Organosilane oxidation by water catalysed by large gold nanoparticles in a membrane reactor

Abstract

We show that gold nanoparticles catalyse the oxidation of organosilanes using water as oxidant at ambient conditions. Remarkably, monodispersions of small gold particles (3.5 nm diameter) and large ones (6–18 nm diameter) give equally good conversion rates. This is important because separating large nanoparticles is much easier, and can be done using ultrafiltration instead of nanofiltration. We introduce a simple setup, constructed in-house, where the reaction products are extracted through a ceramic membrane under pressure, leaving the gold nanoparticles intact in the vessel. The nominal substrate/catalyst ratios are ca. 1800 : 1, with typical TONs of 1500–1600, and TOFs around 800 h⁻¹. But the actual activity of the large nanoparticles is much higher, because most of their gold atoms are “inside”, and therefore unavailable. Control experiments confirm that no gold escapes to the membrane permeate. The role of surface oxygen as a possible co-catalyst is discussed. Considering the ease of product separation and the robustness of the ceramic membrane, this approach opens opportunities for actual applications of gold catalysts in water oxidation reactions.