Polymethylhydrosiloxane-modified gas-diffusion cathode for more efficient and durable H2O2 electrosynthesis in the context of water treatment

On-site H2O2 electrosynthesis via two-electron oxygen reduction reaction (ORR) is attracting great interest forwater treatment. The use of carbon black-based gas-diffusion electrodes (GDEs) is especially appealing, but theiractivity, selectivity and long-term stability must be improved. Here, a facile GDEs modification strategy usingtrace polymethylhydrosiloxane (PMHS) allowed reaching a outstanding H2O2 production, outperforming theconventional polytetrafluoroethylene (PTFE)-GDE (1874.8 vs 1087.4 mg L-1 at 360 min). The superhydrophobicityconferred by PMHS endowed the catalytic layer with high faradaic efficiencies (76.2%-89.7%)during long-term operation for 60 h. The electrochemical tests confirmed the high activity and selectivity of thePMHS-modified GDE. Moreover, the efficient degradation of several micropollutants by the electro-Fentonprocess demonstrated the great potential of the new GDE. An in-depth understanding of the roles of PMHSfunctional groups is provided from DFT calculations: the -CH3 groups contribute to form a superhydrophobicinterface, whereas Si-H and as-formed Si-O-C sites modulate the coordination environment of active carboncenters