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1.
Sci Rep ; 13(1): 4530, 2023 Mar 20.
Article in English | MEDLINE | ID: mdl-36941330

ABSTRACT

The effective removal and displacement of fluids is important in many industrial and environmental applications, such as for operation and cleaning of process equipment, fluid injection in porous media for oil recovery or aquifer remediation, or for achieving subsurface zonal isolation in new or abandoned wells. The accurate measurement of the residual fluid wall film left behind after displacement by a cleaning fluid is a long-standing challenge, particularly so for very thin fluid films where the thickness can be of the order of micrometer. We focus on the characterization of oil films left on the wall of a horizontal pipe after the pipe has been displaced by water, and develop a novel, non-intrusive analytical technique that allows the use of relevant pipe materials. The oil that originally occupies the pipe is stained by a hydrophobic dye Nile red, and an intermediate organic solvent is used to collect the residual oil volume that remains after displacing the pipe with a known volume of water. Finally, ultraviolet-visible spectroscopy is used to measure the Nile red concentration in the collected fluid, which is proportional to the residual volume of oil in the pipe. We demonstrate the methodology by conducting experiments where the displacing fluid is injected at two different imposed velocities, and where the injected fluid volume is varied. As expected, we find a gradual thinning of the oil film with increasing injected fluid volume. We compare the measured film thicknesses to a displacement model based on the steady velocity profile in a pipe, and find that experiments consistently produce smaller film thicknesses. This developed technique allows quantification of displacement and cleaning mechanisms involved in immiscible displacements at laminar, transitional and turbulent regimes, for different non-Newtonian fluid pairs, and for different realistic pipe materials and surface roughnesses.

2.
Glob Chall ; 5(12): 2100001, 2021 Dec.
Article in English | MEDLINE | ID: mdl-34938573

ABSTRACT

Metal-organic frameworks (MOFs) are a class of porous organic-inorganic solids extensively explored for numerous applications owing to their catalytic activity and high surface area. In this work MOF thin films deposited in a one-step, molecular layer deposition (MLD), an all-gas-phase process, on glass wool fibers are characterized by X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, and their capabilities towards toxic industrial chemical (TIC) capture and chemical warfare agents (CWA) degradation are investigated. It is shown that despite low volume of the active material used, MOFs thin films are capable of removal of harmful gaseous chemicals from air stream and CWA from neutral aqueous environment. The results confirm that the MLD-deposited MOF thin films, amorphous and crystalline, are suitable materials for use in air filtration, decontamination, and physical protection against CWA and TIC.

3.
Chem Sci ; 10(12): 3616-3622, 2019 Mar 28.
Article in English | MEDLINE | ID: mdl-30996954

ABSTRACT

C-H activation reactions are generally associated with relatively low turnover numbers (TONs) and high catalyst concentrations due to a combination of low catalyst stability and activity, highlighting the need for recyclable heterogeneous catalysts with stable single-atom active sites. In this work, several palladium loaded metal-organic frameworks (MOFs) were tested as single-site catalysts for the oxidative coupling of arenes (e.g. o-xylene) via C-H/C-H activation. Isolation of the palladium active sites on the MOF supports reduced Pd(0) aggregate formation and thus catalyst deactivation, resulting in higher turnover numbers (TONs) compared to the homogeneous benchmark reaction. Notably, a threefold higher TON could be achieved for palladium loaded MOF-808 due to increased catalyst stability and the heterogeneous catalyst could efficiently be reused, resulting in a cumulative TON of 1218 after three runs. Additionally, the palladium single-atom active sites on MOF-808 were successfully identified by Fourier transform infrared (FTIR) and extended X-ray absorption fine structure (EXAFS) spectroscopy.

