Influence of Tail Groups during Functionalization of ZnO Nanoparticles on Binding Enthalpies and Photoluminescence.

We report on the tailoring of ZnO nanoparticle (NP) surfaces by catechol derivatives (CAT) with different functionalities: tert-butyl group (tertCAT), hydrogen (pyroCAT), aromatic ring (naphCAT), ester group (esterCAT), and nitro group (nitroCAT). The influence of electron-donating/-withdrawing properties on enthalpy of ligand binding (ΔH) was resolved and subsequently linked with optical properties. First, as confirmed by ultraviolet/visible (UV/vis) and Fourier transform infrared (FT-IR) spectroscopy results, all CAT molecules chemisorbed to ZnO NPs, independent of the distinct functionality. Interestingly, the ζ-potentials of ZnO after functionalization shifted to more negative values. Then, isothermal titration calorimetry (ITC) and a mass-based method were applied to resolve the heat release during ligand binding and the adsorption isotherm, respectively. However, both heat- and mass-based approaches alone did not fully resolve the binding enthalpy of each molecule adsorbing to the ZnO surface. This is mainly due to the fact that the Langmuir model oversimplifies the underlying adsorption mechanism, at least for some of the tested CAT molecules. Therefore, a new, fitting-free approach was developed to directly access the adsorption enthalpy per molecule during functionalization by dividing the heat release measured via ITC by the amount of bound molecules determined from the adsorption isotherm. Finally, the efficiency of quenching the visible emission caused by ligand binding was investigated by photoluminescence (PL) spectroscopy, which turned out to follow the same trend as the binding enthalpy. Thus, the functionality of ligand molecules governs the binding enthalpy to the particle surface, which in turn, at least in the current case of ZnO, is an important parameter for the quenching of visible emission. We believe that establishing such correlations is an important step toward a more general way of selecting and designing ligand molecules for surface functionalization. This allows developing strategies for tailored colloidal surfaces beyond empirically driven formulation on a case by case basis.