Reaction stragegies using surfacefunctionalized nanoparticles

Chapter I: The Chapter introduces motivation to work with smart nanomaterials, presents general definition
and classification, describes current and past uses, how to synthesize and functionalize them using various
methods and examples.
Chapter II: The Chapter summarizes published work which investigated NP surface activation with
HNO3, established functionalization methods anchoring ligands and found suitable characterization methods
of TiO2 NPs.17 The Chapter further studied the application of the SALSAC 'surface-as-ligand, surface-ascomplex'
method using several homoleptic copper(I) and iron(II) complexes with f-NPs.
Chapter III: This Chapter attempts to transfer literature homogeneous catalytic reactions onto TiO2 f-
NPs. The methods learned included (i) forming a metal complex catalyst directly on the NP surface instead of
using an in-situ method, (ii) testing metal-to-ligand ratios that might be beneficial, (iii) more cautiously considering
the impact of different ligand functional groups, (iv) moisture-sensitive reactions can be problematic.
Chapter IV: This summarizes published work23 which used stepwise synthesised Rh(3)2@TiO2 NPs as
catalyst to perform an alcohol oxidation with 1-phenylethanol. The Rh(3)2@TiO2 NPs were used to compare
their catalytic activity in contrast to the homogeneous counterpart, [Rh(3)2]Cl3. It was confirmed that catalytic
activity was not lost upon surface-binding. The stability of Rh(3)2@TiO2 NPs was remarkable as they were
able to withstand reaction temperatures of up to 100 °C for 24 days without degradation.
Chapter V: This Chapter focuses on a previously reported system for water reduction under simulated
sunlight irradiation Lehn and Sauvage utilized [Ru(bpy)3]2+ and [Rh(bpy)3]3+ as photo- and electrocatalysts.24
The homogeneous catalysts were replaced with a heterogeneous version anchored onto TiO2 NPs. Using these
ruthenium(II) and rhodium(III) metal complex f-NPs (rR@TiO2 NPs), greater efficiency for the immobilised
systems over the previously reported homogeneous systems was demonstrated and published.25
Chapter VI: This explores water reduction catalysis under the same conditions and metal complex preparations
but now using SrTiO3 and BaTiO3 NPs instead of TiO2. The Chapter further investigated H2O2 surface
activation compared to previous studies with HNO3 activation. Thereby it was found that the metal complex
H2O2 activated BaTiO3 and SrTiO3 NPs were inactive for water reduction. Acid activated NPs were both
active during water reduction, and SrTiO3 NPs being the most efficient while performing worse than comparable
TiO2 NPs. The Chapter further studied pH influence during complexation.
Chapter VII: This Chapter focuses on functionalization of commercial WO3, ZrO2, SnO2, TiO2 and
ZnO NPs with anchoring ligand bearing phosphonic or carboxylic acids using methods established in Chapter
II. Overall, successful functionalization was established with each type of metal oxide NPs. Anchoring ligand
binding preferences were studied by carrying out competition experiments concluding a better binding with
phosphonic acid bearing anchors in most cases.
Chapter VIII: This takes a closer look at ruthenium functionalized ZnO (Ru@uZnO) NPs. They were
able to perform two catalytic reactions relatively well, namely the deuteration of bpy or 4'-aminobenzo-15-
crown-5 (12), and the oxidation of 1-phenylethanol (13). However, the material characterization of Ru@uZnO
NPs using TGA-MS was insufficient to fully characterize the material and further measurements are required
to provide insights into the catalytic activity.
Chapter IX: Ruthenium-complex functionalized TiO2 NPs with 2-(thiophen-2-yl)-2,2'-bipyridine (21)
and/or 2,2'-bipyridine (bpy) as ancillary ligands were prepared. Ligand 21 was selected with the aim of using
the pendant thienyl groups to investigate solution or vapour polymerizations. The project was more successful
in using vapour phase polymerization (VPP) with using either FeCl3 or p-toluenesulfonic acid (PTSa) as oxidant
and 2,2':5',2''-terthiophene (TTh) as building block.
Chapter X: Summarizes the conclusion of each Chapter but being more thorough in its approach than
the work presented here.