Electrochemical reduction of CO2 presents an attractive way to store renewable energy in chemical bonds in a potentially carbon-neutral way. However, the available electrolyzers suffer from intrinsic problems, like flooding and salt accumulation, that must be overcome to industrialize the technology. To mitigate flooding and salt precipitation issues, researchers have used super-hydrophobic electrodes based on either expanded polytetrafluoroethylene (ePTFE) gas-diffusion layers (GDL’s), or carbon-based GDL’s with added PTFE. While the PTFE backbone is highly resistant to flooding, the non-conductive nature of PTFE means that without additional current collection the catalyst layer itself is responsible for electron-dispersion, which penalizes system efficiency and stability. In this work, we present operando results that illustrate that the current distribution and electrical potential distribution is far from a uniform distribution in thin catalyst layers (~50 nm) deposited onto ePTFE GDL’s. We then compare the effects of thicker catalyst layers (~500 nm) and a newly developed non-invasive current collector (NICC). The NICC can maintain more uniform current distributions with 10-fold thinner catalyst layers while improving stability towards ethylene (≥ 30%) by approximately two-fold.@en

Immobilizing molecular catalysts on electrodes is vital for electrochemical applications. However, creating robust electrode-catalyst interactions while maintaining good catalytic performance and rapid electron transfer is challenging. Here, without introducing any foreign elements, we show a bottom-up synthetic approach of constructing the conjugated C−C bond between the commercial Vulcan carbon electrode and an organometallic catalyst. Characterization results from FTIR, XPS, aberration-corrected TEM and EPR confirmed the successful and uniform heterogenization of the complex. The synthesized Vulcan-LN4−Co catalyst is highly active and selective in the oxygen reduction reaction in neutral media, showing an 80 % hydrogen peroxide selectivity and a 0.72 V (vs. RHE) onset potential which significantly outperformed the homogenous counterpart. Based on single-crystal XRD and NMR data, we built a model for density functional theory calculations which showed a nearly optimal binding energy for the *OOH intermediate. Our results show that the direct conjugated C−C bonding is an effective approach for heterogenizing molecular catalysts on carbon, opening new opportunities for employing molecular catalysts in electrochemical applications.@en