Semi-solid electrolyte with layered heterometallic low-valent electron-mediator enabling indirect destruction of gaseous toluene

The electrochemical degradation of air pollutants, particularly volatile organic compounds (VOCs), at their gaseous state is a promising method. However, it remains at an infant stage due to sluggish solid–gas electron transfers at room temperature. We established a triphase reaction condition using a semi-solid electrolyte layer between the electrode and membrane to enhance the electron transfer at room temperature. A polyvinyl alcohol (PVA) gel layer was inserted between a bimetallic layered CuNi(CN)₄ complex coated Cu foam electrode (TCNi-Cu) and Nafion 324 membrane for the degradation of gaseous toluene. The cyclic voltammetry of TCNi-Cu using a sodium hydroxide-coated copper mesh electrode at a triphase showed Cu¹⁺ and Ni¹⁺ stabilization at −0.7 and −0.9 V, respectively, which was similar to the liquid phase electron transfer behavior. The degradation capacity of gaseous toluene without using electrogenerated TCNi-Cu + PVA gel was 0.54 mg cm² min⁻¹, whereas that of TCNi-Cu + PVA gel layers was 1.17 mg cm⁻²min⁻¹, which revealed the mediation effect at a triphase condition. Toluene was converted into oxygen-containing products, such as butanol, propanol, and acetone (without reduction products), which revealed that indirect oxidation occurred at the cathode using an in-situ generated oxidant, such as OH˙ radical. As an electron-mediator, Cu¹⁺ was used to form oxidants for the degradation of toluene at −0.7 V. The toluene removal rate reached 1.4 μmol h⁻¹, with an energy efficiency of 0.15 Wh L⁻¹. This study is the first attempt to describe a liquid-electrolyte-free cathodic half-cell in electrochemical application to VOCs degradation, highlighting the electron transfer at room temperature.