The development of versatile strategies toward two-dimensional (2D) porous nanocomposites with tunable pore structures draws immense scientific attention in view of their attractive physiochemical properties and a wide range of promising applications. This paper describes a self-assembly approach for the directed growth of mesoporous polyaniline (PANi) with tunable pore structures and sizes on ultrathin freestanding MoS2 nanosheets in solution, which produces 2D mesoporous PANi/MoS2 nanocomposites. The strategy employs spherical and cylindrical micelles, which are formed by the controlled solution self-assembly of block copolymers, as the soft templates for the construction of well-defined spherical and cylindrical mesopores in the 2D PANi/MoS2 nanocomposites, respectively. With potential applications as supercapacitor electrode materials, the resultant 2D composites show excellent capacitive performance with a maximum capacitance of 500 F g–1 at a current density of 0.5 A g–1, good rate performance, as well as outstanding stability for charge–discharge cycling. Moreover, the 2D mesoporous nanocomposites offer an opportunity for the study on the influence of different pore structures on their capacitive performance, which helps to understand the pore structure–property relationship of 2D porous electrode materials and to achieve their electrochemical performance control.Keywords: 2D materials; block copolymer; mesoporous; pore structure; self-assembly;

This letter reports the first 2D self-assembly of ABC miktoarm star terpolymers based on dual-responsive polycaprolactone-arm-poly(N-isopropylacrylamide)-arm-poly(2-dimethylaminoethyl methacrylate) (μ-CID), which self-assembled into multilayer nanosheets comprising polycaprolactone single crystals in tetrahydrofuran (THF)/methanol mixed solvents. Interestingly, the nanosheets showed pH-responsive morphological transitions in aqueous solutions, yielding multidimensional assemblies, including 2D hexagonal aggregates, patchy nanofibrils, and patchy vesicles, at different pH values. The nanosheets also exhibited thermoresponsive transition to spherical patchy micelles at a temperature above the lower critical solution temperature (LCST) of the poly(N-isopropylacrylamide) block. This study offers a novel system for fundamental study on the self-assembly of miktoarm star terpolymers.

AbstractWe herein report the tunable self-assembly of simple block copolymers, namely polystyrene-block-poly(ethylene oxide) (PS-b-PEO) diblock copolymers, into porous cubosomes with inverse or mesophases of controlled unit cell parameters as well as hexasomes with an inverse hexagonal (p6mm) structure, which have been rarely observed in polymer self-assembly. A new morphological phase diagram was constructed for the solution self-assembly of PS-b-PEO based on the volume fraction of the PS block against the initial copolymer concentration. The formation mechanisms of the cubosomes and hexasomes have also been revealed. This study not only affords a simple system for the controllable preparation and fundamental studies of ordered bicontinuous structures, but also opens up a new avenue towards porous architectures with highly ordered pores.

AbstractWe herein report the tunable self-assembly of simple block copolymers, namely polystyrene-block-poly(ethylene oxide) (PS-b-PEO) diblock copolymers, into porous cubosomes with inverse or mesophases of controlled unit cell parameters as well as hexasomes with an inverse hexagonal (p6mm) structure, which have been rarely observed in polymer self-assembly. A new morphological phase diagram was constructed for the solution self-assembly of PS-b-PEO based on the volume fraction of the PS block against the initial copolymer concentration. The formation mechanisms of the cubosomes and hexasomes have also been revealed. This study not only affords a simple system for the controllable preparation and fundamental studies of ordered bicontinuous structures, but also opens up a new avenue towards porous architectures with highly ordered pores.

ABSTRACTSolution self-assembly of amphiphilic “rod-coil” copolymers, especially linear block copolymers and graft copolymers (also referred to as polymer brushes), has attracted considerable interest, as replacing one of the blocks of a coil-coil copolymer with a rigid segment results in distinct self-assembly features compared with those of the coil-coil copolymer. The unique interplay between microphase separation of the rod and coil blocks with great geometric disparities can lead to the formation of unusual morphologies that are distinctly different from those known for coil-coil copolymers. This review presents the recent achievements in the controlled self-assembly of rod-coil linear block copolymers and graft copolymers in solution, focusing on copolymer systems containing conjugated polymers, liquid crystalline polymers, polypeptides, and polyisocyanates as the rod segments. The discussions concentrate on the principle of controlling over the morphology of rod-coil copolymer assemblies, as well as their distinctive optical and optoelectronic properties or biocompatibility and stimuli-responsiveness, which afford the assemblies great potential as functional materials particularly for optical, optoelectronic and biological applications. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 1459–1477

