Electrodeless Synthesis of Low Dispersity Au Nanoparticles and Nanoclusters at an Immiscible Micro Water/Ionic Liquid Interface

Owing to their biocompatibility, optical, and catalytic properties, Au nanoparticles (NPs) have been the subject of much research. Since smaller NPs have enhanced catalytic properties and NP morphology greatly impacts their effectiveness, controlled and reproducible methods of generating Au NPs are still being sought. Herein, Au NPs were electrochemically generated at a water|ionic liquid (w|IL) immiscible micro-interface, 25 µm in diameter, using a redox active IL and compared to results at a water|oil (w|o) one. The liquid|liquid interface is advantageous as it is pristine and highly reproducible, as well as an excellent means of species and charge separation. In this system, KAuCl(4) dissolved in the aqueous phase reacts under external potential control at the water|P(8888)TB (tetraoctylphosphonium tetrakis(pentafluorophenyl)borate) with trioctyl(ferrocenylhexanoyl)phosphonium tetrakis(pentafluorophenyl)borate (FcIL), an electron donor and redox active IL. FcIL was prepared with a common anion to P(8888)TB, which greatly enhances its solubility in the bulk IL. Simple ion transfer of AuCl(4)(−) and AuCl((4−γ))(OH)(γ)(−) at the w|P(8888)TB micro-interface were characterized voltammetrically as well as their heterogeneous electron transfer reaction with FcIL. This interfacial reaction generates Au NPs whose size can be thermodynamically controlled by modifying the pH of the aqueous phase. Critically, at low pH, nanoclusters, <1.7 nm in diameter, were generated owing to inhibited thermodynamics in combination with the supramolecular fluidic nature of the IL microenvironment that was observed surrounding the as-prepared NPs.