Vapor-Phase Synthesis of Electrocatalytic Covalent Organic Frameworks.

The inability to process many covalent organic frameworks (COFs) as thin films plagued their widespread utilization. Herein, we present a vapor-phase pathway for the bottom-up synthesis of a class of porphyrin-based COFs. This approach allows for 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, we achieve remarkable electrocatalytic performance, resulting in unprecedentedly high mass activity values. We demonstrate how the choice of metal atoms, i.e., cobalt and copper, can determine the catalytic activities of POR-COFs. The theoretical data proves that the Cu site is highly active for nitrate conversion to ammonia on the synthesized COF. This article is protected by copyright. All rights reserved.