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

Tavakoli, Elham; Kakekhani, Arvin; Kaviani, Shayan; Tan, Peng; Ghaleni, Mahdi Mohammadi; Zaeem, Mohsen Asle; Rappe, Andrew M.; Nejati, Siamak

doi:10.1021/jacs.9b10787

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

Full Record
Other Related Research

Abstract

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.

Authors:

^[1];

^[2];

^[1]; Tan, Peng ^[3];

^[1];

^[4];

^[2];

^[1]

University of Nebraska−Lincoln, NE (United States)
University of Pennsylvania, Philadelphia, PA (United States)
University of Pennsylvania, Philadelphia, PA (United States); Harbin Institute of Technology (China)
Colorado School of Mines, Golden, CO (United States)

Publication Date:: Wed Dec 04 00:00:00 EST 2019

Research Org.:: Univ. of Pennsylvania, Philadelphia, PA (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Contributing Org.:: University of Nebraska, Colorado School of Mines, China Scholarship Council, Harbin Institute of Technology

OSTI Identifier:: 1658238

Grant/Contract Number:: SC0019281

Resource Type:: Accepted Manuscript

Journal Name:: Journal of the American Chemical Society

Additional Journal Information:: Journal Volume: 141; Journal Issue: 50; Journal ID: ISSN 0002-7863

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 30 DIRECT ENERGY CONVERSION; Covalent organic framework (COF); electrochemical deposition; catalysis; nanoporous; catalyst synthesis; oxygen reduction reaction (ORR); redox reactions; pyridines; electrodes; dendrons

Citation Formats


                    Tavakoli, Elham, Kakekhani, Arvin, Kaviani, Shayan, Tan, Peng, Ghaleni, Mahdi Mohammadi, Zaeem, Mohsen Asle, Rappe, Andrew M., and Nejati, Siamak. In Situ Bottom-up Synthesis of Porphyrin-Based Covalent Organic Frameworks.  United States: N. p., 2019. 
Web.  doi:10.1021/jacs.9b10787.

Copy to clipboard


                    Tavakoli, Elham, Kakekhani, Arvin, Kaviani, Shayan, Tan, Peng, Ghaleni, Mahdi Mohammadi, Zaeem, Mohsen Asle, Rappe, Andrew M., & Nejati, Siamak. In Situ Bottom-up Synthesis of Porphyrin-Based Covalent Organic Frameworks.  United States.  https://doi.org/10.1021/jacs.9b10787

Copy to clipboard


                    Tavakoli, Elham, Kakekhani, Arvin, Kaviani, Shayan, Tan, Peng, Ghaleni, Mahdi Mohammadi, Zaeem, Mohsen Asle, Rappe, Andrew M., and Nejati, Siamak. Wed .  
"In Situ Bottom-up Synthesis of Porphyrin-Based Covalent Organic Frameworks".  United States.  https://doi.org/10.1021/jacs.9b10787.  https://www.osti.gov/servlets/purl/1658238.

Copy to clipboard


                    
@article{osti_1658238,

  title        = {In Situ Bottom-up Synthesis of Porphyrin-Based Covalent Organic Frameworks},

  author       = {Tavakoli, Elham and Kakekhani, Arvin and Kaviani, Shayan and Tan, Peng and Ghaleni, Mahdi Mohammadi and Zaeem, Mohsen Asle and Rappe, Andrew M. and Nejati, Siamak},

  abstractNote = {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.},

  doi          = {10.1021/jacs.9b10787},

  journal      = {Journal of the American Chemical Society},

  number       = 50,

  volume       = 141,

  place        = {United States},

  year         = {Wed Dec 04 00:00:00 EST 2019},

  month        = {Wed Dec 04 00:00:00 EST 2019}

}

Copy to clipboard

Journal Article:

Free Publicly Available Full Text

Accepted Manuscript (DOE)

Publisher's Version of Record

https://doi.org/10.1021/jacs.9b10787

Other availability

Search WorldCat to find libraries that may hold this journal

Citation Metrics:

Cited by: 35 works

Citation information provided by
Web of Science

Save / Share:

Export Metadata

Save to My Library

Similar Records in DOE PAGES and OSTI.GOV collections:

Covalent-Organic Frameworks Composed of Rhenium Bipyridine and Metal Porphyrins: Designing Heterobimetallic Frameworks with Two Distinct Metal Sites

Journal Article Johnson, Eric M. ; Haiges, Ralf ; Marinescu, Smaranda C. - ACS Applied Materials and Interfaces

