Porous materials design often faces a trade-off between the requirements of high internal surface area and high reagent flux. Inorganic materials with asymmetric/hierarchical pore structures or well-defined mesopores have been tested to overcome this trade-off, but success has remained limited when the strategies are employed individually. Here, the attributes of both strategies are combined and a scalable path to porous titanium nitride (TiN) and carbon membranes that are conducting (TiN, carbon) or superconducting (TiN) is demonstrated. These materials exhibit a combination of asymmetric, hierarchical pore structures and welldefined mesoporosity throughout the material. Fast transport through such TiN materials as an electrochemical double-layer capacitor provides a substantial improvement in capacity retention at high scan rates, resulting in state-of-the-art power density (28.2 kW kg −1 ) at competitive energy density (7.3 W-h kg −1 ). In the case of carbon membranes, a record-setting power density (287.9 kW kg −1 ) at 14.5 W-h kg −1 is reported. Results suggest distinct advantages of such pore architectures for energy storage and conversion applications and provide an advanced avenue for addressing the trade-off between high-surface-area and high-flux requirements.
Three-dimensional (3D) periodic ordering of silicon (Si), an inorganic semiconductor, on the mesoscale was achieved by combining block copolymer (BCP) self-assembly (SA) based mesoporous alternating gyroidal network formation with nonequilibrium transient laser heating. 3D continuous and periodically ordered alternating gyroidal mesoporous carbon thin-film networks were prepared from spin coating, SA under solvent vapor annealing (SVA), and thermal processing of mixtures of a triblock terpolymer with resorcinol resols. The resulting mesoporous thin films, acting as structure-directing templates, were backfilled with amorphous silicon (a-Si). Nanosecond excimer laser heating led to transient Si melts conformally filling the template pores and subsequent Si crystallization. The ordered mesostructure of the organic polymer-derived templates was kept intact, despite being thermally unstable at the high temperatures around the Si melting point (MP), leading to high pattern transfer fidelity. As evidenced by a combination of grazing incidence small-angle X-ray scattering (GISAXS) and scanning electron microscopy (SEM), after template removal, the crystalline Si (c-Si) inherited the inverse network topology of the 3D mesoporous thin-film templates, but with reduced F222 space group symmetry (D 2 point group symmetry) from compression of the cubic alternating gyroid lattice. Structures with this reduced symmetry have been proposed as photonic and phononic materials exhibiting topologically protected Weyl points, adding to the emerging field of BCP SA-directed quantum materials promising advanced physics and materials properties.
Properties arising from ordered periodic mesostructures are often obscured by small, randomly oriented domains and grain boundaries. Bulk macroscopic single crystals with mesoscale periodicity are needed to establish fundamental structure-property correlations for materials ordered at this length scale (10-100 nm). We report on a solvent evaporation-induced crystallization method providing access to large (mm to cm sized) single crystal mesostructures in thick films (>100 µm), specifically bicontinuous gyroids, derived from block copolymers. After in-depth crystallographic characterization of single-crystal block copolymer-preceramic nanocomposite films, the structures are converted into mesoporous ceramic monoliths, with retention of mesoscale crystallinity. When fractured, these monoliths display single crystal-like cleavage along mesoscale facets. The method
The temperature required to induce cross-linking in typical benzocyclobutene-based thermosets is near 250 °C, which exceeds the use temperature of many chemical components. A new and versatile synthesis of BCB-functionalized monomers has allowed access to monomers that can be incorporated into a variety of macromolecular platforms to enable significantly reduced cure temperatures. Incorporation of BCB-functionalized comonomers in polystyrene and polynorbornene enabled insolublization of thin films by curing at only 120 °C for 1 h.
Block copolymer (BCP)-derived asymmetric ultrafiltration membranes combine the BCP self-assembly with nonsolvent-induced phase separation (SNIPS). To understand the structural evolution in membrane top separation layers made from polyisoprene-b-polystyrene-b-poly(4-vinylpyridine) (ISV) in dioxane (DOX) and tetrahydrofuran (THF) all the way to the final membrane, we combined solution small-angle X-ray scattering (SAXS), estimated solution concentrations and compositions upon solvent evaporation, in situ grazing-incidence SAXS (GISAXS), spin–spin relaxation time (T 2) analysis by solution 1H NMR, and scanning electron microscopy (SEM). Above the critical micelle concentration (<1 wt % ISV), solvent evaporation drives micelles with poly(4-vinylpyridine) (P4VP) in the core across disorder-to-order and order-to-order transitions, the latter in part driven by the segregation of polyisoprene (PI)- from polystyrene (PS)-blocks. Extended to polystyrene-b-poly(4-vinylpyridine) (SV) in dimethylformamide (DMF) and THF, results suggest that, in particular, T 2 relaxation analysis by 1H NMR is a powerful tool in analyzing which blocks form micelle core and which form corona chains. We expect insights to help develop next-generation SNIPS membranes for applications, e.g., in clean water and biopharmaceutical separations.
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