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      Chromium-Based Polypyrrole/MIL-101 Nanocomposite as an Effective Sorbent for Headspace Microextraction of Methyl tert-Butyl Ether in Soil Samples

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      Molecules
      MDPI
      MIL-101(Cr), polypyrrole, headspace microextraction, methyl-tert-butyl ether, soil

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          Abstract

          The performance of headspace solid-phase microextraction (HS-SPME) was upgraded by easy and low-cost preparation of a new nanocomposite fiber. A polypyrrole/chromium-based metal–organic framework, PPy@MIL-101(Cr), nanocomposite was electrochemically synthesized and simultaneously coated on a steel wire as a microextraction sorbent. The morphology and chemical structure of the prepared nanocomposite was characterized by Fourier-transform infrared spectrometry (FT-IR), scanning electron microscopy (SEM), and energy dispersive X-ray analysis (EDX) techniques. The microsorbent was used for sampling of methyl- tert-butyl ether (MTBE) in solid samples, through an HS-SPME sampling strategy, followed by GC-FID measurement. The optimal experimental conditions, including extraction temperature, extraction time, and GC desorption conditions, were evaluated and optimized. The proposed procedure showed good sensitivity (limit of detection was 0.01 ng·g −1) and precision (relative standard deviation was 8.4% for six replicated analyses). The calibration curve was linear over the range of 5–40,000 ng·g −1, with a correlation coefficient of 0.994. The limit of quantification was 0.4 ng·g −1. The fabricated fiber exhibited good repeatability and reproducibility for the sampling of MTBE, with average recovery values of 88–114%. The intra-fiber and inter-fiber precisions were found to be 8.4% and 19%, respectively. The results demonstrated the superiority of the PPy@MIL-101(Cr)-coated fiber in comparison with handmade (polypyrrole, PPY) and commercial fibers (polyacrylate, PA; polydimethylsiloxane, PDMS; and divinylbenzene/carboxen/polydimethylsiloxane, DVB/CAR/PDMS) for the analysis of solid samples. The developed method was successfully employed for the analysis of MTBE in different soil samples contaminated by oil products.

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          Most cited references30

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          Metal-organic framework materials with ultrahigh surface areas: is the sky the limit?

          We have synthesized, characterized, and computationally simulated/validated the behavior of two new metal-organic framework (MOF) materials displaying the highest experimental Brunauer-Emmett-Teller (BET) surface areas of any porous materials reported to date (~7000 m(2)/g). Key to evacuating the initially solvent-filled materials without pore collapse, and thereby accessing the ultrahigh areas, is the use of a supercritical CO(2) activation technique. Additionally, we demonstrate computationally that by shifting from phenyl groups to "space efficient" acetylene moieties as linker expansion units, the hypothetical maximum surface area for a MOF material is substantially greater than previously envisioned (~14600 m(2)/g (or greater) versus ~10500 m(2)/g).
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            Recent advances in post-synthetic modification of metal–organic frameworks: New types and tandem reactions

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              Exceptional hydrogen storage achieved by screening nearly half a million metal-organic frameworks

              Few hydrogen adsorbents balance high usable volumetric and gravimetric capacities. Although metal-organic frameworks (MOFs) have recently demonstrated progress in closing this gap, the large number of MOFs has hindered the identification of optimal materials. Here, a systematic assessment of published databases of real and hypothetical MOFs is presented. Nearly 500,000 compounds were screened computationally, and the most promising were assessed experimentally. Three MOFs with capacities surpassing that of IRMOF-20, the record-holder for balanced hydrogen capacity, are demonstrated: SNU-70, UMCM-9, and PCN-610/NU-100. Analysis of trends reveals the existence of a volumetric ceiling at ∼40 g H2 L−1. Surpassing this ceiling is proposed as a new capacity target for hydrogen adsorbents. Counter to earlier studies of total hydrogen uptake in MOFs, usable capacities in the highest-capacity materials are negatively correlated with density and volumetric surface area. Instead, capacity is maximized by increasing gravimetric surface area and porosity. This suggests that property/performance trends for total capacities may not translate to usable capacities.
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                Author and article information

                Contributors
                Role: Academic Editor
                Journal
                Molecules
                Molecules
                molecules
                Molecules
                MDPI
                1420-3049
                03 February 2020
                February 2020
                : 25
                : 3
                : 644
                Affiliations
                Department of Chemistry, Lorestan University, Khoramabad 6815144316, Iran; jl_kalhor@ 123456yahoo.com
                Author notes
                [* ]Correspondence: ghiasvand.a@ 123456lu.ac.ir or alireza.ghiasvand@ 123456utas.edu.au ; Tel.: +98-66-33120612
                Author information
                https://orcid.org/0000-0002-4570-7988
                Article
                molecules-25-00644
                10.3390/molecules25030644
                7037173
                32028571
                424abf36-b3bf-477d-81f1-802c3e47074d
                © 2020 by the authors.

                Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license ( http://creativecommons.org/licenses/by/4.0/).

                History
                : 13 January 2020
                : 31 January 2020
                Categories
                Article

                mil-101(cr),polypyrrole,headspace microextraction,methyl-tert-butyl ether,soil

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