Adsorptive stripping voltammetric sensor based on Cd zeolitic imidazole framework-67 for electrochemical detection of sarin simulant.

A selective and reliable modified glassy carbon sensor, based on a 1.0% Cd zeolitic imidazole framework-67 modified glassy carbon sensor (GCS2), has been developed for ultrasensitive detection of dimethyl methyl phosphonate (DMMP) in human biological fluid. The synthesis of porous nanoparticles of Cd zeolitic imidazole framework-67 (Cd ZIF-67) was carried out via the hydrothermal method. The resulting Cd ZIF-67 powder emerges with good crystallinity, a rhombic dodecahedral morphology with particle size in the range 300 ~ 500 nm, and a specific surface area of 1780 m2·g-1. Furthermore, the fabricated sensor exhibited superior performance in the detection of DMMP with two linearity ranges of 0.02-2.0 nM and 2.0-9.0 nM and a limit of detection (LOD) of 0.06 pM. The fabricated sensor exhibited good reliability, long-term stability, and repeatability, which are favourable attributes for electroanalytical detection. In addition, the fabricated sensor displayed superior performance without significant interference during the assay of DMMP in a biological fluid (human serum sample) within two linearity ranges of 0.1-1.0 nM and 1.0-6.0 nM and a LOD of 0.03 nM.

Anion-Exchange Electrospun Mixed-Matrix Polymer Fibers of Colesevelam for Water Treatment.

Novel anion-exchange electrospun fiber membranes of polycaprolactone doped with the cationic, cross-linked colesevelam polymer are reported. The weight fraction of cross-linked cationic colesevelam polymer, as the active phase within the PCL matrix, can readily be controlled in the synthesis of the mixed-matrix fibers (Cole@PCL), enabling optimization of the ion-exchange properties of the resulted membranes. This approach enabled adaptation of anion-exchange resins to a permeable, flexible membrane form, which is a significant advancement toward futuristic water treatment applications, demonstrated herein for the removal of trace contaminants, including nitrates and phosphates, as well as anionic dyes. The Cole@PCL membranes demonstrated the dependence of contaminant uptake on the weight percentage of colesevelam in the mixed-matrix membrane. An optimal 10 wt % of colesevelam was identified, demonstrating a staggering ion removal capacity of 155.8 mg/g for nitrate, 177.6 mg/g for phosphate, and 70 mg/g for Methyl Orange.

Effect of sulfur doping of zinc-imidazole coordination polymer (ZnIm CP) as a novel photocatalyst for degradation of ionic dyes.

Zinc-Imidazole coordination polymer (ZnImCP) was simply synthesized hydrothermally at relatively low temperature (70 °C) from zinc acetate and imidazole. ZnImCP was treated by sulfide solution to produce sulfur-doped samples (S-ZnImCPs). Structures of the synthesized ZnImCP and S-ZnImCPs were characterized through FTIR, PXRD, and, Raman, SEM/EDX, N2-BET, UV-VIS DRS, and pHpzc analyses. The photocatalytic performances of pristine CP and sulfur modified CPs under visible and ultra-violet irradiations for degrading the cationic methylene blue (MB) and the anionic methyl orange (MO) were investigated considering different initial pH values 4, 7 and 10. Under visible light, the results indicate that these CPs display considerable photocatalytic degradation towards the cationic MB for the initial pH 4 and 7 where degradation increases with sulfur content. While under ultra-violet, results indicate considerable photocatalytic degradation towards both dyes for the initial pH 7 and 10 where degradation increases with sulfur content which indicates the gainful of non-metal dopping. The buffering nature of CPs and the type of radiation considering determined band-gap values effectively influence the degradation mechanisms.

Designing bimetallic zeolitic imidazolate frameworks (ZIFs) for aqueous catalysis: Co/Zn-ZIF-8 as a cyclic-durable catalyst for hydrogen peroxide oxidative decomposition of organic dyes in water.

ZIF-8 is well known hybrid material that is self-assembled from inorganic and organic moieties. It has several potential applications due to its unique structure. One of these potential applications is in advanced oxidation processes (AOP) via a heterogeneous catalysis system. The use of modified ZIF-8/H2O2 for the destruction of the azo dye methyl orange (MO) is presented in this work to explore its efficacy. This work presents the bimetallic Co/Zn-ZIF-8 as an efficient catalyst to promote H2O2 oxidation of the MO dye. Co/Zn-ZIF-8 was synthesized through a hydrothermal process, and the pristine structure was confirmed using XRD, FTIR, and XPS. The Co/Zn-ZIF-8/H2O2 system successfully decolorized MO at the selected pH 6.5. It was found that more than 90% of MO (10 ppm) was degraded within only about 50 minutes. Proposed radical and redox mechanisms are presented for H2O2 decomposition where the redox mechanism is suggested to predominate via a Co(ii)/Co(iii) redox consecutive cyclic process.

Advances of the highly efficient and stable visible light active photocatalyst Zr(IV)-phthalate coordination polymer for the degradation of organic contaminants in water.