Structurally well-defined graphene nanoribbons (GNRs) have attracted great interest as next-generation semiconductor materials. The functionalization of GNRs with polymeric side chains, which can widely broaden GNR-related studies on physiochemical properties and potential applications, has remained unexplored. Here, we demonstrate the bottom-up solution synthesis of defect-free GNRs grafted with flexible poly(ethylene oxide) (PEO) chains. The GNR backbones possess an armchair edge structure with a width of 1.0–1.7 nm and mean lengths of 15–60 nm, enabling near-infrared absorption and a low bandgap of 1.3 eV. Remarkably, the PEO grafting renders the GNRs superb dispersibility in common organic solvents, with a record concentration of ∼1 mg mL–1 (for GNR backbone) that is much higher than that (<0.01 mg mL–1) of reported GNRs. Moreover, the PEO-functionalized GNRs can be readily dispersed in water, accompanying with supramolecular helical nanowire formation. Scanning probe microscopy reveals raft-like self-assembled monolayers of uniform GNRs on graphite substrates. Thin-film-based field-effect transistors (FETs) of the GNRs exhibit a high carrier mobility of ∼0.3 cm2 V–1 s–1, manifesting promising application of the polymer-functionalized GNRs in electronic devices.

This paper reports a novel and remarkably facile approach towards vertically aligned nanosheets on three-dimensional (3D) Ni foams. Conducting polypyrrole (PPy) sheets were grown on Ni foam through the volatilization of the environmentally friendly solvent from an ethanol–water solution of pyrrole (Py), followed by the polymerization of the coated Py in ammonium persulfate (APS) solution. The PPy-decorated Ni foams and commercial activated carbon (AC) modified Ni foams were employed as the two electrodes for the assembly of flexible all-solid-state asymmetric supercapacitors. The sheet-like structure of PPy and the macroporous feature of the Ni foam, which render large electrode–electrolyte interfaces, resulted in good capacitive performance of the supercapacitors. Moreover, a high energy density of ca. 14 Wh kg−1 and a high power density of 6.2 kW kg−1 were achieved for the all-solid-state asymmetric supercapacitors due to the wide cell voltage window.

This paper reports a simple self-assembly strategy towards bowl-shaped carbon-containing hollow particles, as well as an unprecedented potential application for block copolymer vesicles in energy storage. Kippah vesicles (fully collapsed vesicles), formed by solution self-assembly of an amphiphilic polystyrene-block-poly(ethylene oxide) block copolymer, were employed as the template to guide the formation of bowl-shaped nitrogen-doped carbon hollow particles (BNCHPs). As electrode materials of supercapacitors, BNCHPs exhibit superior electrochemical performance. In particular, compared with their spherical counterpart, BNCHPs largely increase their volumetric packing density, leading to much higher volumetric capacitance or volume reduction of electrodes, which is desired for practical supercapacitor devices.

This communication reports a unique ultra-large sheet formation through hierarchical self-assembly of a rod–coil graft copolymer containing a rigid polyphenylene backbone and flexible poly(ethylene oxide) (PEO) side chains. The hierarchical self-assembly process involved a distinctive morphological transition of 1D helical to 2D superstructures. The graft copolymer offers a new chance for the challenging bottom-up fabrication of ultra-large self-assembled nanosheets in solution, as well as a novel system for fundamental studies on 2D self-assembly of polymers.

We present a novel type of “rod–coil” graft copolymer containing a polyphenylene backbone linked with poly(ethylene oxide) (PEO) side chains. Such graft copolymers manifest unprecedented temperature-dependent one-dimensional (1D) and two-dimensional (2D) self-assembly in solution. At 20 °C, which is higher than the crystallization temperature (Tc) of the PEO chains, the achiral graft copolymers self-organize into nanoribbons that twist into ∼30 μm ultralong helices with controlled pitch depending on the grafting ratio of the PEO chains. At 10 °C, which is lower than the Tc, quadrangular multilayer sheets of over 10 μm in lateral size are obtained. To our knowledge, this work presents the first example of controlled self-assembly of graft polymers into 1D helix and 2D sheet superstructures.

This article presents a facile and effective approach for synthesizing three-dimensional (3D) graphene-coupled Schiff-base hierarchically porous polymers (GS-HPPs). The method involves the polymerization of melamine and 1,4-phthalaldehyde, yielding Schiff-base porous polymers on the interconnected macroporous frameworks of 3D graphene aerogels. The as-synthesized GS-HPPs possess hierarchically porous structures containing macro-/meso-/micropores, along with large specific surface areas up to 776 m2 g−1 and high nitrogen contents up to 36.8 wt%. Consequently, 3D nitrogen-enriched hierarchically porous carbon (N-HPC) materials with macro-/meso-/micropores were obtained by the pyrolysis of the GS-HPPs at a high temperature of 800 °C under a nitrogen atmosphere. With a hierarchically porous structure, good thermal stability and a high nitrogen-doping content up to 7.2 wt%, the N-HPC samples show a high specific capacitance of 335 F g−1 at 0.1 A g−1 in 6 M KOH, a good capacitance retention with increasing current density, and an outstanding cycling stability. The superior electrochemical performance means that the N-HPC materials have great potential as electrode materials for supercapacitors.