A Complementary Experimental and Theoretical Approach for Probing the Surface Functionalization of ZnO with Molecular Catalyst Linkers

Abstract The application of ZnO materials as solid‐state supports for molecular heterogeneous catalysis is contingent on the functionalization of the ZnO surface with stable self‐assembled monolayers (SAMs) of catalyst linker molecules. Herein, experimental and theoretical methods are used to study SAMs of azide‐terminated molecular catalyst linkers with two different anchor groups (silane and thiol) on poly and monocrystalline (0001, ) ZnO surfaces. Angle‐resolved and temperature‐dependent X‐ray photoelectron spectroscopy (XPS) is used to study SAM binding modes, thermal stabilities, and coverages. The binding strengths and atomistic ordering of the SAMs are determined via atom‐probe tomography (APT). Density functional theory (DFT) and ab initio molecular dynamics (AIMD) calculations provide insights on the influence of the ZnO surface polarity on the interaction affinity and conformational behavior of the SAMs. The investigations show that SAMs based on 3‐azidopropyltriethoxysilane possess a higher binding strength and thermal stability than the corresponding thiol. SAM surface coverage is strongly influenced by the surface polarity of ZnO, and the highest coverage is observed on the polycrystalline surface. To demonstrate the applicability of linker‐modified polycrystalline ZnO as a catalyst support, a chiral Rh diene complex is immobilized on the azide‐terminal of the SAM and its coverage is evaluated via XPS.