ABA-triblock copolyethers 1a-1c as linear polymeric binders, in combination with clay nanosheets (CNSs), afford high-water-content moldable supramolecular hydrogels with excellent mechanical properties by constructing a well-developed crosslinked network in water. The linear binders carry in their terminal A blocks guanidinium ion (Gu(+)) pendants for adhesion to the CNS surface, while their central B block comprises poly(ethylene oxide) (PEO) that serves as a flexible linker for adhered CNSs. Although previously reported dendritic binder 2 requires multistep synthesis and purification, the linear binders can be obtained in sizable quantities from readily available starting materials by controlled polymerization. Together with dendritic reference 2, the modular nature of compounds 1a-1c with different numbers of Gu(+) pendants and PEO linker lengths allowed for investigating how their structural parameters affect the gel network formation and hydrogel properties. The newly obtained hydrogels are mechanically as tough as that with 2, although the hydrogelation takes place more slowly. Irrespective of which binder is used, the supramolecular gel network has a shape memory feature upon drying followed by rewetting, and the gelling water can be freely replaced with ionic liquids and organic fluids, affording novel clay-reinforced iono- and organogels, respectively.

A general method to prepare polymer gels containing anisotropically oriented graphene oxide (GO) or reduced graphene oxide (RGO) was developed, by using the magnetically induced orientation of GO. Under a magnetic field, an aqueous dispersion of GO was gelated by in situ cross-linking polymerization of an acryl monomer and a cross-linker. In the resultant hydrogel, the orientation of GO was retained even in the absence of the magnetic field, because the gel network trapped GO via noncovalent interactions and efficiently suppressed the structural relaxation of GO. The locked structure enabled quantitative investigation on the magnetic orientation of GO using 2D small-angle X-ray scattering, which revealed that GO nanosheets orient parallel to the magnetic field with an order parameter of up to 0.80. Systematic studies with varying gelation conditions indicate that the present method can afford a wide range of GO-hybridized anisotropic materials, in terms of GO alignment direction, sample shape, and GO concentration. Also by virtue of the locked structure, the orientation of GO in the hydrogel was well preserved throughout the in situ chemical reduction of GO, yielding an RGO-hybridized anisotropic hydrogel, as well as the conversion of the hydrogel into organo- and ionogels through the replacement of the internal water with solvents. As a preliminary demonstration of the present method for practical application, a polymer-composite film containing RGO oriented vertical to the film surface was prepared, and its anisotropically enhanced electroconductivity along the orientation direction of RGO was confirmed by the flash-photolysis time-resolved microwave conductivity measurement.

A facile anisotropic surface modification and etching strategy is presented for the synthesis of hollow structured ZIF‐67 nanoframes. The strategy uses structural and compositional distinctions between each crystallographic facet of truncated rhombic dodecahedrons ZIF‐67 (tZIF‐67 RDs) and the moderate coordinating and etching effects of cyanuric acid (CA). The CA can anisotropically modify and protect the {110} facets from etching, causing the six {100} facets be selectively etched via an inside‐out manner, and finally forming the hollow nanoframes. The surface‐modified hollow tZIF‐67 RDs can be facet‐selectively etched by metal salts in an outside‐in manner to give metal‐doped tZIF‐67 nanoframes. After calcination, the metal‐tZIF‐67 hybrids are converted into metal‐Co alloy/C composite catalysts with hollow nanoframed structures. The PtCo/C catalyst with only 5.9 wt % Pt exhibits high catalytic activities and stabilities in the hydrogen evolution reaction (HER) in acidic solutions.

Potential distribution at the electrode/solution interface is discussed for metal electrodes coated with a redox-active self-assembled monolayer, taking inclusion of ion pairs and triple ion formation into consideration. Theory on current−voltage curves obtained by potential sweep experiments is derived for these special cases. Explicit expressions derived in this study for the peak current and the peak potential are similar in their forms to those published previously using the Frumkin adsorption isotherm. A graphical method to evaluate the average local potential in the double layer of real systems is proposed.

The electron-transfer reduction of cup-stacked carbon nanotubes (CSCNTs) with sodium naphthalenide and the subsequent treatment with 1-iodododecane results in electrostatically destacking of CSCNTs to afford cup-shaped carbons with controlled diameter and size. The dodecylated cup-shaped carbons were highly dispersed and stable in nonpolar solvents, such as THF, tetrachloroethylene, and chloroform, as compared with the pristine CSCNTs.