Jianwen Jiang

An asymmetric supercapacitor (ASC) was fabricated using reduced graphene oxide (RGO) sheets modified with ruthenium oxide (RGO–RuO2) or polyaniline (RGO–PANi) as the anode and cathode, respectively. The ASC exhibited a significantly improved capacitive performance in comparison with that of the symmetric supercapacitors fabricated with RGO–RuO2 or RGO–PANi as the electrodes. The improvement was attributed to the broadened potential window in an aqueous electrolyte, leading to an energy density of 26.3 W h kg−1, about two-times higher than that of the symmetrical supercapacitors based on RGO–RuO2 (12.4 W h kg−1) and RGO–PANi (13.9 W h kg−1) electrodes. In addition, a power density of 49.8 kW kg−1 was obtained at an energy density of 6.8 W h kg−1.

It is highly desirable to reduce the membrane thickness in order to maximize the throughput and break the trade-off limitation for membrane-based gas separation. Two-dimensional membranes composed of atomic-thick graphene or graphene oxide nanosheets have gas transport pathways that are at least three orders of magnitude higher than the membrane thickness, leading to reduced gas permeation flux and impaired separation throughput. Here we present nm-thick molecular sieving membranes composed of porous two-dimensional metal-organic nanosheets. These membranes possess pore openings parallel to gas concentration gradient allowing high gas permeation flux and high selectivity, which are proven by both experiment and molecular dynamics simulation. Furthermore, the gas transport pathways of these membranes exhibit a reversed thermo-switchable feature, which is attributed to the molecular flexibility of the building metal-organic nanosheets.

Storage of pure CO2 and CH4 and separation of their binary mixture in three different classes of nanostructured adsorbents--silicalite, C168 schwarzite, and IRMOF-1--have been compared at room temperature using atomistic simulation. CH4 is represented as a spherical Lennard-Jones molecule, and CO2 is represented as a rigid linear molecule with a quadrupole moment. For pure component adsorption, CO2 is preferentially adsorbed than CH4 in all the three adsorbents over the pressure range under this study, except in C168 schwarzite at high pressures. The simulated adsorption isotherms and isosteric heats match closely with available experimental data. A dual-site Langmuir-Freundlich equation is used to fit the isotherms satisfactorily. Compared to silicalite and C168 schwarzite, the gravimetric adsorption capacity of pure CH4 and CO2 separately in IRMOF-1 is substantially larger. This implies that IRMOF-1 might be a potential storage medium for CH4 and CO2. For adsorption from an equimolar binary mixture, CO2 is preferentially adsorbed in all three adsorbents. Predictions of mixture adsorption with the ideal-adsorbed solution theory on the basis of only pure component adsorption agree well with simulation results. Though IRMOF-1 has a significantly higher adsorption capacity than silicalite and C168 schwarzite, the adsorption selectivity of CO2 over CH4 is found to be similar in all three adsorbents.

Covalent organic frameworks (COFs) have emerged as a novel platform for material design and functional explorations, but it remains a challenge to synthetically functionalize targeted structures for task-specific applications. Optically pure 1,1'-bi-2-naphthol (BINOL) is one of the most important sources of chirality for organic synthesis and materials science, but it has not yet been used in construction of COFs for enantioselective processes. Here, by elaborately designing and choosing an enantiopure BINOL-based linear dialdehyde and a tris(4-aminophenyl)benzene derivative or tetrakis(4-aminophenyl)ethene as building blocks, two imine-linked chiral fluorescent COFs with a 2D layered hexagonal or tetragonal structure are prepared. The COF containing flexible tetraphenylethylene units can be readily exfoliated into ultrathin 2D nanosheets and electrospun to make free-standing nanofiber membrane. In both the solution and membrane systems, the fluorescence of COF nanosheets can be effectively quenched by chiral odor vapors via supramolecular interactions with the immobilized BINOL moieties, leading to remarkable chiral vapor sensors. Compared to the BINOL-based homogeneous and membrane systems, the COF nanosheets exhibited greatly enhanced sensitivity and enantioselectivity owing to the confinement effect and the conformational rigidity of the sensing BINOL groups in the framework. The ability to place such a useful BINOL chiral auxiliary inside open channels of COFs capable of amplifying chiral discrimination of the analytes represents a major step toward the rational synthesis of porous molecular materials for more chirality applications.

Functionalized graphene was prepared by reducing functionalized graphene oxide with poly(diallyldimethylammonium chloride) (PDDA), transferring the surface charge of reduced graphene oxide (RGO) from negative to positive. A composite material of functionalized RGO with manganese dioxide (MnO2) nanosheets can be obtained by dispersing negatively charged MnO2 nanosheets on the functionalized RGO sheets via an electrostatic coprecipitation method. The structures of composites were investigated by high-resolution transmission electron microscopy (HRTEM), which indicated that the MnO2 nanosheets dispersed on functionalized RGO sheets, exhibiting a layered structure. The composite material exhibited enhanced capacitive performances than those of pure functionalized RGO and Na-typed birnessite (Na/MnO2) sheets, attributing to the synergic effect of both components. Additionally, over 89% of original capacitance was retained after 1000 cycles, indicating a good cycle stability of the composite materials.