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Estimating hydroxyl/epoxy ratio in graphene oxide through adsorption experiment and semiempirical GFN2-xTB quantum method

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Abstract 

Context

The reactivity of graphene oxide (GO) with amines is related to the ring-opening of the epoxy groups in its basal surface, as addressed experimentally. Therefore, discussing the hydroxyl/epoxy ratio for GO is relevant to improve the characterization of such material. As the adsorption of Methylene Blue into GO is related to a graphene derivative’s oxidation degree (OD), we combined adsorption experimental information and theoretical data to estimate the hydroxyl/epoxy ratio. The theoretical data were compared to the experimental adsorption of Methylene Blue and Indigo Carmine into GO synthesized in our department. Our results show GO systems with hydroxyl/epoxy ratios equal to 0.7, 0.8, and 0.9 are the most representative in which the most coherent model corresponds to OH/EP=0.8 for our GO previously synthesized.

Methods

The GO-MODEL software was developed in the present work to obtain cartesian coordinates of GO systems. We investigated 204 systems comprising models with 486 carbon atoms with the GFN2-xTB semiempirical quantum method. The supramolecular arrangements were constructed with the recently developed UD-APARM program.

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Data availability

Starting GO structures (XYZ) obtained through the GO-MODEL software and Supporting Information file comprising: Data for isotherm study (MB/GO); Langmuir parameters for MB/GO system; Data for isotherm study (IC/GO); Langmuir parameters for IC/GO system; Structure information of the GO models; Supramolecular systems for α-Euler = 0 and 1800, and UD-APARM input parameters employed.

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Acknowledgements

Larissa Cristina Aparecida Souza thanks the Brazilian agency Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) for the scholarship. The authors also thank Professor Hélio Ferreira dos Santos for the access to the NEQC (Núcleo de Estudos em Química Computacional, UFJF, Brazil) computer facility and the Laboratório Central de Computação Científica (LCC) da UFLA for providing additional computing resources. Finally, we also thank Sthephano Daniel Santos for the adapted GO models included in the Supplementary Information.

Funding

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES), Fundação de Amparo à Pesquisa do Estado de Minas Gerais (FAPEMIG), and Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) supported this study.

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Authors and Affiliations

  1. Department of Chemistry, Institute of Natural Sciences, University of Lavras, Lavras, 37200900, Brazil

    Larissa. C. A. Souza, Regis V. A. Abreu, Mário C. Guerreiro & Cleber P. A. Anconi

  2. Department of Engineering, School of Engineering, University of Lavras, Lavras, 37200900, Brazil

    Juliano E. Oliveira

Authors
  1. Larissa. C. A. Souza
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  2. Regis V. A. Abreu
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  3. Mário C. Guerreiro
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  4. Juliano E. Oliveira
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  5. Cleber P. A. Anconi
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Contributions

All the authors contributed to the design and implementation of the research and revised the results. Specifically, Regis Vinicius Alves de Abreu and Mário César Guerreiro are responsible for the experimental data. Furthermore, Cleber Anconi developed and wrote the GO-MODEL software in Fortran language, supervised the research, and wrote the manuscript along with inputs from the authors.

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Correspondence to Cleber P. A. Anconi.

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Souza, L.C.A., Abreu, R.V.A., Guerreiro, M.C. et al. Estimating hydroxyl/epoxy ratio in graphene oxide through adsorption experiment and semiempirical GFN2-xTB quantum method. J Mol Model 29, 42 (2023). https://doi.org/10.1007/s00894-023-05444-4

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