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Acetylation of graphite oxide
Umeå universitet, Teknisk-naturvetenskapliga fakulteten, Institutionen för fysik.ORCID-id: 0000-0002-8438-2581
Umeå universitet, Teknisk-naturvetenskapliga fakulteten, Institutionen för fysik.ORCID-id: 0000-0002-1535-9476
echnische Universitat Dresden, Physical Chemistry, Dresden, Sachsen, Germany.
Umeå universitet, Teknisk-naturvetenskapliga fakulteten, Institutionen för fysik.ORCID-id: 0000-0002-3320-8487
2020 (Engelska)Ingår i: Physical Chemistry, Chemical Physics - PCCP, ISSN 1463-9076, E-ISSN 1463-9084, Vol. 22, nr 37, s. 21059-21067Artikel i tidskrift (Refereegranskat) Published
Abstract [en]

Unlike many methods of chemical modification of Graphite Oxide (GO) reported during 1930-1960 and re-studied in much detail over the last decade, acetylation somehow escaped attention and remained almost completely unexplored. Acetylated Graphite Oxide (AcGO) was prepared using a reaction with acetic anhydride. Successful acetylation is evidenced by an increase in the average interlayer distance fromd(001) = 7.8 angstrom in the precursor GO to 10 angstrom in AcGO. The amount of oxygen in AcGO significantly decreased compared to the precursor GO (C/O = 2.2), reflecting partial reduction of GO in the process of acetylation and resulting in a scarcely functionalized material with C/O = 6.2. A theoretical model of the complete acetylation of GO results in a non-porous close packed molecular structure with an interlayer distance of similar to 10 angstrom, in good agreement with experiment. Remarkably, AcGO shows significant swelling despite the oxidation degree being comparable to that of reduced GO, which does not swell in polar solvents. Moreover, AcGO shows swelling in acetonitrile similar to that of the precursor GO but not in water, thus providing an example of selectivity in the sorption of common polar solvents. The low oxidation degree combined with selective swelling properties makes AcGO a promising material for membrane applications.

Ort, förlag, år, upplaga, sidor
Royal Society of Chemistry, 2020. Vol. 22, nr 37, s. 21059-21067
Nationell ämneskategori
Fysikalisk kemi Materialkemi Den kondenserade materiens fysik
Identifikatorer
URN: urn:nbn:se:umu:diva-176074DOI: 10.1039/d0cp03573dISI: 000573875300006PubMedID: 32936159Scopus ID: 2-s2.0-85092331997OAI: oai:DiVA.org:umu-176074DiVA, id: diva2:1478942
Tillgänglig från: 2020-10-23 Skapad: 2020-10-23 Senast uppdaterad: 2023-09-05Bibliografiskt granskad
Ingår i avhandling
1. Properties and applications of materials based on graphite oxide
Öppna denna publikation i ny flik eller fönster >>Properties and applications of materials based on graphite oxide
2023 (Engelska)Doktorsavhandling, sammanläggning (Övrigt vetenskapligt)
Alternativ titel[sv]
Egenskaper och tillämpningar av material baserade på grafitoxid
Abstract [en]

Graphite oxide (GO) is a hydrophilic, layered material prepared by oxidation of graphite. In the first part of this thesis, we studied materials produced from GO by intercalation and functionalization. The second part of the thesis was focused on supercapacitor applications of high surface area carbons prepared from GO using chemical activation. 

A detailed study of acetylated GO (AcGO) was performed to verify structure and properties of this material. Reports from 1960’s suggested that AcGO has “pillared” structure. Our analysis showed that the AcGO demonstrates expanded structure due to acetylation but exhibits negligible specific surface area and should not be considered as a pillared material. 

Pillared reduced GO (prGO) was prepared by applying mild annealing to GO material pillared with tetrapod-shaped amine molecules. PrGO showed relatively high surface area due to remaining pillaring molecules in the structure. The prGO is hydrophobic and exhibits 100x improved conductivity compared to precursor. PrGO is one of few true pillared structures reported in literature so far, and the first ever prepared starting from pillared GO.

We also investigated the sorption of common dyes, methylene blue (MB), rose bengal (RB) and crystal violet (CV), by multilayered graphene oxide materials. We found that MB dissolved in ethanol intercalates the GO structure, as evidenced by significant expansion of inter-layer distance, and increase in weight due to sorption. In contrast to MB, GO is not easily intercalated by CV and RB dyes. We believe that the flat MB molecule shape allows easier insertion between GO layers compared to twisted and non-flat CV and RB molecules. Our results suggest that penetration into GO inter-layers depends not only on the size of molecules, but also on the shape.

Temperature dependent study of structures formed by Brodie GO (BGO) in liquid alkyl alcohols was performed for a set starting from undecyl alcohol (no. of C=11) and up to behenyl alcohol (no. of C=22). We found that BGO exhibits strong swelling in all molten alcohols in this set. Heating just above the melting point of alcohol results in expansion of inter-layer distance of GO due to intercalation of two layers of alcohol molecules in orientation perpendicular to graphene oxide planes (α-phase). Further heating of α-phase results in incongruent melting and formation of new phase with significantly smaller inter-layer distance and amount of intercalated alcohol (β-phase). The transition from α-to β-phase is distinctly different compared to swelling transitions previously observed for BGO in smaller alcohols (no. of C<10). A more detailed study of the BGO-C16 system revealed that β-phase has structure with alcohol molecules forming layers mostly in parallel to graphene oxide orientation.

In the second part of this thesis we studied activated reduced GO (a-rGO) as electrode material in supercapacitors. A-rGO is a high surface material (~3000 m2g-1) obtained by KOH activation of rGO. We developed formulations for stable aqueous dispersions of a-rGO optimized for preparation of electrodes by semi-industrial spray-gun deposition. The electrodes prepared by spray deposition showed energy storage parameters only slightly lower compared to lab scale blade-deposited electrodes. Spray-gun deposition might provide significant advantage for industry over conventional methods to prepare electrodes from a-rGO. 

We also applied KOH activation procedure, optimized for producing high surface area a-rGO, to biochar prepared from pine cones. Using this cost free “waste” picked up in Umeå region forest we produced high quality activated carbon very similar to a-rGO in terms of structure, pore size and surface area. Overall, the energy storage parameters of electrodes prepared using the activated carbon from pine cones were on the same level as a-rGO electrodes, which are produced by a lot more complex and expensive chemical treatments.

Ort, förlag, år, upplaga, sidor
Umeå: Umeå Universitet, 2023. s. 86
Nyckelord
Graphene, Graphite Oxide, Graphene Oxide, Swelling, Phase Transition, Intercalation, Activated Graphene, Activated Carbon, Supercapacitors, Neutron Reflectometry
Nationell ämneskategori
Den kondenserade materiens fysik
Identifikatorer
urn:nbn:se:umu:diva-214116 (URN)978-91-8070-102-0 (ISBN)978-91-8070-103-7 (ISBN)
Disputation
2023-09-29, NAT.D.480, Naturvetarhuset, Umeå, 13:00 (Engelska)
Opponent
Handledare
Tillgänglig från: 2023-09-08 Skapad: 2023-09-05 Senast uppdaterad: 2023-09-05Bibliografiskt granskad

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