Correlation of Gas Permeability in a Metal-Organic Framework MIL-101(Cr)-Polysulfone Mixed-Matrix Membrane with Free Volume Measurements by Positron Annihilation Lifetime Spectroscopy (PALS).
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ABSTRACT:
SUBMITTER: Jeazet HB
PROVIDER: S-EPMC4021949 | biostudies-literature |
REPOSITORIES: biostudies-literature
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Project description:Positron annihilation lifetime spectroscopy (PALS) provides a powerful technique for non-destructive microstructure investigations in a broad field of material classes such as metals, semiconductors, polymers or porous glasses. Even though this method is well established for more than five decades, no proper standardization for the used setup configuration and subsequent data processing exists. Eventually, this could lead to an insufficiency of data reproducibility and avoidable deviations. Here we present experimentally obtained and simulated data of positron lifetime spectra at various statistics measured on pure tin (4N-Sn) by using a semi-analog/digital setup, where the digital section consists of the DRS4 evaluation board, "Design and performance of the 6?GHz waveform digitizing chip DRS4" [1]. The analog section consists of nuclear instrument modules (NIM), which externally trigger the DRS4 evaluation board to reduce the digitization and, thus, increase the acquisition efficiency. For the experimentally obtained lifetime spectra, 22Na sealed in Kapton foil served as a positron source, whereas 60Co was used for the acquisition of the prompt spectrum, i.e. the quasi instrument response function. Both types of measurements were carried out under the same conditions. All necessary data and information regarding the data acquisition and data reduction are provided to allow reproducibility by other research groups.
| S-EPMC6293023 | biostudies-literature
Project description:In this study, hybrids of nanoporous MIL-101(Cr) and MIL-53(Al) were synthesized using a hydrothermal method for various time periods, ranging from 8 to 40 h. The prepared materials were characterized by powder X-ray diffraction (PXRD) and elemental analysis, and their specific surface areas were measured by N2 sorption at 77 K using the Brunauer-Emmett-Teller (BET) method. To investigate the practical application of these materials, the pure carbon dioxide and methane adsorption capacities of the samples were determined using the volumetric method. The Langmuir model was used to fit the CO2 and CH4 isotherms. Extended Langmuir (EL) equations and the ideal adsorbed solution theory (IAST) models were used to obtain the CO2/CH4 selectivity. The sample with the highest BET specific surface area was selected as a candidate for further investigations. The thermal stability of the selected sample was investigated by thermogravimetric analysis (TGA). Scanning electron microscopy (SEM) was used to characterize the sample morphology. XRD results showed that the sample synthesized over the shortest time corresponded to MIL-101(Cr), while the sample synthesized over the longest time was in agreement with MIL-53(Al). Samples synthesized for time periods between these two limits were assumed to be composites of both MIL-53(Al) and MIL-101(Cr). TGA results indicated that the hybrid materials were thermally stable at temperatures about 100 °C higher than for pure MIL-101(Cr). The BET specific surface area (1746 m2 g-1) and CO2 adsorption capacity (16 mmol g-1) of the selected hybrid sample were about 50% and 35% higher, respectively, compared with those of pure MIL-53(Al), but 30% and 20% lower, respectively, compared with those of pure MIL-101(Cr). Binary adsorption modeling showed the high selectivity of the MIL-101(Cr) and MIL-53(Al) hybrid material for CO2 with a minimum separation factor of about 60 at 298 K. This value was much higher than those reported previously and those observed in this work for the original MIL-101(Cr) or MIL-53(Al). These results demonstrated that the hybrid of MIL-101(Cr) and MIL-53(Al) was a promising material for selective CO2 capture from natural and biogas.
| S-EPMC9064224 | biostudies-literature
Project description:MIL-100(Fe, Cr) and MIL-101(Cr) were synthesized by the hydrothermal method and applied to the adsorptions of five aromatic amines from aqueous solutions. These three metal-organic frameworks (MOFs) were well characterized by powder X-ray diffraction (PXRD), scanning electron microscope (SEM), transmission electron microscope (TEM), thermogravimetric analysis (TGA) and surface area analysis. The adsorption mechanism of three MOFs and the effects of the structures of MOFs on the adsorption of aromatic amines were discussed. The results show that the cavity system and suitable hydrogen bond acceptor were important factors for the adsorption for five aromatic amines of aniline, 1-naphthalamine, o-toluidine, 2-amino-4-nitrotoluene and 2-nitroaniline: (a) the saturated adsorption capacity of aniline, 1-naphthylamine and o-toluidine on MIL-100(Fe) were 52.0, 53.4 and 49.6 mg/g, respectively, which can be attributed to the intermolecular hydrogen bond interaction and cavity system diffusion. (b) The adsorption capacity of 2-nitroaniline and 2-amino-4-nitrotoluene on MIL-101(Cr) were 54.3 and 25.0 mg/g, respectively, which can be attributed to the more suitable pore size of MIL-101(Cr) than that of MIL-100(Fe, Cr). The MOFs of MIL-100(Fe) and MIL-101(Cr) can be potential materials for removing aromatic amines from aqueous solutions.
