Recent progress in PIM-1 based membranes for sustainable CO2 separations: Polymer structure manipulation and mixed matrix membrane design

Melanin is a ubiquitous natural pigment found in a diverse array of organisms. Allomelanin is a class of nitrogen-free melanin often found in fungi. Herein, we find artificial allomelanin analogues exhibit high intrinsic microporosity and describe an approach for further increasing and tuning that porosity. Notably, the synthetic method involves an oxidative polymerization of 1,8-DHN in water, negating the need for multiple complex templating steps and avoiding expensive or complex chemical precursors. The well-defined morphologies of these nanomaterials were elucidated by a combination of electron microscopy and scattering methods, yielding to high-resolution 3D reconstruction based on small-angle X-ray scattering (SAXS) results. Synthetic allomelanin nanoparticles exhibit high BET areas, up to 860 m2/g, and are capable of ammonia capture up to 17.0 mmol/g at 1 bar. In addition, these nanomaterials can adsorb nerve agent simulants in solution and as a coating on fabrics with high breathability where they prevent breakthrough. We also confirmed that naturally derived fungal melanin can adsorb nerve gas simulants in solution efficiently despite lower porosity than synthetic analogues. Our approach inspires further analysis of yet to be discovered biological materials of this class where melanins with intrinsic microporosity may be linked to evolutionary advantages in relevant organisms and may in turn inspire the design of new high surface area materials.

Allomelanin: A Biopolymer of Intrinsic Microporosity.

While polymers of intrinsic microporosity (PIMs) possess appealing features such as high surface area, good solubility, and tailorable functional groups on the polymer backbone, their ability to de...

Reactive Porous Polymers for Detoxification of a Chemical Warfare Agent Simulant

Since the emergence of chemical, biological, radiological, and nuclear risks, significant efforts have been made to create efficient personal protection equipment. Recently, metal-organic framework (MOF) materials have emerged as new promising candidates for the capture and degradation of various threats, like chemical warfare agents (CWAs) or radioactive species. Herein, we report a new synthesis method of MOF-textile composites by microwave irradiation, with direct anchoring of MOFs on textiles. The resistance of the composite has been tested using normed abrasion measurements, and non-stable samples were optimized. The protection capacity of the MOF-textile composite has been tested against dimethyl 4-nitrophenyl phosphate, a common CWA simulant, showing short degradation half-life (30 min). Radiological/nuclear protection has also been tested through uranium uptake (up to 15 mg g-1 adsorbent) and the capture of Kr or Xe gas at 0.9 and 2.9 cm3/g, respectively.

Microwave-Assisted Synthesis of Porous Composites MOF-Textile for the Protection against Chemical and Nuclear Hazards.

/pdf/porous-textile-composites-ptcs-for-the-removal-and-the-12hmjndw.pdf

Porous textile composites (PTCs) for the removal and the decomposition of chemical warfare agents (CWAs) – A review

Highly selective and lightweight protective suits featuring excellent breathability, mechanical robustness, and catalytic degradation performance toward chemical warfare agents (CWAs) are highly desirable for first responders and the military However, current multilayered state-of-the-art chemical/biological (CB) protective textiles containing activated carbon and separate aerosol-protective layers exhibit several drawbacks including high thermal burden and secondary contamination Herein, we present for the first time, a highly sorptive, breathable, and mechanically strong aerosol-protective layered fabric with prominent catalytic degradation capability of CWA simulant, through novel material selection and engineering design The electrospun polymer of intrinsic microporosity (PIM-1) fiber web with hierarchical porosity is used as a matrix material, preventing toxic gas penetration while providing pathways for air and water vapor molecules Polyacrylonitrile (PAN) nanofibers assembled with PIM-1 fibers via a layer-by-layer electrospun-deposition approach are shown to achieve significantly enhanced mechanical integrity and filtration efficiency, due to the high polar chemical structure and small fiber diameter of PAN The subsequent incorporation of UiO-66-NH2 particles, a Zr-based metal-organic framework (MOF), further enhances the sorption capacity while maintaining excellent filtration efficiency, mechanical strength, and breathability, and also endows the fiber web with remarkable catalytic degradation towards CWA simulants The resulting PIM/PAN/MOF composite fiber mat demonstrates unprecedented integrated properties with water vapor transmission rate of 1,013 g/m2·24 h, surface area of 574 m2/g, increased tensile strength (more than 70 times compared to neat PIM-1 fiber web), and PM25 and PM10 filtration efficiency of 9988% and 9994%, respectively, comparable to commercial polypropylene (PP) non-woven textile This facile and effective fabrication of such a multifunctional composite fiber mat is valuable for the design of protective garments in health care, personal protective gear, and law enforcement and military uniforms

Polymer of intrinsic microporosity (PIM) based fibrous mat: combining particle filtration and rapid catalytic hydrolysis of chemical warfare agent simulants into a highly sorptive, breathable, and mechanically robust fiber matrix

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Polymer of intrinsic microporosity (PIM) based fibrous mat: combining particle filtration and rapid catalytic hydrolysis of chemical warfare agent simulants into a highly sorptive, breathable, and mechanically robust fiber matrix