Local Environment Sensitivity of the Cu K-Edge XANES Features in Cu-SSZ-13: Analysis from First-Principles

Cu K-edge X-ray absorption near-edge spectra (XANES) have been widely used to study the properties of, 4:10 Cu-SSZ-13. In this Letter, the sensitivity of the XANES features to the local environment for a Cu+ cation with a linear configuration and a Cu2+ cation with a square-linear configuration in Cu-SSZ-13 is reported. When a Cu+ cation is bonded to H2O or NH3 in a linear configuration, the XANES has a strong peak at around 8983 eV. The intensity of this peak decreases as the linear configuration is broken. As for the Cu+ cations in a square-planar configuration with a coordination number of 4, two peaks at around 8986 and 8993 eV are found. An intensity decrease for both peaks at around 8986 and 8993 eV is found in an NH3_4_Z(2)Cu model as the N-Cu-N angle changes from 180 to 100 degrees. We correlate these features to the variation of the 4p state by PDOS analysis. In addition, the feature peaks for both the Cu+ cation and Cu2+ cation do not show a dependence on the Cu-N bond length. We further show that the feature peaks also change when the coordination number of the Cu cation is varied, while these feature peaks are independent of the zeolite topology. These findings help elucidate the experimental XANES features at an atomic and an electronic level.