A DFT study of the interplay between dopants and oxygen functional groups over the graphene basal plane – implications in energy-related applications

Dobrota, Ana S.; Pašti, Igor A.; Mentus, Slavko; Skorodumova, Natalia V.

doi:10.1039/c7cp00344g

Cited by 60 publications

(71 citation statements)

References 48 publications

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“…Atomic hydrogen forms covalent bonds with non-doped, non-strained graphene (C54(0%)), with preferential C-top adsorption site (~1.13 Å directly above one C atom) and the adsorption energy of -0.81 (-0.87) eV (in agreement with previous literature reports [28,40,53,54]). This interaction results in previous report [47]). The preferential H adsorption site on the studied strained surfaces is the same as on the corresponding non-strained surfaces (Fig.…”

Section: Atomic Hydrogen Adsorptionsupporting

confidence: 87%

Altering the reactivity of pristine, N- and P-doped graphene by strain engineering: A DFT view on energy related aspects

Dobrota

Pašti

Mentus

et al. 2020

Applied Surface Science

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For carbon-based materials, in contrast to metal surfaces, the relationship between strain and reactivity is not yet established, even though there are literature reports on strained graphene. Knowledge of such relationships would be extremely beneficial for understanding the reactivity of graphene-based surfaces and finding optimisation strategies which would make these materials more suitable for targeted applications. Here we investigate the effects of compressive and tensile strain (up to ±5%) on the structure, electronic properties and the reactivity of pure, N-doped and P-doped graphene, using DFT calculations. We demonstrate the possibility of tuning the topology of the graphene surface by strain, as well as by the choice of the dopant atom. The reactivity of (doped) strained graphene is probed using H and Na as simple adsorbates of great practical importance. Strain can both enhance and weaken H and Na adsorption on (doped) graphene. In case of Na adsorption, a linear relationship is observed between the Na adsorption energy on P-doped graphene and the phosphorus charge. A linear relationship between the Na adsorption energy on flat graphene surfaces and strain is found.Based on the adsorption energies and electrical conductivity, potentially good candidates for hydrogen storage and sodium-ion battery electrodes are discussed.

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Section: Atomic Hydrogen Adsorptionsupporting

confidence: 87%

Altering the reactivity of pristine, N- and P-doped graphene by strain engineering: A DFT view on energy related aspects

Dobrota

Pašti

Mentus

et al. 2020

Applied Surface Science

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“…The preference of impurity sites towards the oxidation can be explained in terms of charge redistribution upon the introduction of the impurity into graphene matrix and the subsequent disruption of the π electronic system. The electronegativity of B is lower than that of C, hence some charge is transferred from B to C. Based on the above, it is clear that oxygen tends to bind close to the dopant atoms in graphene, suggesting that these sites can be considered as the sites of increased reactivity where functionalization can be performed effectively [27]. Considering our previous results on OH adsorption on doped graphene [27], the O adsorption can be considered as next oxidation step.…”

Section: Graphene Surface Functionalization By Oxygenmentioning

confidence: 81%

“…The electronegativity of B is lower than that of C, hence some charge is transferred from B to C. Based on the above, it is clear that oxygen tends to bind close to the dopant atoms in graphene, suggesting that these sites can be considered as the sites of increased reactivity where functionalization can be performed effectively [27]. Considering our previous results on OH adsorption on doped graphene [27], the O adsorption can be considered as next oxidation step. This also reinforces previous conclusions that during the surface reduction it would be more difficult to remove oxygen functional groups from the area affected by dopants.…”

Section: Graphene Surface Functionalization By Oxygenmentioning

confidence: 81%

“…The plane waves' kinetic energy cut-off was 36 Ry while the charge density cut-off was 576 Ry. Pristine graphene was modelled as one layer consisted out of 24 carbon atoms arranged in a honeycomb lattice (C 24 ), corresponding to the (2√3×2√3)R30° structure, as done in our previous reports [23,27]. Doped graphene was modelled by substituting one C atom with B or N, yielding the dopant concentration of about 4.17 at%.…”

Section: Computational Detailsmentioning

confidence: 99%

“…Doped graphene was modelled by substituting one C atom with B or N, yielding the dopant concentration of about 4.17 at%. A detailed description of the doped graphene models is given in one of our previous reports [27]. The k-point sampling for relaxation calculations was 4×4×1, generated using the scheme of Monkhorst and Pack [28].…”

Section: Computational Detailsmentioning

confidence: 99%

See 2 more Smart Citations

Sodium storage via single epoxy group on graphene – The role of surface doping

Diklić

Dobrota

Pašti

et al. 2019

Electrochimica Acta

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Due to its unique physical and chemical properties, graphene is being considered as a promising material for energy conversion and storage applications. Introduction of functional groups and dopants on/in graphene is a useful strategy for tuning its properties. In order to fully exploit its potential, atomic-level understanding of its interaction with species of importance for such applications is required. We present a DFT study of the interaction of sodium atoms with epoxy-graphene and analyze how this interaction is affected upon doping with boron and nitrogen. We demonstrate how the dopants, combined with oxygencontaining groups alter the reactivity of graphene towards Na. Dopants act as attractors of epoxy groups, enhancing the sodium adsorption on doped oxygen-functionalized graphene when compared to the case of non-doped epoxy-graphene. Furthermore, by considering thermodynamics of the Na interaction with doped epoxy-graphene it has been concluded that such materials are good candidates for Na storage applications. Therefore, we suggest that controlled oxidation of doped carbon materials could lead to the development of advanced anode materials for rechargeable Na-ion batteries.

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Oxygen Clusters Distributed in Graphene with “Paddy Land” Structure: Ultrahigh Capacitance and Rate Performance for Supercapacitors

Liu

Jiang

Sheng

et al. 2017

Adv Funct Materials

104

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The introduction of surface functional groups onto graphene can provide additional pseudocapacitance for supercapacitors. However, the compensation for the loss of electrical conductivity arising from the disruption of the conjugated system remains a big challenge. Here, a novel strategy is reported for the design of oxygen clusters distributed in graphene with "paddy land" structure via a low-temperature annealing process. Moreover, the distribution, content, and variety of oxygen groups and the conductivity of reduced graphene oxide (RGO) can be easily adjusted by annealing temperature and time. First-principles calculations demonstrate that "paddy land" structure exhibits conjugated carbon network, ultralow HOMO-LUMO gap, and long span of atomic charge values, which are beneficial for the enhanced pseudocapacitance and rate performance. As a result, the functionalized graphene (GO-160-8D) exhibits high specific capacitance of 436 F g −1 at 0.5 A g −1 , exceeding the values of previously reported RGO materials, as well as excellent rate performance (261 F g −1 at 50 A g −1 ) and cycling stability (94% of capacitance retention after 10 000 cycles). The findings may open a door for finely controlling the location and density of functionalities on graphene for applications in energy storage and conversion fields via a green and energy-efficient process.

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A DFT study of the interplay between dopants and oxygen functional groups over the graphene basal plane – implications in energy-related applications

Cited by 60 publications

References 48 publications

Altering the reactivity of pristine, N- and P-doped graphene by strain engineering: A DFT view on energy related aspects

Altering the reactivity of pristine, N- and P-doped graphene by strain engineering: A DFT view on energy related aspects

Sodium storage via single epoxy group on graphene – The role of surface doping

Oxygen Clusters Distributed in Graphene with “Paddy Land” Structure: Ultrahigh Capacitance and Rate Performance for Supercapacitors

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