Per- and polyfluoroalkyl substances (PFAS) make up a diverse group of industrially derived organic chemicals that are of significant concern due to their detrimental effects on human health and ecosystems. Although other technologies are available for removing PFAS, adsorption remains a viable and effective method. Accordingly, the current study reported a novel type of graphene oxide (GO)-based adsorbent and tested their removal performance toward removing PFAS from water.
View Article and Find Full Text PDFControlling solid electrolyte interphase (SEI) in batteries is crucial for their efficient cycling. Herein, we demonstrate an approach to enable robust battery performance that does not rely on high fractions of fluorinated species in electrolytes, thus substantially decreasing the environmental footprint and cost of high-energy batteries. In this approach, we use very low fractions of readily reducible fluorinated cations in electrolyte (∼0.
View Article and Find Full Text PDFThe extensive use of per- and polyfluoroalkyl substances (PFAS) in many industrial and consumer contexts, along with their persistent nature and possible health hazards, has led to their recognition as a prevalent environmental issue. While various PFAS removal methods exist, adsorption remains a promising, cost-effective approach. This study evaluated the PFAS adsorption performance of a surfactant-modified clay by comparing it with commercial clay-based adsorbents.
View Article and Find Full Text PDFOne of the iconic characteristics of metal-organic frameworks (MOFs) is the possesssion of guest-accessible pores. Increasing pore size has a direct and often beneficial impact on a MOF's adsorption and separation properties. However, as pore size increases, the resulting void spaces are often filled by interpenetrated frameworks, where one or more networks crystallize within the pore system of another identical network, reducing the MOF's free volume and pore size.
View Article and Find Full Text PDFPost-synthetic modification (PSM) imparts additional functionality to metal-organic frameworks (MOFs) that is often difficult to access using solvothermal synthesis. As such, expanding the repertory of PSM reactions available to the practitioner is of increased importance for the generation of materials tailored for desired applications. Herein, a method is described for the protecting group-free installation of diverse functional groups within the pores of a MIL-53(Al) analogue via disulfide bond formation.
View Article and Find Full Text PDFGreen, renewable, and sustainable materials are needed for removing per- and polyfluoroalkyl substances (PFASs) in water. Herein, we synthesized and tested alginate (ALG) and chitosan (CTN) based and polyethyleneimine (PEI) functionalized fibers/aerogels for the adsorption of mixtures of 12 PFASs (9 short- and long-chain PFAAs, GenX, and 2 precursors) from water at an initial concentration of 10 μg/L each. Out of 11 biosorbents, ALGPEI-3 and GTH CTNPEI aerogels had the best sorption performance.
View Article and Find Full Text PDFWe show here that non-network metallopolymers can possess intrinsic microporosity stemming from contortion introduced by metallocene building blocks. Metallopolymers constructed from ferrocenyl building blocks linked by phenyldiacetylene bridges are synthesized and possess BET surface areas up to 400 m g. As solubility imparted by pendant groups reduces porosity, copolymerization is used to simultaneously improve both accessible surface area and solubility.
View Article and Find Full Text PDFDNA origami is typically used to fold a long single-stranded DNA scaffold into nanostructures with complex geometries using many short DNA staple strands. Integration of RNA into nucleic acid nanostructures is also possible, but has been less studied. In this research, we designed and characterized a hybrid RNA-scaffolded origami nanostructure with dimensions of ∼12 nm.
View Article and Find Full Text PDFRecently, intrinsically conductive metal-organic frameworks (MOFs) have demonstrated promising performance in fast-charging energy storage applications and may outperform some current electrode materials (, porous carbons) for supercapacitors in terms of both gravimetric and volumetric capacitance. In this report, we examine the mechanism of high capacitance in a nickel hexaaminobenzene-based MOF (NiHAB). Using a combination of Raman and X-ray absorption spectroscopies, as well as detailed electrochemical studies in a series of aqueous electrolytes, we demonstrate that the charge storage mechanism is, in fact, a pH-dependent surface pseudocapacitance, and unlike typical inorganic systems, where transition metals change oxidation state during charge/discharge cycles, NiHAB redox activity is ligand-centered.
