Tuning cohesive interactions of porphyrins for selective two‐electron oxygen reductions

Abstract Selective two‐electron oxygen reduction reaction (ORR) provides a sustainable route for hydrogen peroxide production, with broad industrial and environmental applications. However, controlling over ORR selectivity remains challenging due to the competing four‐electron pathway (i.e., over‐reduction of oxygen to water). We propose optimizing catalytic performance by tuning cohesive interactions using pyridine‐based porphyrin catalysts. The positioning of pyridine nitrogen ( ortho ‐, meta ‐, and para ‐N) modulates intra‐ and intermolecular interactions through metal coordination and/or support incorporation. Metal coordination fine‐tunes the catalytic center's electronic structure, significantly enhancing two‐electron selectivity, while carbon nanotube integration boosts activity to industrially relevant current densities. The optimized system demonstrates robust stability in a flow cell prototype, maintaining high performance without degradation. Techno‐economic analysis reveals low production costs (~60% market price), confirming practical viability and profitability. This work advances molecular‐level design principles for microenvironment and cohesive interaction engineering in electrocatalysis.