A5043133065- Metal-Organic Frameworks: Synthesis and Applications
- X-ray Diffraction in Crystallography
- Crystallization and Solubility Studies
- Magnetism in coordination complexes
- Nanomaterials for catalytic reactions
- Catalytic Processes in Materials Science
- Covalent Organic Framework Applications
- Machine Learning in Materials Science
- Nanocluster Synthesis and Applications
- Metal complexes synthesis and properties
- Asymmetric Hydrogenation and Catalysis
- Boron Compounds in Chemistry
- Polyoxometalates: Synthesis and Applications
- Membrane Separation and Gas Transport
- Lanthanide and Transition Metal Complexes
- MXene and MAX Phase Materials
- Electrocatalysts for Energy Conversion
- Organometallic Complex Synthesis and Catalysis
- Crystallography and molecular interactions
- Gold and Silver Nanoparticles Synthesis and Applications
- Carbon dioxide utilization in catalysis
- Fuel Cells and Related Materials
- Advanced Nanomaterials in Catalysis
- Surface Chemistry and Catalysis
- Dendrimers and Hyperbranched Polymers
University of Wisconsin–Stevens Point
2015-2023
Northwestern University
2012-2020
Colorado State University
2008-2018
Northwest University
2014-2015
University of Wisconsin–Madison
2014
Yeshiva University
2010
University of California, Berkeley
2008
Metal–organic frameworks (MOFs) have received attention for a myriad of potential applications including catalysis, gas storage, and separation. Coordinatively unsaturated metal ions often enable key functional behavior these materials. Most commonly, MOFs been metalated from the condensed phase (i.e., solution). Here we introduce new synthetic strategy capable metallating phase: atomic layer deposition (ALD). Key to enabling metalation by ALD In (AIM) was synthesis NU-1000, new, thermally...
A new functionalization technique, solvent-assisted ligand incorporation (SALI), was developed to efficiently incorporate carboxylate-based functionalities in the Zr-based metal-organic framework, NU-1000. Unlike previous metal node strategies, which utilize dative bonding coordinatively unsaturated sites, SALI introduces functional groups as charge compensating and strongly bound moieties Zr6 node. Utilizing SALI, we have attached perfluoroalkane carboxylates of various chain lengths...
Abstract Inspired by biology, in which a bimetallic hydroxide‐bridged zinc(II)‐containing enzyme is utilized to catalytically hydrolyze phosphate ester bonds, the utility of zirconium(IV)‐cluster‐containing metal–organic framework as catalyst for methanolysis and hydrolysis phosphate‐based nerve agent simulants was examined. The combination strong Lewis‐acidic Zr IV bridging hydroxide anions led ultrafast half‐lives these solvolysis reactions. This especially remarkable considering that...
Metal-organic frameworks (MOFs) have gained considerable attention as hybrid materials-in part because of a multitude potential useful applications, ranging from gas separation to catalysis and light harvesting. Unfortunately, de novo synthesis MOFs with desirable function-property combinations is not always reliable may suffer vagaries such formation undesirable topologies, low solubility precursors, loss functionality the sensitive network components. The recently discovered synthetic...
An isoreticular series of metal–organic frameworks (MOFs) with the ftw topology based on zirconium oxoclusters and tetracarboxylate linkers a planar core (NU-1101 through NU-1104) has been synthesized employing linker expansion approach. In this series, NU-1103 pore volume 2.91 cc g–1 geometrically calculated surface area 5646 m2 g–1, which is highest value reported to date for zirconium-based MOF among largest that have any porous material. Successful activation MOFs was proven agreement...
Metal–organic frameworks (MOFs) built up from Zr6-based nodes and multi-topic carboxylate linkers have attracted attention due to their favourable thermal chemical stability. However, the hydrolytic stability of some these MOFs has recently been questioned. Herein we demonstrate that two frameworks, namely UiO-67 NU-1000, are stable towards linker hydrolysis in H2O, but collapse during activation H2O. Importantly, this framework can be overcome by utilizing solvent-exchange solvents...
Using the enzymatic mechanism of phosphoesterase as a template, we were able to modify metal–organic framework such that hydrolysis rates 50 times faster than previously demonstrated with UiO-66.
Crystalline metal–organic frameworks (MOFs) have emerged as a highly desirable class of solid-state materials. Some their most attractive features include exceptionally high porosities well surface areas. A key aspect to the realization porosity is removal guest molecules from framework while still maintaining its structural integrity (i.e., “activation”). This contribution highlights strategies utilized date for activating MOFs, including: (i) conventional heating and vacuum; (ii)...
Abstract The availability of efficient hydrogen evolution reaction (HER) catalysts is high importance for solar fuel technologies aimed at reducing future carbon emissions. Even though Pt electrodes are excellent HER electrocatalysts, commercialization large-scale production technology requires finding an equally efficient, low-cost, earth-abundant alternative. Here, porosity, metal-organic framework (MOF) films have been used as scaffolds the deposition a Ni-S electrocatalyst. Compared with...
