Synthesis and Characterization of Gyroidal Mesoporous Carbons and Carbon Monoliths with Tunable Ultralarge Pore Size

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)-<i>block</i>-poly(styrene)-<i>block</i>-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 cm³ g^–1. Treatment at this temperature induced a high degree of sp²-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