| S-EPMC6832246 | biostudies-literature
Project description:AbstractThe versatility of MOFs as highly porous Lewis acidic supports for precious metal nanoparticles has been exploited for one-pot tandem reductive amination catalysis. MIL-101(Cr) loaded with Pd nanoparticles ca. 3 nm in size at 0.2-1 wt% has been used to catalyse the reaction of 4'-fluoroacetophenone with benzylamine under 10 bar of H2 to give the secondary amine, 4'-fluoro-α-methyl-N-phenylmethylbenzenemethanamine. For the highest Pd loading, major hydrogenolysis of the secondary amine occurs in a second tandem reaction, but by changing the ratio of Pd to Lewis acidic Cr3+ active sites it is possible to tune the catalytic selectivity to the desired 2° amine product. An empirical kinetic analysis was performed to demonstrate this active site complementarity.Graphical abstract
| S-EPMC6566290 | biostudies-literature
Project description:Effectively reducing the concentration of nitrogen-containing compounds (NCCs) remains a significant but challenging task in environmental restoration. In this work, a novel step-scheme (S-scheme) SnO2@MCr heterojunction was successfully fabricated via a facile hydrothermal method. At this heterojunction, MIL-101(Cr) octahedrons are decorated with highly dispersed SnO2 quantum dots (QDs, approximate size 3 nm). The QDs are evenly wrapped around the MIL-101(Cr), forming an intriguing zero-dimensional/three-dimensional (0D/3D) S-scheme heterostructure. Under simulated sunlight irradiation (280 nm < λ < 980 nm), SnO2@MCr demonstrated superior photoactivity toward the denitrification of pyridine, a typical NCC. The adsorption capacity and adsorption site of SnO2@MCr were also investigated. Tests using 20%SnO2@MCr exhibited much higher activity than that of pure SnO2 and MIL-101(Cr); the reduction ratio of Cr(VI) is rapidly increased to 95% after sunlight irradiation for 4 h. The improvement in the photocatalytic activity is attributed to (i) the high dispersion of SnO2 QDs, (ii) the binding of the rich adsorption sites with pyridine molecules, and (iii) the formation of the S-scheme heterojunction between SnO2 and MIL-101(Cr). Finally, the photocatalytic mechanism of pyridine was elucidated, and the possible intermediate products and degradation pathways were discussed.
| S-EPMC8708904 | biostudies-literature
Project description:Surface-enhanced Raman scattering (SERS) is an important and powerful analytical technique in chemical and biochemical analyses. Metal-organic frameworks (MOFs) can effectively capture volatile organic compounds (VOCs) with high adsorption capacity and fast kinetics, and the local surface plasmon resonance characteristics of gold nanoparticles can quickly and effectively distinguish different VOCs by SERS. Combining both, we designed a novel SERS substrate based on embedding gold nanoparticles (AuNPs) within MIL-101(Cr) for the recognition of various VOCs in the gaseous phase. Occupying of AuNPs inside MIL-101(Cr) increased the micropore-specific surface area of AuNPs@MIL-101(Cr), which enabled AuNPs@MIL-101(Cr) to absorb more toluene molecules and consequently realized its high detection sensitivity. The detection limits for toluene, 4-ethylbenzaldehyde, and formaldehyde were down to 6, 5, and 75, ppm respectively. Moreover, this substrate could be used for detecting different VOCs simultaneously. Finally, we discussed the enhancement of AuNPs outside and inside MIL-101(Cr) on the Raman signal.
| S-EPMC9256292 | biostudies-literature
Project description:Lithium-sulfur batteries (LSBs) show excellent performance in terms of specific capacity and energy density. However, the cyclic stability of LSBs is compromised due to the "shuttle effect", which hinders the practical applications of LSBs. Herein, a metal-organic framework (MOF) based on Cr ions as the main body composition, commonly known as MIL-101(Cr), was utilized to minimize the shuttle effect and improve the cyclic performance of LSBs. To obtain MOFs with a certain adsorption capacity for lithium polysulfide and a certain catalytic capacity, we propose an effective strategy of incorporating sulfur-loving metal ions (Mn) into the skeleton to enhance the reaction kinetics at the electrode. Based on the oxidation doping method, Mn2+ was uniformly dispersed in MIL-101(Cr) to produce bimetallic Cr2O3/MnOx as a novel sulfur-carrying cathode material. Then, a sulfur injection process was carried out by melt diffusion to obtain the sulfur-containing Cr2O3/MnOx-S electrode. Moreover, an LSB assembled with Cr2O3/MnOx-S showed improved first-cycle discharge (1285 mAh·g-1 at 0.1 C) and cyclic performance (721 mAh·g-1 at 0.1 C after 100 cycles), and the overall performance was much better than that of monometallic MIL-101(Cr) as a sulfur carrier. These results revealed that the physical immobilization method of MIL-101(Cr) positively affected the adsorption of polysulfides, while the bimetallic composite Cr2O3/MnOx formed by the doping of sulfur-loving Mn2+ into the porous MOF produced a good catalytic effect during LSB charging. This research provides a novel approach for preparing efficient sulfur-containing materials for LSBs.
