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We introduce high-performance supercapacitor electrodes with ternary components prepared from consecutive amphiphilic ligand-exchange-based layer-by-layer (LbL) assembly among amine-functionalized multi-walled carbon nanotubes (NH2-MWCNTs) in alcohol, oleic acid-stabilized Fe3O4 nanoparticles (OA-Fe3O4 NPs) in toluene, and semiconducting polymers (PEDOT:PSS) in water. The periodic insertion of semiconducting polymers within the (OA-Fe3O4 NP/NH2-MWCNT)n multilayer-coated indium tin oxide (ITO) electrode enhanced the volumetric and areal capacitances up to 408 ± 4 F cm−3 and 8.79 ± 0.06 mF cm−2 at 5 mV s−1, respectively, allowing excellent cycling stability (98.8% of the initial capacitance after 5000 cycles) and good rate capability. These values were higher than those of the OA-Fe3O4 NP/NH2-MWCNT multilayered electrode without semiconducting polymer linkers (volumetric capacitance ∼241 ± 4 F cm−3 and areal capacitance ∼1.95 ± 0.03 mF cm−2) at the same scan rate. Furthermore, when the asymmetric supercapacitor cells (ASCs) were prepared using OA-Fe3O4 NP- and OA-MnO NP-based ternary component electrodes, they displayed high volumetric energy (0.36 mW h cm−3) and power densities (820 mW cm−3).

We introduce a general and versatile methodology that allows a facile incorporation of the functional components with completely different chemistry of hydrophilic/hydrophobic properties within nanocomposite films, and furthermore combine a number of the distinctive advantages of traditional electrostatic layer-by-layer (LbL) assembly in aqueous media and covalent LbL assembly in nonpolar media. Our approach, amphiphilic LbL assembly, is based on the high affinity between sulfonic (or phosphonic) acid-functionalized materials in aqueous media and hydrophobic metal oxide (or metal) NPs stabilized by oleic acid (OA) in nonpolar solvent. For demonstrating the effectiveness of our approach, we show that amphiphilic LbL assembly can be easily applied to the preparation of functional colloid materials allowing the reversible phase transfer between aqueous and nonpolar media, and supercapacitor electrodes with high volumetric capacitance (280 F·cm(-3) at 10 mV·s(-1)) using reduced graphene oxide with sulfonic acid moieties and well-defined OA-Fe3O4 NPs.

There is rising demand for metal or metal oxide nanoparticle (NP)/polymer nanocomposite films with desired functionalities. However, it is difficult to directly combine well-defined NPs synthesized using organic fatty acids in nonpolar media with water-soluble polymers, except polyelectrolytes with specific functional moieties, because they differ in their hydrophobic/hydrophilic properties. We have developed a facile and universal hydrophilic/hydrophobic layer-by-layer (LbL) assembly method that enables perfect nanoblending between water-soluble polymers and hydrophobic NPs, maintaining their specific functionalities. Various hydrophobic NPs stabilized by using oleic acid (OA) (e.g., OA-TiO2, OA-Fe3O4, OA-Ag, and OA-Pt NPs) were directly LbL assembled with various water-soluble polymers (including biomaterials) containing carboxylic acid (–COOH), tertiary ammonium (N+), hydroxyl (–OH), and/or ether (–O–) groups. This adsorption behavior is based on the affinities between water-soluble polymers with multidentate binding sites and the surfaces of metal or metal oxide NPs stabilized by OA ligands. Our approach can be used to fabricate unipolar switching nonvolatile memory devices with ON/OFF current ratios greater than ∼1010 and good memory stability, despite the use of water-soluble polymers.

Despite a large number of developments of noble metal (or metal oxide) NP-based catalysts, it has been a great challenge to prepare high-performance recyclable catalysts with integrated functionalities that can be used in various solvent media. Here, we report on layer-by-layer (LbL) assembled multicatalysts with high catalytic performance, showing high dispersion and recycling stability in organic and aqueous media. The remarkable advantages of our approach are as follows. (i) Various metal or metal oxide NPs with desired catalytic performance can be easily incorporated into multilayered shells, forming densely packed arrays that allow one colloid to be used as a multicatalyst with highly integrated and controllable catalytic properties. (ii) Additionally, the dispersion stability of catalytic colloids in a desired solvent can be determined by the type of ultrathin outermost layer coating each colloid. (iii) Lastly, the covalent bonding between inorganic NPs and dendrimers within multilayer shells enhances the recycling stability of multicatalytic colloids. The resulting core-shell colloids including OA-Fe3O4 NPs, TOABr-Pd NPs, and OA-TiO2 NPs exhibited excellent performance in the oxidation of 3,3',5,5'-tetramethylbenzidine (TMB) and photocatalysis in aqueous media and in the Sonogashira coupling reaction (99% yield) in organic media. Given that the catalytic properties of recyclable colloids reported to date have entirely depended on the functionality of a single catalytic NP layer deposited onto colloids in selective solvent media, our approach provides a basis for the design and exploitation of high-performance recyclable colloids with integrated multicatalytic properties and high dispersion stability in a variety of solvents.

We introduce a general and facile method for the preparation of organic/inorganic nanoparticle (NP) nanocomposite multilayer films that allows vertical growth of various NP layers (i.e., metal or transition metal oxide NPs) in a densely packed structure. Our approach is based on the successive photo-crosslinking layer-by-layer (LbL) assembly between hydrophobic ligands onto a NP surface and photoinitiator (PI) molecules. Therefore, our approach requires neither the additional surface modification needed for well-defined NPs synthesized in organic media nor the deposition step that inserts a polymer layer bridge between adjacent inorganic NP layers in the preparation of traditional LbL-assembled NP films. We also demonstrate that photo-crosslinking LbL-assembled (metal oxide NP)n films could be used as a nonvolatile memory layer without a high-temperature thermal treatment, unlike conventional vacuum-deposition- or sol–gel-derived memory devices, which require thermal treatments at temperatures greater than 200 °C. This robust method could open a facile route for the design of functional NP-based electronic devices.