Vapor‐Phase Synthesis of Electrocatalytic Covalent Organic Frameworks

• Published in: Advanced materials (Weinheim) 2024-04, Vol.36 (14), p.e2309302-n/a
• Main Authors: Mohamed, Syed Ibrahim Gnani Peer, Namvar, Shahriar, Zhang, Tan, Shahbazi, Hessam, Jiang, Zhen, Rappe, Andrew M., Salehi‐Khojin, Amin, Nejati, Siamak
• Format: Article
• Language: English
• Subjects: Ammonia; Atomic properties; catalysis; Copper; covalent organic frameworks; DFT; Electrocatalysts; ENERGY STORAGE; Li-O2 battery; MATERIALS SCIENCE; nitrate reduction; oxygen reduction and evolution reaction; Porphyrins; Synthesis; Thin films; vapor phase synthesis
• ISSN: 0935-9648; 1521-4095
• DOI: 10.1002/adma.202309302

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. A solvent‐free pathway for synthesizing metal‐containing porphyrin‐based Covalent Organic Frameworks (MPOR‐COFs) is presented. The roles of synthetic conditions and the transition metals chelating with porphyrin are highlighted through both experimental and computational works. This study sets forth a unique approach to the synthesis and integration of electrocatalysts into electrode architectures, propelling applications into the cutting‐edge realm.