Tracking Coordination Environment and Reaction Intermediates in Homo- and Heterogeneous Epoxidation Catalysts via Ti L2,3-edge NEXAFS

Ti-based molecules and materials are ubiquitous, and play a major role in both homogeneous and heterogeneous catalytic processes. Understanding the electronic structures of their active sites (oxidation state, local symmetry and ligand environment) is key to developing molecular-level structure-property relationships. In that context, X-ray absorption spectroscopy (XAS) offers a unique combination of element selectivity and sensitivity to local symmetry. Commonly, for early transition metals such as Ti, K-edge XAS is applied for in situ characterization and subsequent structural analysis with high sensitivity towards tetrahedral species. Ti L2,3-edge spectroscopy is in principle complementary and offers specific opportunities to interrogate the electronic structure of five-and six-coordinated species. It is, however, much more rarely implemented, because the use of soft X-rays implies ultra-high vacuum conditions. Furthermore, the interpretation of the data can be challenging. Here, we show how Ti L2,3-edge spectroscopy can help to obtain unique information about both homogeneous and heterogeneous epoxidation catalysts and to develop a molecular-level relationship between spectroscopic signatures and electronic structures. Towards this goal, we first establish a spectral library of molecular Ti reference compounds, comprising various coordination environments with mono- and dimeric Ti species having O, N and Cl-ligands. We next implemented a computational methodology based on multiplet ligand field theory and maximally localized Wannier orbitals benchmarked on our library to understand Ti L2,3-edge spectroscopic signatures. We finally used this approach to track and predict spectra of catalytically relevant intermediates, focusing on Ti-based olefin epoxidation catalysts.