| S-EPMC10223926 | biostudies-literature
Project description:Bone is a hierarchical material primarily composed of collagen, water, and mineral that is organized into discrete molecular, nano-, micro-, and macroscale structural components. In contrast to the structural knowledge of the collagen and mineral domains, the nanoscale porosity of bone is poorly understood. In this study, we introduce a well-established pore characterization technique, positron annihilation lifetime spectroscopy (PALS), to probe the nanoscale size and distribution of each component domain by analyzing pore sizes inherent to hydrated bone together with pores generated by successive removal of water and then organic matrix (including collagen and noncollagenous proteins) from samples of cortical bovine femur. Combining the PALS results with simulated pore size distribution (PSD) results from collagen molecule and microfibril structure, we identify pores with diameter of 0.6 nm that suggest porosity within the collagen molecule regardless of the presence of mineral and water. We find that water occupies three larger domain size regions with nominal mean diameters of 1.1, 1.9, and 4.0 nm-spaces that are hypothesized to associate with intercollagen molecular spaces, terminal segments (d-spacing) within collagen microfibrils, and interface spacing between collagen and mineral structure, respectively. Subsequent removal of the organic matrix determines a structural pore size of 5-6 nm for deproteinized bone-suggesting the average spacing between mineral lamella. An independent method to deduce the average mineral spacing from specific surface area (SSA) measurements of the deproteinized sample is presented and compared with the PALS results. Together, the combined PALS and SSA results set a range on the mean mineral lamella thickness of 4-8 nm.
| S-EPMC8176962 | biostudies-literature
Project description:Hierarchically porous MIL-101(Cr) (H-MIL-101(Cr)) with meso/macro-pores was directly prepared via nanofusion progress by using butyric acid as a modulating agent. In the methyl orange (MO) adsorption experiments, H-MIL-101(Cr) showed a high adsorption capability of 369.8 mg g-1, which was 1.52-fold greater than that of pristine MIL-101(Cr) (P-MIL-101(Cr)). While in the oxidation reaction of indene and 1-dodecene tests, H-MIL-101(Cr) presented much higher catalytic efficiency, with turnover frequency (TOF) values of 0.7242 mmol g-1 min-1 and 0.1492 mmol g-1 min-1, respectively, which were 28% and 34% greater than that in the case of P-MIL-101(Cr). Thus, compared with P-MIL-101(Cr), H-MIL-101(Cr) exhibited better removal efficiency and higher levels of activity in the oxidation reactions of indene and 1-dodecene. The unique structure of H-MIL-101(Cr) also contributed to its superior performance in these processes.
| S-EPMC9146841 | biostudies-literature
Project description:Membrane separation technologies have great promising potential for applications in several industries. Metal-organic frameworks (MOFs), for their large surface areas, low framework densities, transition-metal ions in the skeleton and high pore volumes relative to other porous matrices, have great potential for the removal of sulfur from gasoline with high efficiency. In the present study, a novel porous membrane adsorbent MIL-101(Cr)/SA was prepared by immobilizing MIL-101(Cr) onto sodium alginate (SA) matrix, which can combine the size/shape selectivity of MIL-101(Cr) with the processability and mechanical stability of SA polymer. The physico-chemical properties of MIL-101(Cr)/SA were investigated by FT-IR, SEM, BET, XRD and EDX methods. To investigate the effects of some important factors on the adsorption behavior for thiophene, a batch of experiments were performed by changing the concentration of porogen polyethylene glycol in the MIL-101(Cr)/SA, solution temperature, initial thiophene concentration and contact time. Meanwhile, benzothiophene, thiophene and 3-methyl thiophene were used to test the selectivity of MIL-101(Cr)/SA. The MIL-101(Cr)/SA showed an excellent uptake capacity of 671 mg g-1 under the optimal adsorption conditions. Selectivity testing indicated that the uptake capacity of MIL-101(Cr)/SA follows the order of benzothiophene > thiophene > 3-methyl thiophene. Kinetics experiments indicated the pseudo-second-order model displayed good correlation with adsorption kinetics data. The Crank model showed that the intraparticle solute diffusion is the rate-controlling adsorption step. Regeneration experiment result shows that the prepared MIL-101(Cr)/SA has excellent adsorption and desorption efficiencies.
| S-EPMC9091623 | biostudies-literature