How Long to Read Speciation of Ions Generated from Laser Ablation of Graphite Fluoride and Its Derivatives

By Brett A. Williams (Chemist)

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Description

A mass spectrometric analysis of the ions generated from laser ablation of graphite, graphite fluoride (GF), and derivatives of GF will be presented. Ablation of graphite and GF under identical conditions yields mass spectra with very different profiles. The mass spectra of graphite exhibit typical Cn- cluster mass distributions, whereas the mass spectra from the ablation of GF are congested and exhibit numerous stoichiometric cluster distributions. Many ions with more pronounced abundance in the GF mass spectra have m/z values which coincide with particularly stable perfluorocarbons (PFCs), such as C6F6-, C7F8-, C6F12-, and C8F16-. Photoelectron (PE) spectra were collected for several of these species and compared to the PE spectra of PFCs introduced into the gas phase and ionized through gentle electron attachment to the neutral PFC molecule. The PE spectra of C6F6-, C7F8-, and C5F8− generated from GF ablation and from gentle electron attachment were nearly identical, indicating that stable perfluorocarbons can form under the highly hyperthermal conditions that are characteristic of laser ablation. In a separate study, two nitrogen-doped derivatives of GF were produced by reacting GF with NaNO3 and NaN3. A mass spectral analysis of these two materials was conducted to determine the anionic products of laser ablation. Furthermore, two different gas-phase syntheses were done to investigate whether clusters formed in these studies are from atomization followed by coalescence, or by desorption processes. In the first, laser irradiation was used to react NaNO3 with GF, and in the second, gaseous NH3 was reacted with GF and, separately, graphite during laser irradiation. The gas-phase products of these reactions were analyzed. The mass spectra of the N-doped carbon material ablation products and the mass spectra of products from the laser-induced carbon-nitrogen reaction contain the stoichiometric series Cx- and C(x-1)N-.

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