Osama Shekhah

Tunable Rare Earth fcu-MOF Platform: Access to Adsorption Kinetics Driven Gas/Vapor Separations via Pore Size Contraction

Reticular chemistry approach was successfully employed to deliberately construct new rare-earth (RE, i.e., Eu(3+), Tb(3+), and Y(3+)) fcu metal-organic frameworks (MOFs) with restricted window apertures. Controlled and selective access to the resultant contracted fcu-MOF pores permits the achievement of the requisite sorbate cutoff, ideal for selective adsorption kinetics based separation and/or molecular sieving of gases and vapors. Predetermined reaction conditions that permitted the formation in situ of the 12-connected RE hexanuclear molecular building block (MBB) and the establishment of the first RE-fcu-MOF platform, especially in the presence of 2-fluorobenzoic acid (2-FBA) as a modulator and a structure directing agent, were used to synthesize isostructural RE-1,4-NDC-fcu-MOFs based on a relatively bulkier 2-connected bridging ligand, namely 1,4-naphthalenedicarboxylate (1,4-NDC). The subsequent RE-1,4-NDC-fcu-MOF structural features, contracted windows/pores and high concentration of open metal sites combined with exceptional hydrothermal and chemical stabilities, yielded notable gas/solvent separation properties, driven mostly by adsorption kinetics as exemplified in this work for n-butane/methane, butanol/methanol, and butanol/water pair systems.

The liquid phase epitaxy approach for the successful construction of ultra-thin and defect-free ZIF-8 membranes: pure and mixed gas transport study

The liquid-phase epitaxy (LPE) method was effectively implemented to deliberately grow/construct ultrathin (0.5-1 μm) continuous and defect-free ZIF-8 membranes. Permeation properties of different gas pair systems (O2-N2, H2-CO2, CO2-CH4, C3H6-C3H8, CH4-n-C4H10) were studied using the time lag technique.

A novel series of isoreticular metal organic frameworks: realizing metastable structures by liquid phase epitaxy

A novel class of metal organic frameworks (MOFs) has been synthesized from Cu-acetate and dicarboxylic acids using liquid phase epitaxy. The SURMOF-2 isoreticular series exhibits P4 symmetry, for the longest linker a channel-size of 3 × 3 nm2 is obtained, one of the largest values reported for any MOF so far. High quality, ab-initio electronic structure calculations confirm the stability of a regular packing of (Cu++)2- carboxylate paddle-wheel planes with P4 symmetry and reveal, that the SURMOF-2 structures are in fact metastable, with a fairly large activation barrier for the transition to the bulk MOF-2 structures exhibiting a lower, twofold (P2 or C2) symmetry. The theoretical calculations also allow identifying the mechanism for the low-temperature epitaxial growth process and to explain, why a synthesis of this highly interesting, new class of high-symmetry, metastable MOFs is not possible using the conventional solvothermal process.

Defects in MOFs: a thorough characterization.

As indicated by nearly perfect XRD data, but challenged by a two-signal IR spectrum of CO guest molecules, it is confirmed by computer simulations and XPS experiments that the most defect-free SURMOFs contain about 4% defective Cu sites.

Grafting of Monocarboxylic Substituted Polychlorotriphenylmethyl Radicals onto a COOH-Functionalized Self-Assembled Monolayer through Copper (II) Metal Ions

A monocarboxylic substituted polychlorotriphenylmethyl radical (PTMCOOH) has been grafted onto a COOH-functionalized SAM (mercaptohexadecanoic acid, MHDA SAM), using copper (II) metal ions as linkers between the carboxyl groups of the SAM and the ligand. The metal-radical adlayer has been characterized thoroughly using different surface analysis techniques, such as contact angle, IRRAS, XPS, SPR, ToF-SIMS, SFM, and NEXAFS. The magnetic character was confirmed by EPR. The density of unoccupied states was investigated using X-ray absorption spectroscopy. A low-energy peak in the NEXAFS spectrum directly revealed the presence of partially occupied electronic levels, thus proving the open-shell character of the grafted ligands. SEM measurements on a laterally patterned sample prepared by muCP of MHDA in a matrix of hexadecane thiolate (a CH 3-terminated SAM) was performed to demonstrate that the metal-assisted anchoring of the open-shell ligand occurs selectively on the COOH terminated SAM. These results represent an easy and new approach to anchor organic radicals on surfaces and constitute a first step toward the growth of magnetic metal-organic radical-based frameworks on solid substrates.

H2S Sensors: Fumarate‐Based fcu‐MOF Thin Film Grown on a Capacitive Interdigitated Electrode

Herein we report the fabrication of an advanced sensor for the detection of hydrogen sulfide (H2 S) at room temperature, using thin films of rare-earth metal (RE)-based metal-organic framework (MOF) with underlying fcu topology. This unique MOF-based sensor is made via the in situ growth of fumarate-based fcu-MOF (fum-fcu-MOF) thin film on a capacitive interdigitated electrode. The sensor showed a remarkable detection sensitivity for H2 S at concentrations down to 100 ppb, with the lower detection limit around 5 ppb. The fum-fcu-MOF sensor exhibits a highly desirable detection selectivity towards H2 S vs. CH4 , NO2 , H2 , and C7 H8 as well as an outstanding H2 S sensing stability as compared to other reported MOFs.

