Photo-induced surface functionalization of carbon surfaces: The role of photoelectron ejection
XPS spectra of amorphous carbon sample after H termination (⋯) and after reaction with TFAAD (—) in the (a), (b), and regions. Upon grafting peaks associated with the C, F, and N atoms of the TFA group appear.
IRRAS spectra of layers resulting from the photochemical reaction of H-terminated with (from top to bottom) TFAAD, 1-dodecene, UA-Me, and tBOC for . Spectra were baseline corrected and offset for clarity.
Photoemission studies at the H-terminated surface. (a) He(I) UPS spectrum of H-terminated . The prominent feature at assigned to the states is indicated with an arrow. (b) Photocurrent measurements carried out using interdigitated electrodes covered by a thin film of TFAAD; indicates the time at which UV illumination starts.
Effect of TFAAD pregrafting on the reactivity of toward tBOC. (a) IRRAS spectra of tBOC layers obtained after illumination time (bottom trace) on TFAAD-terminated (top trace). TFAAD-terminated surfaces were obtained by carrying out the reaction with TFAAD on H-terminated for only . Spectra were baseline corrected and offset for clarity. (b) XPS in the region (high binding energy peaks only) of two samples prepared as in (a).
Proposed mechanism for the grafting of TFAAD on H-terminated .
Electron affinities (EA) and ionization potentials (IP) calculated using the B3LYP hybrid functional and the D95 basis set. Values are in eV and were calculated using Eq. (1).
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