Despite considerable efforts toward fabricating ordered, water-permeable, mesoporous films from block copolymers, fine control over pore dimensions, structural characteristics, and mechanical behavior of graded structures remains a major challenge. To this end, we describe the fabrication and performance characteristics of graded mesoporous and hybrid films derived from the newly synthesized triblock terpolymer, poly(isoprene-b-styrene-b-4-vinylpyridine). A unique morphology, unachievable in diblock copolymer systems, with enhanced mechanical integrity is evidenced. The film structure comprises a thin selective layer containing vertically aligned and nearly monodisperse mesopores at a density of more than 10(14) per m(2) above a graded macroporous layer. Hybridization via homopolymer blending enables tuning of pore size within the range of 16 to 30 nm. Solvent flow and solute separation experiments demonstrate that the terpolymer films have permeabilities comparable to commercial membranes, are stimuli-responsive, and contain pores with a nearly monodisperse diameter. These results suggest that moving to multiblock polymers and their hybrids may open new paths to produce high-performance graded membranes for filtration, separations, nanofluidics, catalysis, and drug delivery.

Development of rapid processes combining hierarchical self-assembly with mesoscopic shape control has remained a challenge. This is particularly true for high-surface-area porous materials essential for applications including separation and detection, catalysis, and energy conversion and storage. We introduce a simple and rapid laser writing method compatible with semiconductor processing technology to control three-dimensionally continuous hierarchically porous polymer network structures and shapes. Combining self-assembly of mixtures of block copolymers and resols with spatially localized transient laser heating enables pore size and pore size distribution control in all-organic and highly conducting inorganic carbon films with variable thickness. The method provides all-laser-controlled pathways to complex high-surface-area structures, including fabrication of microfluidic devices with high-surface-area channels and complex porous crystalline semiconductor nanostructures.

Ordered mesoporous carbons with high pore accessibility are of great interest as electrodes in energy conversion and storage applications due to their high electric and thermal conductivity, chemical inertness, and low density. The metal- and halogen-free synthesis of gyroidal bicontinuous mesoporous carbon materials with uniform and tunable pore sizes through bottom-up self-assembly of block copolymers thus poses an interesting challenge. Four double gyroidal mesoporous carbons with pore sizes of 12, 15, 20, and 39 nm were synthesized using poly(isoprene)-block-poly(styrene)-block-poly(ethylene oxide) (ISO) as structure-directing triblock terpolymer and phenol-formaldehyde resols as carbon precursors. The highly ordered materials were thermally stable to at least 1600 °C with pore volumes of up to 1.56 cm(3) g(-1). Treatment at this temperature induced a high degree of sp(2)-hybridization and low microporosity. Increasing the resols/ISO ratio led to hexagonally packed cylinders with lower porosity. A single gyroid carbon network with high porosity of 80 vol % was obtained using a similar synthesis strategy. Furthermore, we present a method to fabricate monolithic materials of the gyroidal carbons with macroscopic shape and thickness control that exhibit an open and structured surface with gyroidal features. The gyroidal materials are ideally suited as electrode materials in fuel cells, batteries, and supercapacitors as their high, three-dimensionally connected porosity is expected to allow for good fuel or electrolyte accessibility and to prevent total pore blockage.

Multifunctional three-dimensional (3-D) nano-architectures, integrating all device components within tens of nanometers, offer great promise for next generation electrical energy storage applications, but have remained challenging to achieve. The lack of appropriate synthesis methods, enabling precise 3-D spatial control at the nanoscale, remains a key issue holding back the development of such intricate architectures. Here we present an approach to such systems based on the bottom-up synthesis of penta-continuous nanohybrid monoliths with four functional components integrated in a triblock terpolymer derived core-shell double gyroid architecture. Two distinct 3-D interpenetrating networks serving as cathode and current collector are separated from a carbon anode matrix by continuous, ultrathin polymer electrolyte shells. All periodically ordered domains are less than 20 nm in their layer dimensions and integrated throughout the macroscopic monolith. Initial electrochemical measurements with the Li-ion/S system exhibit reversible batterylike charge-discharge characteristics with orders of magnitude decreases in footprint area over conventional flat thin layer designs.Nanostructured materials have dramatically impacted fundamental and applied research as well as applications due to their unique properties arising from well-defined spatial confinement and large surface area-to-volume ratios 1-3 . Co-continuous nanohybrids of multiple distinct functional materials offer the potential for great advances in catalysis, energy conversion, and optical devices due to their large interfacial areas combined with three-dimensional (3-D) continuity of all phases 4-6 . While developments in top-down photolithographic techniques and materials have enabled access to ever decreasing feature sizes in two-and three-dimensional (2-D and 3-D) architectures for transistors and other circuit elements 7,8 , leading to widespread deployment of electronics 9 , rapid 3-D nanohybrid device formation remains challenging and