title: Synthesis and characterization of functionalized metal-organic frameworks.
abstract: Metal-organic frameworks have attracted extraordinary amounts of research attention, as they are attractive candidates for numerous industrial and technological applications. Their signature property is their ultrahigh porosity, which however imparts a series of challenges when it comes to both constructing them and working with them. Securing desired MOF chemical and physical functionality by linker/node assembly into a highly porous framework of choice can pose difficulties, as less porous and more thermodynamically stable congeners (e.g., other crystalline polymorphs, catenated analogues) are often preferentially obtained by conventional synthesis methods. Once the desired product is obtained, its characterization often requires specialized techniques that address complications potentially arising from, for example, guest-molecule loss or preferential orientation of microcrystallites. Finally, accessing the large voids inside the MOFs for use in applications that involve gases can be problematic, as frameworks may be subject to collapse during removal of solvent molecules (remnants of solvothermal synthesis). In this paper, we describe synthesis and characterization methods routinely utilized in our lab either to solve or circumvent these issues. The methods include solvent-assisted linker exchange, powder X-ray diffraction in capillaries, and materials activation (cavity evacuation) by supercritical CO2 drying. Finally, we provide a protocol for determining a suitable pressure region for applying the Brunauer-Emmett-Teller analysis to nitrogen isotherms, so as to estimate surface area of MOFs with good accuracy.
authors.affiliation: Department of Chemistry, Northwestern University.
authors.forename: Olga
authors.initials: O
authors.lastname: Karagiaridi
authors.affiliation: Department of Chemistry, Northwestern University; Department of Chemistry, Warsaw University of Technology.
authors.forename: Wojciech
authors.initials: W
authors.lastname: Bury
authors.affiliation: Department of Chemistry, Northwestern University.
authors.forename: Amy A
authors.initials: AA
authors.lastname: Sarjeant
authors.affiliation: Department of Chemistry, Northwestern University.
authors.forename: Joseph T
authors.initials: JT
authors.lastname: Hupp
authors.affiliation: Department of Chemistry, Northwestern University; Department of Chemistry, Faculty of Science, King Abdulaziz University; o-farha@northwestern.edu.
authors.forename: Omar K
authors.initials: OK
authors.lastname: Farha
mesh_terms: D056831:Coordination Complexes / Q000138:chemical synthesis / Q000737:chemistry*; D003460:Crystallization; D007094:Imides / Q000737:chemistry; D009566:Nitrates / Q000737:chemistry; D011725:Pyridines / Q000737:chemistry; D014961:X-Ray Diffraction; D017967:Zinc Compounds / Q000737:chemistry
chemical_list: D056831:Coordination Complexes; D007094:Imides; D009566:Nitrates; D011725:Pyridines; D017967:Zinc Compounds; C042103:zinc nitrate