A uniform and crack-free metal–organic framework (MOF) thin film composed of free-standing acicular nanorods was grown on a transparent conducting glass substrate. The MOF exhibits electrochromic switching between yellow deep blue by means one-electron redox reaction at its pyrene-based linkers. rigid stabilizes the radical cations pyrene linkers positive applied potential, resulting in reversible color change film. regular channels allow ions to migrate through entire thus remarkable rapid rate.
Metal-organic frameworks (MOFs) constructed from Zr6-based nodes have recently received considerable attention given their exceptional thermal, chemical, and mechanical stability. Because of this, the structural diversity MOFs has expanded considerably in turn rise to difficulty precise characterization. In particular it been difficult assign where protons (needed for charge balance) reside on some nodes. Elucidating proton topologies will wide ranging implications defining chemical...
A metal–organic framework (MOF) with high volumetric deliverable capacity for methane was synthesized after being identified by computational screening of 204 hypothetical MOF structures featuring (Zr6O4)(OH)4(CO2)n inorganic building blocks. The predicted (NU-800) has an fcu topology in which zirconium nodes are connected via ditopic 1,4-benzenedipropynoic acid linkers. Based on our computer simulations, alkyne groups adjacent to the provide more efficient packing around at pressures. gas...
We designed, synthesized, and characterized a new Zr-based metal-organic framework material, NU-1100, with pore volume of 1.53 ccg(-1) Brunauer-Emmett-Teller (BET) surface area 4020 m(2) g(-1) ; to our knowledge, currently the highest published for MOFs. CH4 /CO2 /H2 adsorption isotherms were obtained over broad range pressures temperatures are in excellent agreement computational predictions. The total hydrogen at 65 bar 77 K is 0.092 g , which corresponds 43 L(-1) . volumetric gravimetric...
Thin films of the metal-organic framework (MOF) NU-1000 were grown on conducting glass substrates. The uniformly cover substrates and are composed free-standing sub-micrometer rods. Subsequently, atomic layer deposition (ALD) was utilized to deposit Co(2+) ions throughout entire MOF film via self-limiting surface-mediated reaction chemistry. Co bind at aqua hydroxo sites lining channels NU-1000, resulting in three-dimensional arrays separated thin film. Co-modified demonstrate promising...
The nerve agent VX is among the most toxic chemicals known to mankind, and robust solutions are needed rapidly selectively deactivate it. Herein, we demonstrate that three Zr6-based metal–organic frameworks (MOFs), namely, UiO-67, UiO-67-NH2, UiO-67-N(Me)2, selective highly active catalysts for hydrolysis of VX. Utilizing UiO-67-N(Me)2 in a pH 10 buffered solution N-ethylmorpholine, P–S bond was observed. In addition, found catalyze with an initial half-life 1.8 min. This nearly 3 orders...
A Cu–carborane-based metal–organic framework (MOF), NU-135, which contains a quasi-spherical para-carborane moiety, has been synthesized and characterized. NU-135 exhibits pore volume of 1.02 cm3/g gravimetric BET surface area ca. 2600 m2/g, thus represents the first highly porous carborane-based MOF. As consequence unique geometry carborane unit, very high volumetric 1900 m2/cm3. CH4, CO2, H2 adsorption isotherms were measured over broad range pressures temperatures are in good agreement...
Abstract Inspired by biology, in which a bimetallic hydroxide‐bridged zinc(II)‐containing enzyme is utilized to catalytically hydrolyze phosphate ester bonds, the utility of zirconium(IV)‐cluster‐containing metal–organic framework as catalyst for methanolysis and hydrolysis phosphate‐based nerve agent simulants was examined. The combination strong Lewis‐acidic Zr IV bridging hydroxide anions led ultrafast half‐lives these solvolysis reactions. This especially remarkable considering that...
The rapid destruction of chemical threats, such as phosphate-based nerve agents, is considerable current interest. hydrolysis the nerve-agent simulant methylparaoxon, catalyzed by UiO-66 and UiO-67, was examined a function pH. Surprisingly, even though typical phosphate–ester mechanisms entail nucleophilic attack aqueous hydroxide, rate accelerates solution pH lowered. unexpected behavior attributed to pH-dependent composition change followed ligand substitution at Zr6-based node.
Detachment (desorption) of molecular dyes from photoelectrodes is one the major limitations for long-term operation dye-sensitized solar cells. Here we demonstrate a method to greatly inhibit this loss by growing transparent metal oxide (TiO2) on dye-coated photoelectrode via atomic layer deposition (ALD). TiO2-enshrouded sensitizers largely resist detachment, even in pH 10.7 ethanol, standard solution intentional removal photoelectrodes. Additionally, ALD post-treatment renders otherwise...
Methyl-, hydroxymethyl-, and phthalimidomethyl-functionalized versions of the porous organic polymer PAF-1 have been obtained through de novo synthesis. The CO2 adsorption capacity PAF-1–CH2NH2, post-synthesis deprotection PAF-1–CH2–phthalimide, has shown to exceed that PAF-1.