Graphene functionalization

Mechanism of carboxyl group formation

Ljubisa R. Radovic, Camila V. Mora-Vilches, Adolfo J.A. Salgado-Casanova, Antonio Buljan

Research output: Contribution to journalArticle

5 Citations (Scopus)

Abstract

Carboxyl groups are ubiquitous in graphene-based materials. Decades ago, they were important in conferring cation-exchange properties to coal and coal-derived chars; today they are instrumental in converting graphite to graphene as well as in a wide variety of surface functionalization processes. And yet the essential mechanistic details of their formation have not received the attention they deserve. Here we perform quantum chemical calculations based on the density functional theory to reveal the elementary oxygen-transfer processes that are consistent with the abundant experimental literature on the oxidation of sp2-hybridized carbon materials. Prototypical graphene clusters decompose nitric acid to nitrogen oxides and the reactive hydroxyls. Carboxyl groups are thus formed by virtue of sequential hydroxyl attack at the carbon active sites (Cf) which weakens and cleaves the contiguous aromatic C-C bonds. A comparison with the other common oxidants (X, e.g., chlorate or permanganate) is carried out by distinguishing the 1O-down and 2O-down oxygen-transfer pathways. This constitutes an essential step toward the unification of a wide variety of oxidation processes involving semiquinone or dioxirane surface intermediates: Cf + XO3 - = C(O) + NO2 (or ClO2 ) vs. Cf + XO3 - = C(O2 ) + NO (or ClO) vs. Cf + XO4 - = C(O2) + XO2 -.

Original languageEnglish (US)
Pages (from-to)340-349
Number of pages10
JournalCarbon
Volume130
DOIs
StatePublished - Apr 1 2018

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Graphite
Graphene
Coal
Hydroxyl Radical
Oxidation
Carbon
Oxygen
Nitrogen oxides
Chlorates
Nitric acid
Nitrogen Oxides
Oxidants
Nitric Acid
Density functional theory
Ion exchange
Positive ions
Cations

All Science Journal Classification (ASJC) codes

  • Chemistry(all)

Cite this

Radovic, L. R., Mora-Vilches, C. V., Salgado-Casanova, A. J. A., & Buljan, A. (2018). Graphene functionalization: Mechanism of carboxyl group formation. Carbon, 130, 340-349. https://doi.org/10.1016/j.carbon.2017.12.112
Radovic, Ljubisa R. ; Mora-Vilches, Camila V. ; Salgado-Casanova, Adolfo J.A. ; Buljan, Antonio. / Graphene functionalization : Mechanism of carboxyl group formation. In: Carbon. 2018 ; Vol. 130. pp. 340-349.
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Radovic, LR, Mora-Vilches, CV, Salgado-Casanova, AJA & Buljan, A 2018, 'Graphene functionalization: Mechanism of carboxyl group formation', Carbon, vol. 130, pp. 340-349. https://doi.org/10.1016/j.carbon.2017.12.112

Graphene functionalization : Mechanism of carboxyl group formation. / Radovic, Ljubisa R.; Mora-Vilches, Camila V.; Salgado-Casanova, Adolfo J.A.; Buljan, Antonio.

In: Carbon, Vol. 130, 01.04.2018, p. 340-349.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Graphene functionalization

T2 - Mechanism of carboxyl group formation

AU - Radovic, Ljubisa R.

AU - Mora-Vilches, Camila V.

AU - Salgado-Casanova, Adolfo J.A.

AU - Buljan, Antonio

PY - 2018/4/1

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N2 - Carboxyl groups are ubiquitous in graphene-based materials. Decades ago, they were important in conferring cation-exchange properties to coal and coal-derived chars; today they are instrumental in converting graphite to graphene as well as in a wide variety of surface functionalization processes. And yet the essential mechanistic details of their formation have not received the attention they deserve. Here we perform quantum chemical calculations based on the density functional theory to reveal the elementary oxygen-transfer processes that are consistent with the abundant experimental literature on the oxidation of sp2-hybridized carbon materials. Prototypical graphene clusters decompose nitric acid to nitrogen oxides and the reactive hydroxyls. Carboxyl groups are thus formed by virtue of sequential hydroxyl attack at the carbon active sites (Cf) which weakens and cleaves the contiguous aromatic C-C bonds. A comparison with the other common oxidants (X, e.g., chlorate or permanganate) is carried out by distinguishing the 1O-down and 2O-down oxygen-transfer pathways. This constitutes an essential step toward the unification of a wide variety of oxidation processes involving semiquinone or dioxirane surface intermediates: Cf + XO3 - = C(O) + NO2 − (or ClO2 −) vs. Cf + XO3 - = C(O2 −) + NO (or ClO) vs. Cf + XO4 - = C(O2) + XO2 -.

AB - Carboxyl groups are ubiquitous in graphene-based materials. Decades ago, they were important in conferring cation-exchange properties to coal and coal-derived chars; today they are instrumental in converting graphite to graphene as well as in a wide variety of surface functionalization processes. And yet the essential mechanistic details of their formation have not received the attention they deserve. Here we perform quantum chemical calculations based on the density functional theory to reveal the elementary oxygen-transfer processes that are consistent with the abundant experimental literature on the oxidation of sp2-hybridized carbon materials. Prototypical graphene clusters decompose nitric acid to nitrogen oxides and the reactive hydroxyls. Carboxyl groups are thus formed by virtue of sequential hydroxyl attack at the carbon active sites (Cf) which weakens and cleaves the contiguous aromatic C-C bonds. A comparison with the other common oxidants (X, e.g., chlorate or permanganate) is carried out by distinguishing the 1O-down and 2O-down oxygen-transfer pathways. This constitutes an essential step toward the unification of a wide variety of oxidation processes involving semiquinone or dioxirane surface intermediates: Cf + XO3 - = C(O) + NO2 − (or ClO2 −) vs. Cf + XO3 - = C(O2 −) + NO (or ClO) vs. Cf + XO4 - = C(O2) + XO2 -.

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