Evaluating the Structure of Catalysts Using Core-Level Binding Energies Calculated from First Principles

Abstract

X-ray photoelectron spectroscopy (XPS) is a powerful and popular surface characterization technique, and the measured shifts in the core electron binding energies are sensitive to the chemical structure and local environment of the surface species. C 1s binding energies were calculated with density functional theory (DFT) for 17 structures including eight well-characterized structures on a Co(0001) surface and nine on a Pt(111) surface, while B 1s binding energies were calculated for six well-characterized structures and compared with experimental values. DFT calculations describe the 2.8 eV variation in the C 1s binding energies on Co surfaces, the 4.2 eV variation in the C 1s binding energies on Pt surfaces, and the 5.5 eV variation in the B 1s binding energies in the test sets with average deviations of 85, 73, and 53 meV, respectively. The shift in the C 1s and the B 1s binding energies can be correlated with the calculated charges, though only within homologous series. To illustrate how binding energ...