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The inability to process many covalent organic frameworks (COFs) as thin films plagues their widespread utilization. Herein, a vapor‐phase pathway for the bottom‐up synthesis of a class of porphyrin‐based COFs is presented. This approach allows integrating electrocatalysts made of metal‐ion‐containing COFs into the electrodes’ architectures in a single‐step synthesis and deposition. By precisely controlling the metal sites at the atomic level, remarkable electrocatalytic performance is achieved, resulting in unprecedentedly high mass activity values. How the choice of metal atoms, i.e., cobalt and copper, can determine the catalytic activities of POR‐COFs is demonstrated. The theoretical data proves that the Cu site is highly active for nitrate conversion to ammonia on the synthesized COFs.

The main drawbacks of today's state‐of‐the‐art lithium–air (Li–air) batteries are their low energy efficiency and limited cycle life due to the lack of earth‐abundant cathode catalysts that can drive both oxygen reduction and evolution reactions (ORR and OER) at high rates at thermodynamic potentials. Here, inexpensive trimolybdenum phosphide (Mo₃P) nanoparticles with an exceptional activity—ORR and OER current densities of 7.21 and 6.85 mA cm⁻²at 2.0 and 4.2 V versus Li/Li⁺, respectively—in an oxygen‐saturated non‐aqueous electrolyte are reported. The Tafel plots indicate remarkably low charge transfer resistance—Tafel slopes of 35 and 38 mV dec⁻¹for ORR and OER, respectively—resulting in the lowest ORR overpotential of 4.0 mV and OER overpotential of 5.1 mV reported to date. Using this catalyst, a Li–air battery cell with low discharge and charge overpotentials of 80 and 270 mV, respectively, and high energy efficiency of 90.2% in the first cycle is demonstrated. A long cycle life of 1200 is also achieved for this cell. Density functional theory calculations of ORR and OER on Mo₃P (110) reveal that an oxide overlayer formed on the surface gives rise to the observed high ORR and OER electrocatalytic activity and small discharge/charge overpotentials.