The incorporation of homogeneous catalysts for CO₂ reduction into extended frameworks has been a successful strategy for increasing catalyst lifetime and activity, but the effects of the linkers on catalysis are underexplored. In this work, a novel rhenium bipyridine complex was synthesized for the purpose of designing a covalent-organic framework (COF) with both metalloporphyrin and metal bipyridine moieties. Investigation of the rhenium complex as a homogeneous catalyst shows a faradaic efficiency of 81(8)% for the electrocatalytic conversion of CO₂ to CO upon the addition of methanol as the proton source. Treatment of the rhenium complex with tetra(4-aminophenyl)porphyrin under Schiff basemore »« less
Cited by 80
https://doi.org/10.1021/acsami.8b07795

Full Text Available
Electronic, structural, and substrate effect properties of single-layer covalent organic frameworks

Journal Article Liang, Liangbo ; Zhu, Pan ; Meunier, Vincent ; ... - Journal of Chemical Physics

Recently synthesized two-dimensional covalent organic frameworks (COFs) exhibit high surface area, large pore size, and unique structural architectures, making them promising materials for various energy applications. Here, a total of nine COFs structures, including two deposited on a hexagonal boron nitride substrate, are investigated using density functional theory, quasi-particle many-body theory within the GW approximation, and an image charge model. The structures considered belong to two major families (thiophene-based COF-n (T-COF-n) and tetrakis (4-aminophenyl) porphyrin-x (TAPP-x)) differing from the presence of B—O or C=N linkers. While T-COF-n structures are shown to constitute planar networks, TAPP-x systems can display non-negligible corrugationmore »« less
https://doi.org/10.1063/1.4919682
3D Covalent Organic Frameworks Selectively Crystallized through Conformational Design

Journal Article Nguyen, Ha L. ; Gropp, Cornelius ; Ma, Yanhang ; ... - Journal of the American Chemical Society

In this work, we present a strategy whereby selective formation of imine covalent organic frameworks (COFs) based on linking of triangles and squares into the fjh topology was achieved by the conformational design of the building units. 1,3,5-Trimethyl-2,4,6-tris(4-formylphenyl)benzene (TTFB, triangle) and 1,1,2,2-tetrakis(4-aminophenyl)ethene (ETTA, square) were reticulated into [(TTFB)₄(ETTA)₃]_imine, termed COF-790, which was fully characterized by spectroscopic, microscopic, and X-ray diffraction techniques. COF-790 exhibits permanent porosity and a Brunauer-Emmett-Teller (BET) surface area of 2650 m² g^-1. Key to the formation of this COF in crystalline form is the pre-designed conformation of the triangle and the square units to give dihedral anglesmore »« less
https://doi.org/10.1021/jacs.0c11064

Full Text Available
Reticular Electronic Tuning of Porphyrin Active Sites in Covalent Organic Frameworks for Electrocatalytic Carbon Dioxide Reduction

Journal Article Diercks, Christian S. ; Lin, Song ; Kornienko, Nikolay ; ... - Journal of the American Chemical Society

Here, the electronic character of porphyrin active sites for electrocatalytic reduction of CO₂ to CO in a two-dimensional covalent organic framework (COF) was tuned by modification of the reticular structure. Efficient charge transport along the COF backbone promotes electronic connectivity between remote functional groups and the active sites and enables the modulation of the catalytic properties of the system. A series of oriented thin films of these COFs was found to reduce CO₂ to CO at low overpotential (550 mV) with high selectivity (faradaic efficiency of 87%) and at high current densities (65 mA/mg), a performance well beyond related molecularmore »« less
Cited by 348
https://doi.org/10.1021/jacs.7b11940

Full Text Available
Catalytic Porphyrin Framework Compounds

Journal Article Feng, Liang ; Wang, Kun-Yu ; Joseph, Elizabeth ; ... - Trends in Chemistry

Porphyrins are frequently observed in nature and play a vital role in many biological functions, including light-harvesting, oxygen transport, and catalytic transformations. The rigid, robust, and multifunctional features of porphyrins enable the construction of framework compounds such as metal–organic frameworks (MOFs) and covalent organic frameworks (COFs) for use in several important applications. This short review here summarizes the types of porphyrin building blocks with varying connectivity, their assembly into framework compounds, and key structural factors governing porphyrin ligand design. Furthermore, we highlight emerging catalytic applications of these porphyrin framework compounds as Lewis acid catalysts, oxidation catalysts, photocatalysts, and electrocatalysts. Together,more »« less
https://doi.org/10.1016/j.trechm.2020.01.003

Full Text Available

Similar Records