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| Covalent organic framework | |
|---|---|
| Name | Covalent organic framework |
| Other names | COF |
| Type | Organic crystalline polymer |
| First reported | 2005 |
| Pioneers | Omar M. Yaghi, Michael J. Smith |
Covalent organic framework
Covalent organic frameworks are crystalline, porous polymers built from organic monomers linked by strong covalent bonds, developed in the early 21st century and spearheaded by laboratories such as University of California, Berkeley groups. They occupy a position among advanced porous materials alongside Zeolite, Metal–organic framework, Activated carbon, and Mesoporous silica. Researchers from institutions including Massachusetts Institute of Technology, Harvard University, California Institute of Technology, Princeton University, University of California, Los Angeles and industrial labs at BASF, Dow Chemical Company, DuPont have advanced COF chemistry through collaborations and conferences such as the American Chemical Society meetings and the International Conference on Porous Organic Polymers.
Covalent organic frameworks emerged from work in reticular chemistry and crystallography, influenced by figures like Omar M. Yaghi and concepts developed at ETH Zurich and University of California, Berkeley. Early demonstrations paralleled developments in Metal–organic framework research and drew attention from journals such as Nature, Science, Journal of the American Chemical Society and Angewandte Chemie. Funding and recognition came from agencies and prizes including the National Science Foundation, European Research Council, Royal Society, Davy Medal, and conferences at Brookhaven National Laboratory and Lawrence Berkeley National Laboratory.
COFs are synthesized by connecting organic building blocks—often heteroaromatic or polyfunctional molecules—through reactions such as imine condensation, boronate ester formation, triazine linking, and olefin metathesis. Key synthetic strategies were developed in labs at University of California, Berkeley, University of Cambridge, University of Oxford, Tohoku University, Riken, and University of Tokyo. Representative monomers include derivatives of Benzene, Pyrene, Porphyrin, Phthalocyanine, Triphenylene, and Tetrakis(4-aminophenyl)methane; polymerization conditions often reference protocols from groups at ETH Zurich, Massachusetts Institute of Technology, and National Institute of Standards and Technology. Techniques such as solvothermal synthesis, mechanochemical methods popularized by researchers at University of Manchester, and interfacial polymerization used by teams at Columbia University enable control over layer stacking, pore size, and crystallinity. Collaborations with companies like Sigma-Aldrich and instrumentation centers at Argonne National Laboratory have standardized reagents and reactors.
COFs exhibit high surface areas, tunable pore sizes, low densities, and thermal stability, making them comparable to Zeolites and Metal–organic frameworks characterized by groups at Pacific Northwest National Laboratory and Oak Ridge National Laboratory. Electronic properties—semiconducting behavior, charge mobility, and light absorption—have been modulated using building blocks inspired by Tetrathiafulvalene, Perylene, Anthracene, Carbazole, and Triphenylamine motifs studied at Stanford University and Yale University. Chemical stability against moisture and acids has been improved through design principles from University of Illinois Urbana-Champaign and University of Texas at Austin. Mechanical properties and thin-film formation have been investigated at Max Planck Institute for Polymer Research, Rensselaer Polytechnic Institute, and Pennsylvania State University.
Crystallographic and spectroscopic characterization draws on methods from Brookhaven National Laboratory, Lawrence Berkeley National Laboratory, European Synchrotron Radiation Facility, and Diamond Light Source. Powder X-ray diffraction, single-crystal X-ray diffraction when available, solid-state nuclear magnetic resonance developed at Bruker collaborations, transmission electron microscopy used at Harvard University, scanning electron microscopy at IBM Research, and gas adsorption analysis following standards from International Union of Pure and Applied Chemistry are routine. Complementary techniques include Fourier-transform infrared spectroscopy from Shimadzu labs, thermogravimetric analysis at PerkinElmer facilities, X-ray photoelectron spectroscopy pioneered at Bell Labs, ultraviolet–visible spectroscopy at Royal Institution collaborations, and computational modelling at Argonne Leadership Computing Facility and Oak Ridge Leadership Computing Facility.
Proposed and demonstrated applications span gas storage and separation (CO2 capture, H2 storage) pursued by Air Products and Chemicals, Inc., TotalEnergies, U.S. Department of Energy, and academic groups at Imperial College London and University of California, Santa Barbara. Catalysis employing embedded metal centers relates to work at Max Planck Institute for Coal Research and Scripps Research, while optoelectronic and photovoltaic uses intersect with research at Bell Labs, NREL, University of Cambridge, and EPFL. Sensing applications tie to projects at Siemens, NEC Corporation, Toshiba, and medical diagnostics collaborations at Mayo Clinic and Johns Hopkins University. Membrane separations, heterogeneous catalysis, and drug delivery studies involve partnerships with Pfizer, Roche, GlaxoSmithKline, and materials consortia at National Institute for Materials Science.
Reproducible synthesis and scaling have posed challenges encountered by industrial partners like BASF and DuPont and discussed at World Economic Forum technology panels. Stability under ambient conditions, defect control, integration into devices, and limited single-crystal availability remain obstacles noted by researchers at MIT, Harvard Medical School, and Columbia University. Standardization for commercialization requires engagement with agencies such as U.S. Environmental Protection Agency and European Chemicals Agency and coordination across consortia including Advanced Research Projects Agency-Energy and national laboratories.
Future research will likely deepen connections with quantum materials studies at CERN-linked institutes, scalable manufacturing initiatives led by DARPA and Department of Defense, and translational efforts by startups incubated in Silicon Valley and Cambridge, UK. Integrating COFs with two-dimensional materials explored at National Graphene Institute and coupling to biological systems investigated at National Institutes of Health offer multidisciplinary pathways. Funding and recognition from bodies such as Wellcome Trust, Bill & Melinda Gates Foundation, Japan Society for the Promotion of Science, and awards like the Wolf Prize in Chemistry will shape trajectories. Continued cross-institutional work among universities, national labs, and industry—examples include collaborations between Lawrence Livermore National Laboratory and Stanford University—will determine which applications mature into commercial technologies.
Category:Porous materials