Experimental and computational insights into the aminopropylphosphonic acid modification of mesoporous TiO2 powder: The role of the amine functionality on the surface interaction and coordination

[Display omitted] •Surface functionalization of TiO2 with 3-aminopropylphosphonic acid.•Combination of experimental and computational approaches.•Coexistence of free NH2 groups and aminopropyl chains flipped back in interaction with the surface.•Surface adsorbed H2O results in a strong stabilization for all modelled conformations.•Validation between calculated 31P chemical shifts and experimental 31P NMR spectra. Recently, interest has been directed towards the grafting of metal oxides with organophosphonic acids bearing terminal amine groups to extend the functionality and applicability of these materials. Previous reports mainly focus on the application perspective, while a detailed characterization of the surface properties at the molecular level and the correlation with the synthesis conditions are missing. In this work, mesoporous TiO2 powder is grafted with 3-aminopropylphosphonic acid (3APPA) under different concentrations (20, 75, 150 mM) and temperatures (50, 90 °C) and compared with propylphosphonic acid (3PPA) grafting to unambiguously reveal the impact of the amine group on the surface properties. A combination of complementary spectroscopic techniques and Density Functional Theory-Periodic Boundary Conditions (DFT/PBC) calculations are used. At 90 °C and high concentrations, lower modification degrees are obtained for 3APPA compared to 3PPA, due to amine-induced surface interactions. Both X-ray Photoelectron Spectroscopy (XPS) and Diffuse Reflectance Infrared Fourier Transform (DRIFT) spectroscopy reveal that both NH2 and NH3+ groups are present, with also contributions of NH2 groups involved in hydrogen bonding interactions. A similar ratio of NH2/NH3+ (65:35) is obtained irrespective of the modification conditions, suggesting similar relative contributions of different surface conformations. Calculated adsorption energies from DFT calculations on 3APPA adsorption on anatase (101) in relation to the water coverage reveals a coexistence of various structures with the amine group involved in intra-adsorbate, inter-adsorbate and adsorbate–surface interactions. Further validation is obtained from the strong overlap of different 31P environments represented by the broad band (35-12 ppm) in experimental 31P Nuclear Magnetic Resonance (NMR) spectra and calculated 31P chemical shifts of all modelled monodentate and bidentate structures. Structures related to the tridentate binding mode are not formed due to geometric restrictions of the anatase (101)