Thus, we come to a possible mechanism in which the self-assembled Co Terpy-RF molecules create a hydrophobic environment on the GDE surface (Fig. ). This is ideal in allowing CO2 permeation directly from the gas phase and electron transfer from the electrode. At the same time, protons may transfer not directly through free water but, at least in part, via a pyridine-assisted proton conduit and specific channels within these structured films and this acts to hydrogenate the CO2R intermediates. Proton conduction has previously been implicated within MOFs that accelerated their performance towards hydrogen evolution. Further, the catalytic mechanism proposed bears similarity to observations of ligand-assisted protonation in CO2 methanation in molecular 48 and heterogeneous 49 systems, as well as terpyridine units playing the same role in CO2R to CO 20 ; proton channels are also a key factor in the performance of CO2reducing enzymes. The creation of a hydrophobic pocket stabilizes CO and other CO2R intermediates for further hydrogenation all the way to the CH4 final product and is an example of environment-dictated electrocatalysis. This is in line with previous work highlighting the beneficial effects of increased hydrophobicity on the multi-electron reduction of CO2, as well as the impact of substrate diffusion in the catalyst environment 53 on its performance. As a last endeavor, we moved to demonstrate a possible route for optimizing the system by taking advantage of the perfluorinated side chains and their strong interaction with other fluorinated species. A challenge we encountered with Co Terpy-RF was that only 1% of the total immobilized catalyst was 'wired' to the electrode, as quantified through integrating the Co(II/III) redox wave. To enhance the catalyst wiring, we added fluorinated carbon nanotubes (F-CNTs) into the catalyst dispersion prior to drop casting it onto the GDE (Fig. and S24-25). A CV of the system under CO2R flow showed enhanced waves of the Co(III/II) and Co(II/I) redox couples despite using the same catalyst concentration (Fig. ), indicative of better electrical connection to the electrode via the F-CNT electron conduits. Measuring the CO2R reactivity showed both an enhanced CH4 FE of up to 80% (Fig. and) and an increased CH4 partial current density of 10 mA cm -2 (Fig. ) at -0.79 V vs. RHE. Finally, using an electrolyzer in flow, the catalyst displayed constant CH4 production over a period of 9 hours at -0.59 V vs. RHE (Fig. and). Variations in FE may originate from changes in wetting and hydration of the gas-liquid-solid interface over time. While the system is still far from optimized, such experiments present a viable route forward towards attaining industrially relevant current densities of 200 mA cm -2 or more. This performance particularly stands out amongst Co Terpy molecular electrocatalysts or those adsorbed onto GDEs reported to date, both of which tend to be selective for CO.