4.7 Article

Photolysis of Fluorinated Graphites with Embedded Acetonitrile Using a White-Beam Synchrotron Radiation

Journal

NANOMATERIALS
Volume 12, Issue 2, Pages -

Publisher

MDPI
DOI: 10.3390/nano12020231

Keywords

fluorinated graphite; acetonitrile; non-monochromatized synchrotron radiation; photolysis; XPS; NEXAFS

Funding

  1. Russian Foundation [18-29-19073]
  2. Ministry of Science and Higher Education of the Russian Federation [121031700314-5]
  3. BMBF [05K19KER, 0519ODR]

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In this study, the photolysis of fluorinated graphites with interlayer embedded acetonitrile was investigated, and it was found that the photolysis products depend on the photon irradiation duration and composition of the initial CFx matrix. The obtained results are important for evaluating the radiation damage of fluorinated graphites and synthesizing nitrogen-doped graphene materials.
Fluorinated graphitic layers with good mechanical and chemical stability, polar C-F bonds, and tunable bandgap are attractive for a variety of applications. In this work, we investigated the photolysis of fluorinated graphites with interlayer embedded acetonitrile, which is the simplest representative of the acetonitrile-containing photosensitizing family. The samples were continuously illuminated in situ with high-brightness non-monochromatized synchrotron radiation. Changes in the compositions of the samples were monitored using X-ray photoelectron spectroscopy and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. The NEXAFS N K-edge spectra showed that acetonitrile dissociates to form HCN and N-2 molecules after exposure to the white beam for 2 s, and the latter molecules completely disappear after exposure for 200 s. The original composition of fluorinated matrices CF0.3 and CF0.5 is changed to CF0.10 and GF(0.17), respectively. The highly fluorinated layers lose fluorine atoms together with carbon neighbors, creating atomic vacancies. The edges of vacancies are terminated with the nitrogen atoms and form pyridinic and pyrrolic units. Our in situ studies show that the photolysis products of acetonitrile depend on the photon irradiation duration and composition of the initial CFx matrix. The obtained results evaluate the radiation damage of the acetonitrile-intercalated fluorinated graphites and the opportunities to synthesize nitrogen-doped graphene materials.

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