title: Facile Conversion of Hydroxy Double Salts to Metal-Organic Frameworks Using Metal Oxide Particles and Atomic Layer Deposition Thin-Film Templates.
abstract: Rapid room-temperature synthesis of metal-organic frameworks (MOFs) is highly desired for industrial implementation and commercialization. Here we find that a (Zn,Cu) hydroxy double salt (HDS) intermediate formed in situ from ZnO particles or thin films enables rapid growth (<1 min) of HKUST-1 (Cu3(BTC)2) at room temperature. The space-time-yield reaches >3 × 10(4) kg·m(-3)·d(-1), at least 1 order of magnitude greater than any prior report. The high anion exchange rate of (Zn,Cu) hydroxy nitrate HDS drives the ultrafast MOF formation. Similarly, we obtained Cu-BDC, ZIF-8, and IRMOF-3 structures from HDSs, demonstrating synthetic generality. Using ZnO thin films deposited via atomic layer deposition, MOF patterns are obtained on pre-patterned surfaces, and dense HKUST-1 coatings are grown onto various form factors, including polymer spheres, silicon wafers, and fibers. Breakthrough tests show that the MOF-functionalized fibers have high adsorption capacity for toxic gases. This rapid synthesis route is also promising for new MOF-based composite materials and applications.
authors.affiliation: Department of Chemical and Biomolecular Engineering, North Carolina State University , Raleigh, North Carolina 27695, United States.
authors.forename: Junjie
authors.initials: J
authors.lastname: Zhao
authors.affiliation: Department of Chemical and Biomolecular Engineering, North Carolina State University , Raleigh, North Carolina 27695, United States.
authors.forename: William T
authors.initials: WT
authors.lastname: Nunn
authors.affiliation: Department of Chemical and Biomolecular Engineering, North Carolina State University , Raleigh, North Carolina 27695, United States.
authors.forename: Paul C
authors.initials: PC
authors.lastname: Lemaire
authors.affiliation: Department of Chemical and Biomolecular Engineering, North Carolina State University , Raleigh, North Carolina 27695, United States.
authors.forename: Yiliang
authors.initials: Y
authors.lastname: Lin
authors.affiliation: Department of Chemical and Biomolecular Engineering, North Carolina State University , Raleigh, North Carolina 27695, United States.
authors.forename: Michael D
authors.initials: MD
authors.lastname: Dickey
authors.affiliation: Department of Chemical and Biomolecular Engineering, North Carolina State University , Raleigh, North Carolina 27695, United States.
authors.forename: Christopher J
authors.initials: CJ
authors.lastname: Oldham
authors.affiliation: RTI International , Research Triangle Park, North Carolina 27709, United States.
authors.forename: Howard J
authors.initials: HJ
authors.lastname: Walls
authors.affiliation: Edgewood Chemical Biological Center , Aberdeen Proving Ground, Maryland 21010, United States.
authors.forename: Gregory W
authors.initials: GW
authors.lastname: Peterson
authors.affiliation: School of Materials Science and Engineering, Georgia Institute of Technology , Atlanta, Georgia 30332, United States.
authors.forename: Mark D
authors.initials: MD
authors.lastname: Losego
authors.affiliation: Department of Chemical and Biomolecular Engineering, North Carolina State University , Raleigh, North Carolina 27695, United States.
authors.forename: Gregory N
authors.initials: GN
authors.lastname: Parsons