4.
Inorg Chem ; 58(2): 1607-1620, 2019 Jan 22.
Article in English | MEDLINE | ID: mdl-30624909

ABSTRACT

We describe the synthesis and corresponding full characterization of the set of UiO-66 metal-organic frameworks (MOFs) with 1,4-benzenedicarboxylate (C6H4(COOH)2, hereafter H2BDC) and 1,4-naphthalenedicarboxylate (C10H6(COOH)2, hereafter H2NDC) mixed linkers with NDC contents of 0, 25, 50, and 100%. Their structural (powder X-ray diffraction, PXRD), adsorptive (N2, H2, and CO2), vibrational (IR/Raman), and thermal stability (thermogravimetric analysis, TGA) properties quantitatively correlate with the NDC content in the material. The UiO-66 phase topology is conserved at all relative fractions of BDC/NDC. The comparison between the synchrotron radiation PXRD and 77 K N2-adsorption isotherms obtained on the 50:50 BDC/NDC sample and on a mechanical mixture of the pure BDC and NDC samples univocally proves that in the mixed linkers of the MOFs the BDC and NDC linkers are shared in each MOF crystal, discarding the hypothesis of two independent phases, where each crystal contains only BDC or NDC linkers. The careful tuning of the NDC content opens a way for controlled alteration of the sorption properties of the resulting material as testified by the H2-adsorption experiments, showing that the relative ranking of the materials in H2 adsorption is different in different equilibrium-pressure ranges: at low pressures, 100NDC is the most efficient sample, while with increasing pressure, its relative performance progressively declines; at high pressures, the ranking follows the BDC content, reflecting the larger internal pore volume available in the MOFs with a higher fraction of smaller linkers. The H2-adsorption isotherms normalized by the sample Brunauer-Emmett-Teller specific surface area show, in the whole pressure range, that the surface-area-specific H2-adsorption capabilities in UiO-66 MOFs increase progressively with increasing NDC content. Density functional theory calculations, using the hybrid B3LYP exchange correlation functional and quadruple-ζ with four polarization functions (QZ4P) basis set, show that the interaction of H2 with the H2NDC linker results in an adsorption energy larger by about 15% with respect to that calculated for adsorption on the H2BDC linker.

5.
Inorg Chem ; 53(18): 9509-15, 2014 Sep 15.
Article in English | MEDLINE | ID: mdl-25148242

ABSTRACT

A series of amine-functionalized mixed-linker metal-organic frameworks (MOFs) of idealized structural formula Zr6O4(OH)4(BDC)(6-6X)(ABDC)6X (where BDC = benzene-1,4-dicarboxylic acid, ABDC = 2-aminobenzene-1,4-dicarboxylic acid) has been prepared by solvothermal synthesis. The materials have been characterized by thermogravimetric analysis (TGA), powder X-ray diffraction (PXRD), and Fourier transform infrared (FTIR) spectroscopy with the aim of elucidating the effect that varying the degrees of amine functionalization has on the stability (thermal and chemical) and porosity of the framework. This work includes the first application of ultraviolet-visible light (UV-vis) spectroscopy in the quantification of ABDC in mixed-linker MOFs.

6.
Dalton Trans ; 42(35): 12586-95, 2013 Sep 21.
Article in English | MEDLINE | ID: mdl-23861014

ABSTRACT

Systematic studies of H2 adsorption by variable temperature infrared (VTIR) spectroscopy have added value in the characterization of hydrogen storage materials. As a key study to describe the potential of the method, here we report VTIR spectroscopy results of H2 adsorption at isostructural MOFs CPO-27-M (M = Mg, Mn, Co, Ni, Zn). The strongest perturbation of H2 vibrational frequency is due to the interaction with an open metal site. Although ionic radius is an empirical value, the direct correlation between ionic radii of the metal cation and H2 interaction energy is found in MOFs of the same topology. The highest enthalpy of hydrogen adsorption 15 ± 1 kJ mol(-1) was found for Ni(2+). VTIR results of H2 adsorption at isostructural MOFs CPO-27-M (M = Mg, Mn, Co, Ni, Zn) were compared with data obtained from analogous studies performed on a large variety of microporous materials (MOFs and zeolites), underlining the relevance of the approach to get reliable energetic and entropic (ΔH(0) and ΔS(0)) values to be compared with computational data and isosteric heats.

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