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Dynamic Study of Intercalation/Deintercalation of Ionic Liquids in Multilayer Graphene Using an Alternating Current Raman Spectroscopy Technique.

ABSTRACT: We report Raman spectra and infrared (IR) imaging collected during the intercalation-deintercalation half cycles in a multilayer graphene (MLG) device (∼100 layers) operating at 0.2-10 Hz. The device consists of a MLG/alumina membrane/copper stack, in which the alumina membrane is filled with ionic liquid [DEME][TFSI], forming an electrochemical cell. Upon the application of a positive voltage, the TFSI^- anions intercalate into the interstitial spaces in the MLG. The incident laser light is modulated using an optical chopper wheel that is synchronized with (and delayed with respect to) a 0.2-10 Hz alternating current (AC) voltage signal. Raman spectra taken just 200 ms apart show the emergence and disappearance of the intercalated G band mode at around 1610 cm^-1. By integration of over hundreds of cycles, a significant Raman signal can be obtained. The intercalation/deintercalation is also monitored with thermal imaging via voltage-induced changes in the carrier density, complex dielectric function ε(ω), and thermal emissivity of the device.

SUBMITTER: Cai Z

PROVIDER: S-EPMC10440811 | biostudies-literature | 2023 Aug

REPOSITORIES: biostudies-literature

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Dynamic Study of Intercalation/Deintercalation of Ionic Liquids in Multilayer Graphene Using an Alternating Current Raman Spectroscopy Technique.

Cai Zhi Z Weinstein Haley H Aravind Indu I Li Ruoxi R Weng Sizhe S Zhang Boxin B Habif Jonathan L JL Cronin Stephen B SB

The journal of physical chemistry letters 20230808 32

We report Raman spectra and infrared (IR) imaging collected during the intercalation-deintercalation half cycles in a multilayer graphene (MLG) device (∼100 layers) operating at 0.2-10 Hz. The device consists of a MLG/alumina membrane/copper stack, in which the alumina membrane is filled with ionic liquid [DEME][TFSI], forming an electrochemical cell. Upon the application of a positive voltage, the TFSI<sup>-</sup> anions intercalate into the interstitial spaces in the MLG. The incident laser li ...[more]

PMID: 37552573

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Project description:In this work, the configuration and stability of 15 geminal dicationic ionic liquids (GDILs) and their adsorption mechanism on the graphene nanoflake (GNF) are investigated using the density functional theory (DFT) method. We find that the interactions of dications ([DAm]+, [DIm]+, [DImDm]+, [DPy]+, and [DPyrr]+)) are stabilized near the anions ([BF4]-, [PF6]-, and [Tf2N]-) in the most stable configurations of GDILs through electrostatic interactions, van der Waals (vdW) interactions, and hydrogen bonding (H-bonding). Our calculations show that the adsorption of the GDILs on the GNF is consistent with the charge transfer and occurs via X···π (X = N, O, F), C-H···π, and π···π noncovalent interactions, leading to a decrease in the strength of the intermolecular interactions between the dications and anions in the GDILs. The thermochemistry calculations reveal that the formation of GDIL@GNF complexes is an exothermic and favorable reaction. The adsorption energy (Eads) calculations show that the highest Eads values for the interaction of GDILs containing [BF4]-, [PF6]-, and [Tf2N]- anions with the GNF are observed for the [DPy][BF4]@GNF (-23.56 kcal/mol), [DPy][PF6]@GNF (-29.29 kcal/mol), and [DPyrr][Tf2N]@GNF (-24.74 kcal/mol) complexes, respectively. Our results show that the adsorption of the GDILs on the GNF leads to the decrease of the chemical potential (μ), chemical hardness (η), and HOMO-LUMO energy gap (Eg) values and an increase in the electrophilicity index (ω) value of the GNF. In addition, the effect of GDIL adsorption on the UV-vis absorption spectrum was studied at the TD-M06-2X/cc-pVDZ level of theory. We find that the adsorption of GDILs results in minimal change in the shape of the main absorption peak (at λ = 363 nm) in the GNF spectrum and only shifts it to higher wavelengths. On the other hand, a new peak appears in the GNF spectrum upon adsorption of [DPy][Y] (Y = [BF4]-, [PF6]-, and [Tf2N]-) due to the relatively strong π···π interactions between the [DPy]+ dication and GNF. Finally, the transition density matrix (TDM) heat maps show that electron transfers related to the excitation states in the GDIL@GNF complexes occur mainly through π(C=C) → π*(C=C) transitions in the GNF and the transitions from [DPy]+ dication to the GNF.

Dataset Information

Dynamic Study of Intercalation/Deintercalation of Ionic Liquids in Multilayer Graphene Using an Alternating Current Raman Spectroscopy Technique.

Publications

Dynamic Study of Intercalation/Deintercalation of Ionic Liquids in Multilayer Graphene Using an Alternating Current Raman Spectroscopy Technique.

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