X-ray photoelectron spectra of N-methyltetraphenylporphyrins: evidence for a correlation of binding energies with metal-nitrogen bond distances

Probing the Reactivity of Functionalized Surfaces by Porphyrin Metalation

“…The N1s spectra (Figure a) show that before Ni deposition there are two N1s signatures, about equal in intensity as typical for non‐metalated porphyrins (plotted in blue). After depositing Ni and after subsequent annealing two main N1s features remain, but the ratios between their intensities changes significantly, to ∼1:3 at 540 K. Such an inequivalency in the N1s intensities has been observed earlier for metalated porphyrins in which one of the pyrrole rings has been reduced by Cl . Therefore, we assign this peculiar evolution of the N1s spectra to the changing ratio of two different adsorbed species: (A) An intermediate compound H‐bonded to Cl/Cu in which the Ni atom is coordinated by the porphyrin, but without breaking the pyrrolic N−H bonds and (B) the final product of the on‐surface reaction with Ni, a NiTPP−Cl complex bound to ad‐surface Cl via one of the pyrrole rings .…”

“…After depositing Ni and after subsequent annealing two main N1s features remain, but the ratios between their intensities changes significantly, to ∼1:3 at 540 K. Such an inequivalency in the N1s intensities has been observed earlier for metalated porphyrins in which one of the pyrrole rings has been reduced by Cl . Therefore, we assign this peculiar evolution of the N1s spectra to the changing ratio of two different adsorbed species: (A) An intermediate compound H‐bonded to Cl/Cu in which the Ni atom is coordinated by the porphyrin, but without breaking the pyrrolic N−H bonds and (B) the final product of the on‐surface reaction with Ni, a NiTPP−Cl complex bound to ad‐surface Cl via one of the pyrrole rings . The precursor A is recognized by a characteristic N1s XPS signal at 399 eV and 400.5 eV (plotted in green) while the metalated form B is identified by signals at 398 eV and 400.2 eV (plotted in red).…”

“…[36] Therefore, we assign this peculiar evolution of the N1s spectra to the changing ratio of two different adsorbed species: (A) An intermediate compound H-bonded to Cl/Cu in which the Ni atom is coordinated by the porphyrin, but without breaking the pyrrolic NÀH bonds [23] and (B) the final product of the onsurface reaction with Ni, a NiTPPÀCl complex bound to ad-surface Cl via one of the pyrrole rings. [36] The precursor A is recognized by a characteristic N1s XPS signal at 399 eV and 400.5 eV (plotted in green) while the metalated form B is identified by signals at 398 eV and 400.2 eV (plotted in red). An estimate of the N1s peak intensities indicates a 45:55 ratio of the two compounds after deposition of Ni at RT.…”

Electroless synthesis of two-dimensional sandwich-like Pt/Mn3O4/reduced-graphene-oxide nanocomposites with enhanced electrochemical performance for methanol oxidation

“…High resolution XPS spectra of the N 1 s in Mn 3 O 4 /RGO (insert of Fig. S2a) indicated the probably new metal-N-C bonds [11,25,26]. In the deconvoluted C 1 s spectrum of GO (Fig.…”

Organic Matrix Stabilized Ultra‐Fine Bismuth Oxide Particles for Electrochemical Energy Storage Application

“…After deconvolution, three nitrogen peaks centered at 399.06, 403.05 and 405.01 eV are obtained. The peak with the binding energy values of 399.06 and 403.05 associated with metal‐nitrogen (Bi−N) and N–C bond, respectively ,. The other peak at 405.01 eV could be the presence of nitrate from the bismuth nitrate precursor.…”