Species mass transfer governs the selectivity of gas diffusion electrodes toward H2O2 electrosynthesis

The meticulous design of advanced electrocatalysts and their integration into gas diffusion electrode (GDE) architectures is emerging as a prominent research paradigm in the H 2 O 2 electrosynthesis community. However, it remains perplexing that electrocatalysts and assembled GDE frequently exhibit substantial discrepancies in H 2 O 2 selectivity during bulk electrolysis. Here, we elucidate the pivotal role of mass transfer behavior of key species (including reactants and products) beyond the intrinsic properties of the electrocatalyst in dictating electrode-scale H 2 O 2 selectivity. This tendency becomes more pronounced in high reaction rate (current density) regimes where transport limitations are intensified. By utilizing diffusion-related parameters (DRP) of GDEs (i.e., wettability and catalyst layer thickness) as probe factors, we employ both short- and long-term electrolysis in conjunction with in-situ electrochemical reflection-absorption imaging and theoretical calculations to thoroughly investigate the impact of DRP and DRP-controlled local microenvironments on O 2 and H 2 O 2 mass transfer. The mechanistic origins of diffusion-dependent conversion selectivity at the electrode scale are unveiled accordingly. The fundamental insights gained from this study underscore the necessity of architectural innovations for mainstream hydrophobic GDEs that can synchronously optimize mass transfer of reactants and products, paving the way for next-generation GDEs in gas-consuming electroreduction scenarios. Electrocatalysts and assembled gas diffusion electrodes frequently exhibit discrepancies in selectivity during H 2 O 2 electrosynthesis. Here, the authors report the pivotal role of key species transport beyond the intrinsic properties of electrocatalysts in dictating electrode-scale H 2 O 2 selectivity.