Abstract
Understanding the general electronic principles underlying molecule-surface interactions at the nanoscale is crucial for revealing the processes based on chemisorption,like catalysis, surface ligation, surface fluorescence, etc. However, the electronic mechanisms of how surface states affect and even dominate the properties of nanomaterials have long remained unclear. Here, using one-unit-thin TiO2 nanosheet as a model surface platform, we find that surface ligands can competitively polarize and confine the valence 3d orbitals of surface Ti atoms from delocalized energy band states to localized chemisorption bonds, through probing the surface chemical interaction at the orbital level with near-edge X-ray absorption fine structure (NEXAFS). Such ligand-induced orbital redistributions, which are revealed by combining experimental discoveries, quantum calculations, and theoretical analysis, are cooperative with ligand coverages and can enhance the strength of chemisorption and ligation-induced surface effects on nanomaterials. The model and concept of nanoscale cooperative chemisorption reveal the general physical principle that drives the coverage-dependent ligand-induced surface effects on regulating the electronic structures, surface activity, optical properties, and chemisorption strength of nanomaterials.
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Disclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.