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Title: In Situ Bottom-up Synthesis of Porphyrin-Based Covalent Organic Frameworks

Journal Article · · Journal of the American Chemical Society

Synthesis and processing of two- or three- dimensional covalent organic frameworks (COFs) have been limited by solvent intractability and sluggish condensation kinetics. Here, we report on the electro- chemical deposition of poly(5,10,15,20-tetrakis(4- aminophenyl)porphyrin)-covalent organic frameworks (POR-COFs) via formation of phenazine linkages. Here, by adjusting the synthetic parameters, we demonstrate the rapid and bottom-up synthesis of COF dendrites. Both experiment and density functional theory underline the prominent role of pyridine, not only as a polymerization promoter but as a stabilizing sublattice, cocrystallizing with the framework. The crucial role of pyridine in dictating the structural properties of such a cocrystal (Py- POR-COF) is discussed. Also, a structure-to-function relationship for this class of materials, governing their electrocatalytic activity for the oxygen reduction reaction in alkaline media, is reported.

Research Organization:
Univ. of Pennsylvania, Philadelphia, PA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Contributing Organization:
University of Nebraska, Colorado School of Mines, China Scholarship Council, Harbin Institute of Technology
Grant/Contract Number:
SC0019281
OSTI ID:
1658238
Journal Information:
Journal of the American Chemical Society, Vol. 141, Issue 50; ISSN 0002-7863
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English