Rapidly Constructing Meter‐Scale Single‐Molecule Integrated Catalytic Electrode with Hydrophobic Microenvironment for pH‐Universal CO2 Electroreduction

Abstract The massive production of cost‐effective and highly‐efficient electrode materials is crucial for industrial CO 2 electroconversion. Herein, this work breaks away from conventional approaches by directly constructing an integrated single‐molecule catalytic electrode (7F‐CoPc@GF) at the meter scale, through the integration of π‐extended macrocyclic structures into commercial carbon‐based collectors with strong interfacial interactions. This innovative method reshapes traditional electrode design by using a liquid‐phase self‐adaptive anchoring strategy, eliminating the need for conductive adducts and binders. In addition, through introducing the perfluoroalkyl chain, the built‐in hydrophobic microenvironment in the heterogenized macrocycles optimizes the electron migration and interfacial water interaction around active sites, suppressing the hydrogen evolution reaction and thereby enhancing the pH‐universal CO 2 electroreduction reaction across a broad potential range. Significantly, the mechanistic study reveals that the hydrophobic interfacial microenvironment not only enhances effective collisions between active sites and reactants but also facilitates the immediate removal of products from the electrode surface. Further development of dual value‐added electrolysis systems, incorporating industrial waste gas treatment, highlights the versatility and extensibility of this meter‐scale integrated catalytic electrode material. These findings offer a promising methodology for rational design of stable, binder‐free, large‐size electrodes, advancing sustainable CO 2 electrolysis at scale.