ, Laure
GEBEL, Gérard
Mattevi, Cecilia
Shaffer, Milo
author_facet Rubio Carrero, Noelia
Au, Heather
Coulter, Gabriel
GUETAZ, Laure
GEBEL, Gérard
Mattevi, Cecilia
Shaffer, Milo
contents <p>Here, the locus of functionalisation on graphene-related materials and the progress of the reaction is shown<br>to depend strongly on the starting feedstock. Five characteristically different graphite sources were<br>exfoliated and functionalized using a non-destructive chemical reduction method. These archetypical<br>examples were compared via a model reaction, grafting dodecyl addends, evaluated with TGA-MS, XPS<br>and Raman data. A general increase in grafting ratio (ranging from 1.1 wt% up to 25 wt%) and an<br>improvement in grafting stoichiometry (C/R) were observed as flake radius decreased. Raman spectrum<br>imaging of the functionalised natural flake graphite identified that grafting is directed towards flake<br>edges. This behaviour was further corroborated, at atomistic resolution, by functionalising the graphene<br>layers with bipyridine groups able to complex single platinum atoms. The distribution of these groups<br>was then directly imaged using aberration-corrected HAADF-STEM. Platinum atoms were found to be<br>homogeneously distributed across smaller graphenes; in contrast, a more heterogeneous distribution,<br>with a predominance of edge grafting was observed for larger graphites. These observations show that<br>grafting is directed towards flake edges, but not necessary at edge sites; the mechanism is attributed to<br>the relative inaccessibility of the inner basal plane to reactive moieties, resulting in kinetically driven<br>grafting nearer flake edges. This phenomenology may be relevant to a wide range of reactions on<br>graphenes and other 2d materials.</p>
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spellingShingle Effect of graphene flake size on functionalisation: quantifying reaction extent and imaging locus with single Pt atom tags
Rubio Carrero, Noelia
Au, Heather
Coulter, Gabriel
GUETAZ, Laure
GEBEL, Gérard
Mattevi, Cecilia
Shaffer, Milo
<p>Here, the locus of functionalisation on graphene-related materials and the progress of the reaction is shown<br>to depend strongly on the starting feedstock. Five characteristically different graphite sources were<br>exfoliated and functionalized using a non-destructive chemical reduction method. These archetypical<br>examples were compared via a model reaction, grafting dodecyl addends, evaluated with TGA-MS, XPS<br>and Raman data. A general increase in grafting ratio (ranging from 1.1 wt% up to 25 wt%) and an<br>improvement in grafting stoichiometry (C/R) were observed as flake radius decreased. Raman spectrum<br>imaging of the functionalised natural flake graphite identified that grafting is directed towards flake<br>edges. This behaviour was further corroborated, at atomistic resolution, by functionalising the graphene<br>layers with bipyridine groups able to complex single platinum atoms. The distribution of these groups<br>was then directly imaged using aberration-corrected HAADF-STEM. Platinum atoms were found to be<br>homogeneously distributed across smaller graphenes; in contrast, a more heterogeneous distribution,<br>with a predominance of edge grafting was observed for larger graphites. These observations show that<br>grafting is directed towards flake edges, but not necessary at edge sites; the mechanism is attributed to<br>the relative inaccessibility of the inner basal plane to reactive moieties, resulting in kinetically driven<br>grafting nearer flake edges. This phenomenology may be relevant to a wide range of reactions on<br>graphenes and other 2d materials.</p>
title Effect of graphene flake size on functionalisation: quantifying reaction extent and imaging locus with single Pt atom tags
url https://doi.org/10.1039/d1sc01958a