Ultrasound-assisted synthesis of mesoporous β-Ni(OH)2 and NiO nano-sheets using ionic liquids

Via a facile ultrasound synthesis from nickel acetate and sodium hydroxide with ionic liquids as the solvent and template it is possible to obtain nano-β-Ni(OH)2 of various dimensionalities depending on the reaction conditions with the ionic liquid (IL) being the most important factor. Scanning electron microscopy (SEM) imaging showed β-Ni(OH)2 to form as nanosheets, nanorods and nanospheres depending on the IL. ILs with strong to moderate hydrogen bonding capability like [C3mimOH][Tf2N] (1-(3-hydroxypropyl)-3-methylimidazolium bis(trifluoromethanesulfonylamide)), [C4mim][Tf2N] (1-butyl-3-methylimidazolium bis(trifluoromethanesulfonylamide)) and [Edimim][Tf2N] (1-ethyl-2,3-diemethylimidazolium bis(trifluoromethanesulfonylamide)) lead to the formation of nanosheets whilst [Py4][Tf2N] (butyl-pyridinium bis(trifluoromethanesulfonylamide)) leads to nanoparticles and [N1888][Tf2N] (methyltrioctylammonium bis(trifluoromethanesulfonylamide)) to nanorods. Subsequent calcination of the materials at elevated temperatures (285–425 °C) leads to the conversion of β-Ni(OH)2 to NiO under preservation of the nanostructure. Scanning electron microscopy (SEM), X-ray diffraction (XRD), TG-DTA, X-ray photoelectron spectroscopy (XPS), and energy dispersive X-ray spectroscopy (EDX) were used to observe the morphology, crystallinity, and chemical composition in more detail. Mesoporous NiO nanosheets obtained in [C4mim][Tf2N] possess an exceptionally high surface area of 141.28 m2 g−1 and a pore volume of 0.2 cm3 g−1 at 285 °C. As a result of calcination at 425 °C the surface area decreased to 92.84 m2 g−1, but the pore volume increased to 0.48 cm3 g−1. In addition, the product has an extraordinarily high saturation magnetization of 1.38 emu g−1, a coercivity of 117 Oe and an excellent specific capacitance of 199.4 F g−1 which renders the material highly interesting for application in supercapacitors.

Insights on Capacitive Interdigitated Electrodes Coated with MOF Thin Films: Humidity and VOCs Sensing as a Case Study

A prototypical metal-organic framework (MOF), a 2D periodic porous structure based on the assembly of copper ions and benzene dicarboxylate (bdc) ligands (Cu(bdc)·xH2O), was grown successfully as a thin film on interdigitated electrodes (IDEs). IDEs have been used for achieving planar CMOS-compatible low-cost capacitive sensing structures for the detection of humidity and volatile organic compounds (VOCs). Accordingly, the resultant IDEs coated with the Cu(bdc)·xH2O thin film was evaluated, for the first time, as a capacitive sensor for gas sensing applications. A fully automated setup, using LabVIEW interfaces to experiment conduction and data acquisition, was developed in order to measure the associated gas sensing performance.

Oriented Circular Dichroism Analysis of Chiral Surface‐Anchored Metal–Organic Frameworks Grown by Liquid‐Phase Epitaxy and upon Loading with Chiral Guest Compounds

Oriented circular dichroism (OCD) is explored and successfully applied to investigate chiral surface-anchored metal-organic frameworks (SURMOFs) based on camphoric acid (D- and Lcam) with the composition [Cu2(Dcam)(2x)(Lcam)(2-2x)(dabco)]n (dabco = 1,4-diazabicyclo-[2.2.2]-octane). The three-dimensional chiral SURMOFs with high-quality orientation were grown on quartz glass plates by using a layer-by-layer liquid-phase epitaxy method. The growth orientation, as determined by X-ray diffraction (XRD), could be switched between the [001] and [110] direction by using either OH- or COOH-terminated substrates. These SURMOFs were characterized by using OCD, which confirmed the ratio as well as the orientation of the enantiomeric linker molecules. Theoretical computations demonstrate that the OCD band intensities of the enantiopure [Cu2(Dcam)2(dabco)]n grown in different orientations are a direct result of the anisotropic nature of the chiral SURMOFs. Finally, the enantiopure [Cu2(Dcam)2(dabco)]n and [Cu2(Lcam)2(dabco)]n SURMOFs were loaded with the two chiral forms of ethyl lactate [(+)-ethyl-D-lactate and (-)-ethyl-L-lactate)]. An enantioselective enrichment of >60 % was observed by OCD when the chiral host scaffold was loaded from the racemic mixture.

Advanced Fabrication Method for the Preparation of MOF Thin Films: Liquid-Phase Epitaxy Approach Meets Spin Coating Method

Here, we report a new and advanced method for the fabrication of highly oriented/polycrystalline metal-organic framework (MOF) thin films. Building on the attractive features of the liquid-phase epitaxy (LPE) approach, a facile spin coating method was implemented to generate MOF thin films in a high-throughput fashion. Advantageously, this approach offers a great prospective to cost-effectively construct thin-films with a significantly shortened preparation time and a lessened chemicals and solvents consumption, as compared to the conventional LPE-process. Certainly, this new spin-coating approach has been implemented successfully to construct various MOF thin films, ranging in thickness from a few micrometers down to the nanometer scale, spanning 2-D and 3-D benchmark MOF materials including Cu2(bdc)2·xH2O, Zn2(bdc)2·xH2O, HKUST-1, and ZIF-8. This method was appraised and proved effective on a variety of substrates comprising functionalized gold, silicon, glass, porous stainless steel, and aluminum oxide. The facile, high-throughput and cost-effective nature of this approach, coupled with the successful thin film growth and substrate versatility, represents the next generation of methods for MOF thin film fabrication. Therefore, paving the way for these unique MOF materials to address a wide range of challenges in the areas of sensing devices and membrane technology.