This work presents the restoration of the Zr-phthalate coordination polymer (Zr-Ph CP) via valuable application in photocatalysis. Zr-Ph CP was facilely synthesized using a soft hydrothermal method at 70 °C, and was characterized utilizing FTIR, Raman Spectrosopy, XPS, PXRD, SEM/EDX, BET, and a hyperspectral camera. Assessment of its photocatalytic degradation potential was performed against two different dyes, the cationic methylene blue (MB) and the anionic methyl orange (MO), as frequent models of organic contaminants, under properly selected mild visible illumination (9 W) where the bandgap energy (Eg) was determined to be 2.72 eV. Effects of different initial pH values and different dyes' initial concentrations were covered. Photocatalytic degradation studies showed that Zr-Ph CP effectively degraded both dyes for initial pH 7 within about 40-60 minutes. Degradation rate constants were calculated as 0.17 and 0.13 min-1 for MB and MO, respectively. Generally, both direct and indirect mechanisms share in the degradation, where adsorption has shown an important role. The repeated use of Zr-Ph CP does not significantly affect its photocatalytic performance suggesting high water stability.

Facile and rapid synthesis of functionalized Zr-BTC for the optical detection of the blistering agent simulant 2-chloroethyl ethyl sulfide (CEES).

2-Chloroethyl ethyl sulfide (CEES) is a simulant for the chemical warfare agent, bis(2-chloroethyl) sulfide, also known as mustard gas. Here, we demonstrate a facile and rapid method to synthesize a functionalized metal-organic framework (MOF) material for the detection of CEES at trace level. During the synthesis of Zr-BTC, the in situ encapsulation of a fluorescent material (fluorescein) into Zr-BTC voids is performed by a simple solvothermal reaction. The produced F@Zr-BTC is used as a fluorescent probe for CEES detection. The synthesized material shows fluorescence quenching under illumination at an excitation wavelength of 470 nm when F@Zr-BTC is exposed to CEES. This sensing material shows the highest fluorescence quenching at an emission wavelength of 534 nm with a CEES concentration as low as 50 ppb. Therefore, the demonstrated sensing method with F@Zr-BTC is a fast and convenient protocol for the selective and sensitive detection of CEES in practical applications.

Highly selective and sensitive fluorescent zeolitic imidazole frameworks sensor for nitroaromatic explosive detection.

Nitroaromatic explosives, such as 2-4-6 trinitrotoluene (TNT) are dangerous materials that pose safety and environmental risks. Even though many sensors have been reported for the detection of nitroaromatic explosives, a facile, rapid, cost-effective sensor is still sought-after in the field. Here we demonstrate a facile and rapid method to synthesize a fluorescent metal-organic framework for the highly selective and sensitive detection of nitroaromatic explosives. Zeolitic imidazole framework-8 (ZIF-8) is synthesized and enhanced with fluorescent 8-hydroxyquinoline zinc (ZnQ). The synthesized material shows visible colour changes upon exposure to TNT from ivory to light red. In addition, fluorescence quenching is noted under UV illumination when the ZnQ@ZIF-8 is exposed to TNT. The ZnQ@ZIF-8-coated paper sensors show the highest fluorescence quenching at an emission wavelength of 455 nm with TNT concentration as low as 1 ppm. Therefore, the proposed strategy not only offers a fast and convenient protocol for selective detection of TNT but also offers great potential in practical applications, especially for airport/railway security inspection and prevention of terrorist attacks.

Intense Pulsed Light-Treated Near-Field Electrospun Nanofiber on a Quartz Tuning Fork for Multimodal Gas Sensors.

Accurate and portable gas sensors are required for environmental monitoring, locating leakages, and detecting trace chemical vapors or gases. Although many sensors have been developed, few can rapidly and selectively detect parts per million (ppm) concentration changes. In this work, we fabricate multimodal gas sensors by depositing a single nanocomposite fiber between the prongs of a quartz tuning fork (QTF). The resulting sensors are portable and integrate multimodal approaches by applying both chemo-mechanical sensing for sensitivity and electrochemical sensing for selectivity. Near-field electrospinning (NFES) produces a flexible and semiconductive nanocomposite fiber with ∼500 nm diameter that can be integrated into electronic systems as environmental gas sensors. Intense pulsed light (IPL) and sputter coating improve adhesion of the nanocomposite fiber onto a QTF. Furthermore, IPL offers improved sensing performance due to the higher specific surface area and reduction in polymer content. In this study, hydrogen gas (H2) is chosen as a target gas since it is a common energy source in fuel cell applications and byproduct in chemical reactions. An electrospinning solution containing polyaniline, multiwalled carbon nanotubes, and platinum nanoparticles is used to test H2 gas sensing performance. The resulting multimodal sensors are selective to hydrogen versus other gases and vapors including methane, hexane, toluene, ammonia, ethanol, carbon dioxide, and oxygen. Furthermore, the sensors detect ppm levels of hydrogen gas even in the presence of high humidity that typically hinders gas sensor performance. The development of this sensor leads to a new method for compact and portable multimodal gas sensing.

Sonochemical fabrication of Cu(II) and Zn(II) metal-organic framework films on metal substrates.

In this article, we demonstrate a rapid and facile method for in-situ growth of metal-organic framework (MOF) films on Cu or Zn metal substrates by sonochemical techniques. The substrates were first treated with a strong oxidizing agent to convert the metal to the corresponding metal hydroxide. Ultrasonic irradiation provided the energy to drive the reaction between the metal ion sources and organic ligands. Four MOF films (Cu-BTC, Cu-BDC, ZIF-8 and MOF-5) were successfully fabricated by this approach. The produced films were characterized by scanning electron microscopy and X-ray diffraction analysis. The effects of organic ligand concentration and ultrasonic irradiation time on MOF film synthesis were also systematically investigated. The rapid and facile fabrication method presented in this article could serve a new route to grow MOF films on various gas sensor surfaces. Of the MOF films, ZIF-8 film was tested as a potential methane sensor.