Performance Fabrics Obtained by In Situ Growth of Metal-Organic Frameworks in Electrospun Fibers

Metal–organic frameworks (MOFs) exhibit an exceptional surface area-to-volume ratio, variable pore sizes, and selective binding, and hence, there is an ongoing effort to advance their processability for broadening their utilization in different applications. In this work, we demonstrate a general scheme for fabricating freestanding MOF-embedded polymeric fibers, in which the fibers themselves act as microreactors for the in situ growth of the MOF crystals. The MOF-embedded fibers are obtained via a two-step process, in which, initially, polymer solutions containing the MOF precursors are electrospun to obtain microfibers, and then, the growth of MOF crystals is initiated and performed via antisolvent-induced crystallization. Using this approach, we demonstrate the fabrication of composite microfibers containing two types of MOFs: copper (II) benzene-1,3,5-tricarboxylic acid (HKUST-1) and zinc (II) 2-methylimidazole (ZIF-8). The MOF crystals grow from the fiber’s core toward its outer rims, leading to exposed MOF crystals that are well rooted within the polymer matrix. The MOF fibers obtained using this method can reach lengths of hundreds of meters and exhibit mechanical strength that allows arranging them into dense, flexible, and highly durable nonwoven meshes. We also examined the use of the MOF fiber meshes for the immobilization of the enzymes catalase and horse radish peroxidase (HRP), and the enzyme-MOF fabrics exhibit improved performance. The MOF-embedded fibers, demonstrated in this work, hold promise for different applications including separation of specific chemical species, selective catalysis, and sensing and pave the way to new MOF-containing performance fabrics and active membranes

Direct fabrication of graphene on SiO[subscript 2] enabled by thin film stress engineering

We demonstrate direct production of graphene on SiO[subscript 2] by CVD growth of graphene at the interface between a Ni film and the SiO[subscript 2] substrate, followed by dry mechanical delamination of the Ni using adhesive tape. This result is enabled by understanding of the competition between stress evolution and microstructure development upon annealing of the Ni prior to the graphene growth step. When the Ni film remains adherent after graphene growth, the balance between residual stress and adhesion governs the ability to mechanically remove the Ni after the CVD process. In this study the graphene on SiO[subscript 2] comprises micron-scale domains, ranging from monolayer to multilayer. The graphene has >90% coverage across centimeter-scale dimensions, limited by the size of our CVD chamber. Further engineering of the Ni film microstructure and stress state could enable manufacturing of highly uniform interfacial graphene followed by clean mechanical delamination over practically indefinite dimensions. Moreover, our findings suggest that preferential adhesion can enable production of 2-D materials directly on application-relevant substrates. This is attractive compared to transfer methods, which can cause mechanical damage and leave residues behind.Guardian IndustriesNational Science Foundation (U.S.). Graduate Research Fellowship Progra

Hierarchically Functionalized Magnetic Core/Multishell Particles and Their Postsynthetic Conversion to Polymer Capsules

The controlled synthesis of hierarchically functionalized core/multishell particles is highly desirable for applications in medicine, catalysis, and separation. Here, we describe the synthesis of hierarchically structured metal–organic framework multishells around magnetic core particles (magMOFs) <i>via</i> layer-by-layer (LbL) synthesis. The LbL deposition enables the design of multishell systems, where each MOF shell can be modified to install different functions. Here, we used this approach to create controlled release capsules, in which the inner shell serves as a reservoir and the outer shell serves as a membrane after postsynthetic conversion of the MOF structure to a polymer network. These capsules enable the controlled release of loaded dye molecules, depending on the surrounding media