Aqueous Electrochemical Partial Oxidation of Gaseous Ethylbenzene by a Ru-Modified Covalent Triazine Framework.

Abstract

Aqueous electrochemical oxidation of hydrocarbons into valuable compounds, such as alcohols and carbonyl compounds, has attracted much attention because these systems can operate under mild conditions without toxic oxidants or flammable solvents. The key requirements to achieve such oxidation reactions are (1) highly reactive species on an electrocatalyst for the activation of C-H bonds and (2) efficient transportation pathway for water-insoluble hydrocarbons to an electrode surface. We have determined that a gas diffusion electrode (GDE) supporting Ru atom-modified covalent triazine frameworks (Ru-CTF) has an activity for the electrooxidation of gaseous ethylbenzene to acetophenone using an aqueous electrolyte. A high-valency Ru═O species was formed in Ru-CTF as an effective active site for O-atom insertion into stable C-H bonds. Furthermore, Ru-CTF showed excellent stability during four consecutive cycles with the replacement of the electrolyte every 12 h, although the reactive Ru═O species is generated. As for the transportation pathway for substrates, the amount of acetophenone generated from gaseous ethylbenzene was much larger than that from ethylbenzene dissolved in an electrolyte. This result indicates that the three-dimensional microstructures in the GDE maximize the transportation of gaseous hydrocarbons and the oxidation reaction occurs at the triple-phase boundary, which enables the use of aqueous electrolytes.