Effective removal of chemical warfare agent simulants using water stable metal–organic frameworks: mechanistic study and structure–property correlation

Asha, Padmaja; Sinha, Mekhola; Mandal, Sukhendu

doi:10.1039/c6ra28131a

Cited by 38 publications

(68 citation statements)

References 68 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The pure MOF is referred to as UiO66, while the composite is UiO66-C. The obtained dried powders were activated in high vacuum (10 −4 Torr) at 150 • C (using ASAP 2020, Micromeritics) and were kept in hermetically closed vials prior the use [63].…”

Section: Methodsmentioning

confidence: 99%

Building MOF Nanocomposites with Oxidized Graphitic Carbon Nitride Nanospheres: The Effect of Framework Geometry on the Structural Heterogeneity

Giannakoudakis

Bandosz

2019

Molecules

View full text Add to dashboard Cite

Composite of two MOFs, copper-based Cu-BTC (HKUST-1) and zirconium-based Zr-BDC (UiO-66), with oxidized graphitic carbon nitride nanospheres were synthesized. For comparison, pure MOFs were also obtained. The surface features were analyzed using x-ray diffraction (XRD), sorption of nitrogen, thermal analysis, and scanning electron microscopy (SEM). The incorporation of oxidized g-C 3 N 4 to the Cu-BTC framework caused the formation of a heterogeneous material of a hierarchical pores structure, but a decreased surface area when compared to that of the parent MOF. In the case of UiO-66, functionalized nanospheres were acting as seeds around which the crystals grew. Even though the MOF phases were detected in both materials, the porosity analysis indicated that in the case of Cu-BTC, a collapsed MOF/nonporous and amorphous matter was also present and the MOF phase was more defectous than that in the case of UiO-66. The results suggested different roles of oxidized g-C 3 N 4 during the composite synthesis, depending on the MOF geometry. While spherical units of UiO-66 grew undisturbed around oxidized and spherical g-C 3 N 4 , octahedral Cu-BTC units experienced geometrical constraints, leading to more defects, a disturbed growth of the MOF phase, and to the formation of mesopores at the contacts between the spheres and MOF units. The differences in the amounts of CO 2 adsorbed between the MOFs and the composites confirm the proposed role of oxidized g-C 3 N 4 in the composite formation.Molecules 2019, 24, 4529 2 of 14 for some applications, might limit the number of specific interactions/adsorption or catalytic centers. Therefore, the efforts have been intensified to introduce defects to the MOF structure targeting specific applications. Examples include mixed linkers [28][29][30], HCl treatment [31,32], variations in the synthesis conditions [33], the addition of molecular guests [34][35][36][37][38] or the incorporation of modified linkers [39,40]. These processes result in crystal imperfection, partial ligand replacement, or in nonbridging ligands, affecting the porosity, and the population, dispersion, and availability of active centers.The composites of MOFs with graphite oxide (GO) showed an increased pore volume, conductivity, and chemical heterogeneity [41][42][43]. This trend was an outcome of the reaction of the copper centers of Cu-BTC and the O-containing (epoxy, carboxylic, hydroxyl, and sulfonic) or N-containing functional groups of the 2-D GO phase [42][43][44]. The oxygen groups of GO were suggested to act either as equatorial or axial linkers, replacing BTC or water molecules, respectively.Since for building MOF-based composites, the geometry and morphology of the modifier is important, graphitic carbon nitride, g-C 3 N 4 , has also been used for this purpose. In its unoxidized form, it is an n-type semiconductor with a tunable band gap near 2.7 eV. g-C 3 N 4 has a flake-like structure similar to that of graphite with mainly carbon and nitrogen organized in triazine and tri-s-triazine (or s-heptazine...

show abstract

Section: Methodsmentioning

confidence: 99%

Building MOF Nanocomposites with Oxidized Graphitic Carbon Nitride Nanospheres: The Effect of Framework Geometry on the Structural Heterogeneity

Giannakoudakis

Bandosz

2019

Molecules

View full text Add to dashboard Cite

show abstract

“…Single-crystal X-ray diffraction showed that ReO 4 À ions bind in a unique chelating mode in both small pore and mesopore of NU-1000 in addition to two non-chelating modes in each pore, resulting in a promising adsorption efficiency. Asha et al 210 investigated NU-1000 toward the capture of two CWA simulants, 2-chloroethyl ethyl sulfide (2-CEES, the simulant of sulfur mustard gas), and dimethyl methyl phosphonate (DMMP, the simulant of sarin). NU-1000 performed efficient and reusable adsorption of the simulants from the aqueous medium.…”

