469036 Precursor Ion-Ion Aggregation in the Brust-Schiffrin Synthesis of Alkanethiol Nanoparticles

Monday, November 14, 2016
Grand Ballroom B (Hilton San Francisco Union Square)
Trent Graham1, Ryan Renslow1,2, Niranjan Govind2 and Steven R. Saunders3, (1)Gene and Linda Voiland School of Chemical Engineering and Bioengineering, Washington State University, Pullman, WA, (2)Earth and Biological Sciences Directorate, Pacific Northwest National Laboratory, Richland, WA, (3)Voiland School of Chemical Engineering and Bioengineering, Washington State University, Pullman, WA

Tetraoctylammonium bromide is used in the Brust-Schiffrin nanoparticle synthesis to phase-transfer chloroaurate ions from the aqueous phase to the organic phase. While it is established that the quaternary ammonium complex self-associates in the organic phase, the actual self-assembled structure is debated. We have confirmed the presence of ion-ion aggregates through quantitative 1H Nuclear Magnetic Resonance spectroscopy (NMR), pulsed field gradient, diffusion-ordered NMR (DOSY-NMR) and density functional theory (DFT) based NMR chemical shift calculations. Tetraoctylammonium complexes (TOA-X, where X = Br, Cl, AuCl4-x­Brx, AuBr4/Br and AuCl4-xBrx/Br) were investigated to measure the extraction of water into the organic phase. 1H NMR and DFT based NMR shielding calculations indicated that deshielding of water is due to hydration of the anion and not the formation of the aqueous core of a reverse micelle. DOSY-NMR results were consistent with the formation of small aggregates at typical Brust-Schiffrin synthesis concentrations. The extent of aggregation correlated with the size and electronegativity of the anion and was analyzed with a modified, isodesmic, indefinite aggregation model. The substitution of bromoauric acid for chlororoauric acid at conditions emulating the Brust-Schiffrin synthesis increased the aggregation of the quaternary ammonium complex. The increase in aggregation corresponded with an increase in the size of the produced nanoparticles from 4.3 to 4.6 nm. Understanding the self-assembly and supramolecular structure of precursors in the Brust-Schiffrin synthesis will enable further refinement of models that predict the growth of noble metal nanoparticles.

Extended Abstract: File Not Uploaded
See more of this Session: Poster Session: Nanoscale Science and Engineering
See more of this Group/Topical: Nanoscale Science and Engineering Forum