ABSTRACT
The routine study of the solid-water interface by XPS is potentially revolutionary as this development opens up whole new areas of study for photoelectron spectroscopy. To date this has been realised by only a few groups worldwide and current techniques have significant restrictions on the type of samples which can be studied. Here we present a novel and uniquely flexible approach to the problem. By introducing a thin capillary into the NAP-XPS, a small droplet can be injected onto the sample surface, offset from the analysis area by several mm. By careful control of the droplet size a water layer of controllable thickness can be established in the analysis area-continuous with the bulk droplet. We present results from the solid-water interface on a vacuum prepared TiO2(110) single crystal and demonstrate that the solid/liquid interface is addressable.
ABSTRACT
The mechanism of the two-phase Brust-Schiffrin synthesis of alkane thiol protected metal nanoparticles is known to be highly sensitive to the precursor species and reactant conditions. In this work X-ray absorption spectroscopy is used in conjunction with liquid/liquid electrochemistry to highlight the significance of Br- in the reaction mechanism. The species [AuBr4]- is shown to be a preferable precursor in the Brust-Schiffrin method as it is more resistant to the formation of Au(i) thiolate species than [AuCl4]-. Previous literature has demonstrated that avoidance of the Au(i) thiolate is critical to achieving a good yield of nanoparticles, as [Au(i)X2]- species are more readily reduced by NaBH4. We propose that the observed behavior of [AuBr4]- species described herein explains the discrepancies in reported behavior present in the literature to date. This new mechanistic understanding should enable nanoparticle synthesis with a higher yield and reduce particle size polydispersity.