Section: Adsorption and Separation Of Moleculesmentioning

confidence: 99%

Pyrene-based metal organic frameworks: from synthesis to applications

et al. 2021

View full text Add to dashboard Cite

show abstract

“…Besides, the FT-IR spectra implied that the coordination of UiO-66-NH 2 after treatment with CEES was nearly similar to that of the original. However, there was a weak peak at around 1277 cm −1 (C−O−C vibration) and another two peaks at 1273 and 1065 cm −1 (CEES), 48 indicating the decomposition products of ether, bis [2-(ethylthio)ethyl], and less CEES remaining. Both these excellent characteristics and high catalytic detoxification further ensure engineering UiO-66- NH 2 @PAN fabrics for CWAs removal as a promising protection gear.…”

Section: Catalysis and Adsorption Of Ceesmentioning

confidence: 99%

UiO-66-NH₂ Fabrics: Role of Trifluoroacetic Acid as a Modulator on MOF Uniform Coating on Electrospun Nanofibers and Efficient Decontamination of Chemical Warfare Agent Simulants

Zhang

Sun

Liu

et al. 2021

ACS Appl. Mater. Interfaces

View full text Add to dashboard Cite

Protective fabrics with air-permeable and flexible features are crucial for practical application in the detoxification of chemical warfare agents (CWAs). Zr-based metal−organic frameworks (Zr-MOFs) are desirable to exhibit outstanding degradation toward CWAs. However, generally, MOFs with powders cannot afford the utilization as a protective layer directly; meanwhile, it is still a puzzling challenge to integrate MOFs with textiles efficiently. Herein, we develop a scalable and controllable strategy to fabricate UiO-66-NH 2 on electrospun polyacrylonitrile nanofibers (UiO-66-NH 2 fabrics) firmly and uniformly to capture and catalyze 2chloroethyl ethyl sulfide (CEES) effectively for self-detoxification. The obtained UiO-66-NH 2 fabrics are greatly capable of specific surface area, ample porosity, excellent crystallinity, and abundant catalytic active sites. Consequently, CEES can be removed efficiently up to 97.7% after 48 h by reaction and adsorption. The degradation products mainly including ethyl-2-hydroxyethyl sulfide, ether, bis [2-(ethylthio)ethyl], and 2-(2-(ethylthio)ethylamino) terephthalic acid are detected. Moreover, the obtained nanofibrous fabrics possess air-permeable, washable, and flexible as well as lightweight merits, totally ensuring their promising engineering applications for protective clothing.

show abstract

Effective removal of chemical warfare agent simulants using water stable metal–organic frameworks: mechanistic study and structure–property correlation

Abstract: Water stable zirconium based MOFs are used for the efficient adsorptive removal of chemical warfare agent simulants from aqueous medium.

Cited by 38 publications

References 68 publications

Building MOF Nanocomposites with Oxidized Graphitic Carbon Nitride Nanospheres: The Effect of Framework Geometry on the Structural Heterogeneity

Building MOF Nanocomposites with Oxidized Graphitic Carbon Nitride Nanospheres: The Effect of Framework Geometry on the Structural Heterogeneity

Pyrene-based metal organic frameworks: from synthesis to applications

UiO-66-NH₂ Fabrics: Role of Trifluoroacetic Acid as a Modulator on MOF Uniform Coating on Electrospun Nanofibers and Efficient Decontamination of Chemical Warfare Agent Simulants

Contact Info

Product

Resources

About

Effective removal of chemical warfare agent simulants using water stable metal–organic frameworks: mechanistic study and structure–property correlation

Abstract: Water stable zirconium based MOFs are used for the efficient adsorptive removal of chemical warfare agent simulants from aqueous medium.

Cited by 38 publications

References 68 publications

Building MOF Nanocomposites with Oxidized Graphitic Carbon Nitride Nanospheres: The Effect of Framework Geometry on the Structural Heterogeneity

Building MOF Nanocomposites with Oxidized Graphitic Carbon Nitride Nanospheres: The Effect of Framework Geometry on the Structural Heterogeneity

Pyrene-based metal organic frameworks: from synthesis to applications

UiO-66-NH2 Fabrics: Role of Trifluoroacetic Acid as a Modulator on MOF Uniform Coating on Electrospun Nanofibers and Efficient Decontamination of Chemical Warfare Agent Simulants

Contact Info

Product

Resources

About

UiO-66-NH₂ Fabrics: Role of Trifluoroacetic Acid as a Modulator on MOF Uniform Coating on Electrospun Nanofibers and Efficient Decontamination of Chemical Warfare Agent Simulants