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Development of Mild Methods for Selective Covalent Functionalization of Graphene
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC.ORCID iD: 0000-0003-3150-0748
2017 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis discusses methods for the comparatively mild covalent functionalization of graphene. Several graphene models were investigated: polycyclic aromatic hydrocarbons (PAHs), chemical vapor deposition (CVD)-graphene on SiO2/Si substrate, graphite foil, graphite flakes, kish graphite and highly oriented pyrolytic graphite. The PAHs were viewed as graphene edge analogs with the following molecules representing different edge motifs: pyrene, perylene, benzo[a]pyrene, benzo[e]pyrene, triphenylene, acenapthylene, and anthracene.

Ozone was used in combination with different solvents to functionalize PAHs, graphite, and CVD-graphene on SiO2/Si. Ozonation in water or methanol resulted in trapping of the carbonyl oxide intermediate that was formed in the reaction, producing a variety of functional groups. Ozonation in hydrogen peroxide solution with sonication promoted radical formation, possibly resulting in edge-oxidation of graphite. The regioselectivity for addition reactions (ozonolysis) and electrophilic aromatic substitution reactions with graphene edges is discussed.

To achieve functionalization of the basal plane of graphite or graphene, white light irradiation was used in combination with several transfer hydrogenation reagents. Formic acid treatment under irradiation resulted in the expected hydrogenation, whereas iso-propanol treatment resulted in iso-propanol attachment to the graphene.

The developed methods provide opportunities for graphene functionalization without the need for metal based reagents or harsh conditions.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2017. , p. 48
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 1593
Keyword [en]
Polycyclic aromatic hydrocarbons, graphene models, graphite, local ionization energy surfaces, graphene functionalization
National Category
Organic Chemistry
Research subject
Chemistry with specialization in Organic Chemistry
Identifiers
URN: urn:nbn:se:uu:diva-332004ISBN: 978-91-513-0135-8 (print)OAI: oai:DiVA.org:uu-332004DiVA, id: diva2:1152413
Public defence
2017-12-14, A1:107a, Husargatan 3, Uppsala, 09:15 (English)
Opponent
Supervisors
Available from: 2017-11-21 Created: 2017-10-24 Last updated: 2018-03-07
List of papers
1. Ozonolysis of triphenylene in acetone
Open this publication in new window or tab >>Ozonolysis of triphenylene in acetone
(English)Manuscript (preprint) (Other academic)
National Category
Organic Chemistry
Research subject
Chemistry with specialization in Organic Chemistry
Identifiers
urn:nbn:se:uu:diva-332003 (URN)
Available from: 2017-10-20 Created: 2017-10-20 Last updated: 2017-10-24
2. Ozonolysis of polycyclic aromatic hydrocarbons in participating solvents
Open this publication in new window or tab >>Ozonolysis of polycyclic aromatic hydrocarbons in participating solvents
2017 (English)In: RSC Advances, ISSN 2046-2069, E-ISSN 2046-2069, Vol. 7, no 10, p. 6152-6159Article in journal (Refereed) Published
Abstract [en]

Seven polycyclic aromatic hydrocarbon (PAH) compounds that can be considered small models for graphene edges have been treated with ozone in solution. The presence of participating solvents such as water or methanol had a pronounced influence on conversion and identity of the functional groups formed, whereas the regioselectivity of the ozonation remained unaffected. Six previously unreported compounds have been isolated from the ozonolysis of pyrene 1, perylene 2 and benzo[e] pyrene 4. Comparison of the experimental data with calculated local ionization energy surfaces (IES) shows a good correlation, and indicates that this computational tool would be useful to predict the regioselectivity of ozone also for larger PAHs, including graphene and graphene nanoribbons.

National Category
Organic Chemistry
Identifiers
urn:nbn:se:uu:diva-316964 (URN)10.1039/c6ra26248a (DOI)000393754100073 ()
Funder
Swedish Research CouncilKnut and Alice Wallenberg Foundation
Available from: 2017-03-08 Created: 2017-03-08 Last updated: 2017-11-29Bibliographically approved
3. Edge oxidation of graphite using a combined hydrogen peroxide - ozone treatment under sonication conditions
Open this publication in new window or tab >>Edge oxidation of graphite using a combined hydrogen peroxide - ozone treatment under sonication conditions
(English)Manuscript (preprint) (Other academic)
Abstract [en]

A mild method for edge oxidation of graphite using ultrasonication in the presence of ozone and hydrogen peroxide is described. The method benefits from sustainable reagents - no metals or oxidising mineral acids are involved; and easy purification of the resulting material. Initial characterisation of the material and its dispersibility by spectroscopic methods and thermogravimetric analysis is presented.