View Article and Find Full Text PDFIn this work, we synthesize large-area thin films of a conjugated, imine-based, two-dimensional covalent organic framework at the solution/air interface. Thicknesses between ∼2-200 nm are achieved. Films can be transferred to any desired substrate by lifting from underneath, enabling their use as the semiconducting active layer in field-effect transistors.
View Article and Find Full Text PDFThe application of a core-shell architecture allows the formation of a polymer-coated metal-organic framework (MOF) maintaining high surface area (2289-2857 m(2) g(-1)). The growth of a MOF shell from a MOF core was used to spatially localize initiators by post-synthetic modification. The confinement of initiators ensures that polymerization is restricted to the outer shell of the MOF.
View Article and Find Full Text PDFSemiconducting, single-walled carbon nanotubes (SWNTs) are promising candidates for applications in thin-film transistors, solar cells, and biological imaging. To harness their full potential, however, it is necessary to separate the semiconducting from the metallic SWNTs present in the as-synthesized SWNT mixture. While various polymers are able to selectively disperse semiconducting SWNTs, the subsequent removal of the polymer is challenging.
View Article and Find Full Text PDFA strategy that allows the tuning of pore size in microporous coordination polymers (MCPs) through modification of their organic linkers is presented. When large substituents are introduced onto the linker, these pendent groups partially occupy the pores, thus reducing pore size while serving as additional adsorption sites for gases. The approach takes advantage of the fact that, for methane storage materials, small pores (0.
View Article and Find Full Text PDFMicroporous coordination polymers (MCPs) have emerged as strong contenders for adsorption-based fuel storage and delivery in large part because of their high specific surface areas. The strategy of increasing surface area by increasing organic linker length has shown only sporadic success; as demonstrated by many members of the iconic Zn4O-based IRMOF series, for example, accessible porosity is often limited by interpenetration or pore collapse upon guest removal. In this work, we focus on Zn4O(ndc)3 (IRMOF-8, ndc = 2,6-naphthalene dicarboxylate), which exhibits typical surface areas of only 1000-2000 m(2)/g even though a surface area of more than 4000 m(2)/g is expected from geometric analysis of the originally reported crystal structure.
View Article and Find Full Text PDFPositronium (Ps) is shown to exist in a delocalized state in self-assembled metalorganic crystals that have large 1.3-1.5 nm cell sizes.
View Article and Find Full Text PDFChem Commun (Camb)
October 2012
The synthesis and successful activation of IRMOF-8 (Zn(4)O(ndc)(3), ndc = naphthalene-2,6-dicarboxylate) is presented. Room temperature synthesis effectively suppresses interpenetration. Although conventional activation under reduced pressure leads to structural collapse, activation by flowing supercritical CO(2) yields a guest-free material with a BET surface area of 4461 m(2) g(-1).
View Article and Find Full Text PDFThere are several compounds for which there exists a disconnect between porosity as predicted by crystallography and porosity measured by gas sorption analysis. In this paper, the Zn-based analogue of Cu(3)(btc)(2) (HKUST-1), Zn(3)(btc)(2) (Zn-HKUST-1; btc = 1,3,5-benzenetricarboxylate) is investigated. Conventional analysis of Zn-HKUST-1 by powder X-ray diffraction and gas sorption indicates retention of crystalline structure but negligible nitrogen uptake at 77 K.
View Article and Find Full Text PDFQuantitative techniques are essential to analyze the structure of soft multicomponent nanobioclusters. Here, we combine electrospray differential mobility analysis (ES-DMA), which rapidly measures the size of the entire cluster, with transmission electron microscopy (TEM), which detects the hard components, to determine the presence and composition of the softer components. Coupling analysis of TEM and ES-DMA derived data requires the creation and use of analytical models to determine the size and number of constituents in nanoparticle complexes from the difference between the two measurements.
View Article and Find Full Text PDFBackground: Most emerging health threats are of zoonotic origin. For the overwhelming majority, their causative agents are RNA viruses which include but are not limited to HIV, Influenza, SARS, Ebola, Dengue, and Hantavirus. Of increasing importance therefore is a better understanding of global viral diversity to enable better surveillance and prediction of pandemic threats; this will require rapid and flexible methods for complete viral genome sequencing.
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