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Monitoring Thiol–Ligand Exchange on Au Nanoparticle Surfaces

Surface functionalization of nanoparticles (NPs) plays a crucial role in particle solubility and reactivity. It is vital for particle nucleation and growth as well as for catalysis. This raises the quest for functionalization efficiency and new approaches to probe the degree of surface coverage. We present an (in situ) proton nuclear magnetic resonance (1H NMR) study on the ligand exchange of oleylamine by 1-octadecanethiol as a function of the particle size and repeated functionalization on Au NPs. Ligand exchange is an equilibrium reaction associated with Nernst distribution, which often leads to incomplete surface functionalization following “standard” literature protocols. Here, we show that the surface coverage with the ligand depends on the (i) repeated exchange reactions with large ligand excess, (ii) size of NPs, that is, the surface curvature and reactivity, and (iii) molecular size of the ligand. As resonance shifts and extensive line broadening during and after the ligand exchange impede the ev...

Authors:   Martin Kluenker; Mihail Mondeshki; Muhammad Nawaz Tahir; Wolfgang Tremel
Journal:   Langmuir
Year:   2018
DOI:   10.1021/acs.langmuir.7b04015
Publication date:   19-Jan-2018
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