Keyword
Edge oxidation, Graphite, Graphene, Hydrogen peroxide, Ozone
National Category
Materials Chemistry Organic Chemistry
Identifiers
urn:nbn:se:uu:diva-327165 (URN)
Available from: 2017-08-06 Created: 2017-08-06 Last updated: 2017-10-24
4. Metal-free photochemical silylations and transfer hydrogenations of benzenoid hydrocarbons and graphene
Open this publication in new window or tab >>Metal-free photochemical silylations and transfer hydrogenations of benzenoid hydrocarbons and graphene
Show others...
2016 (English)In: Nature Communications, ISSN 2041-1723, E-ISSN 2041-1723Article in journal (Refereed) Published
Abstract [en]

The first hydrogenation step of benzene, which is endergonic in the electronic ground state (S0), becomes exergonic in the first triplet state (T1). This is in line with Baird’s rule, which tells that benzene is antiaromatic and destabilized in its T1 state and also in its first singlet excited state (S1), opposite to S0, where it is aromatic and remarkably unreactive. Here we utilized this feature to show that benzene and several polycyclic aromatic hydrocarbons (PAHs) to various extents undergo metal-free photochemical (hydro)silylations and transfer-hydrogenations at mild conditions, with the highest yield for naphthalene (photosilylation: 21%). Quantum chemical computations reveal that T1-state benzene is excellent at H-atom abstraction, while COT, aromatic in the T1 and S1 states according to Baird’s rule, is unreactive. Remarkably, also CVD-graphene on SiO2 is efficiently transfer-photohydrogenated using formic acid/water mixtures together with white light or solar irradiation under metal-free conditions.

National Category
Chemical Sciences Chemical Engineering
Identifiers
urn:nbn:se:uu:diva-303639 (URN)10.1038/ncomms12962 (DOI)000385553900001 ()27708336 (PubMedID)
Funder
Wenner-Gren FoundationsSwedish Research CouncilKnut and Alice Wallenberg FoundationÅForsk (Ångpanneföreningen's Foundation for Research and Development)Magnus Bergvall Foundation
Available from: 2016-09-21 Created: 2016-09-21 Last updated: 2018-04-23Bibliographically approved
5. White-light photoassisted covalent functionalization of graphene using 2-propanol
Open this publication in new window or tab >>White-light photoassisted covalent functionalization of graphene using 2-propanol
Show others...
2017 (English)In: Small Methods, ISSN 2366-9608, Vol. 1, no 11, article id 1700214Article in journal (Refereed) Published
Abstract [en]

Herein, a photochemical method for functionalization of graphene using 2-propanol is reported. The functionalization method which is catalyst-free operates at ambient temperature in neat 2-propanol under an inert atmosphere of argon. The equipment requirement is a white-light source for the irradiation. The same methodology when applied to kish graphite results in a novel material, exhibiting significantly higher wettability than the starting material according to water contact angle measurements. Furthermore, the materials generated from both graphene and kish graphite exhibit increased adhesion energy, attributed to the fixation of isopropyl alcohol fragments onto graphene and graphite, respectively. The presence of hydroxyl groups and the possibility for further reactions on the functionalized graphene material are demonstrated through a substitution reaction with thionyl chloride, where the hydroxyl groups are replaced with chlorides, as confirmed through X-ray photoelectron spectroscopy analysis.

Place, publisher, year, edition, pages
John Wiley & Sons, 2017
National Category
Materials Engineering Materials Chemistry
Identifiers
urn:nbn:se:uu:diva-314171 (URN)10.1002/smtd.201700214 (DOI)000417488900006 ()
Funder
Wenner-Gren FoundationsSwedish Research CouncilKnut and Alice Wallenberg FoundationÅForsk (Ångpanneföreningen's Foundation for Research and Development)Magnus Bergvall Foundation
Available from: 2017-01-29 Created: 2017-01-29 Last updated: 2018-03-09Bibliographically approved

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