Preparation and Electrocatalytic Application of Composites Containing Gold Nanoparticles Protected with Rhodium-Substituted Polyoxometalates.

Substitution of a metal center of phosphomolybdate, PMo(12)O(40) (3-) (PMo(12)), or its tungsten analogue with dirhodium(II) and subsequent stabilization of gold nanoparticles, AuNPs, with Rh(2)PMo(11) is demonstrated. The AuNP-Rh(2)PMo(11) mediates oxidations but adsorbs too weakly for direct modification of electrode materials. Stability in quiescent solution was achieved by modifying glassy carbon (GC) with 3-aminopropyltriethoxysilane (APTES) and then electrostatically assembling AuNP-Rh(2)PMo(11). At GC|APTES|AuNP-Rh(2)PMo(11), cyclic voltammetry showed the expected set of three reversible peak-pairs for PMo(11) in the range -0.2 to 0.6 vs (Ag/AgCl)/V and the reversible Rh(II,III) couple at 1.0 vs (Ag/AgCl)/V. The presence of AuNPs increased the current for the reduction of bromate by a factor of 2.5 relative to that at GC|Rh(2)PMo(11), and the electrocatalytic oxidation of methionine displayed characteristics of synergism between the AuNP and Rh(II). To stabilize AuNP-Rh(2)PMo(11) on a surface in a flow system, GC was modified by electrochemically assisted deposition of a sol-gel with templated 10-nm pores prior to immobilizing the catalyst in the pores. The resulting electrode permitted determination of bromate by flow-injection amperometry with a detection limit of 4.0 × 10(-8) mol dm(-3).