Kie Yong Cho

Rational design of multiamphiphilic polymer compatibilizers: Versatile solubility and hybridization of noncovalently functionalized CNT nanocomposites

The design of amphiphilic polymer compatibilizers for solubility manipulation of CNT composites was systematically generalized in this study. Structurally tailored multiamphiphilic compatibilizer were designed and synthesized by applying simple, high-yield reactions. This multiamphiphilic compatibilizer was applied for noncovalent functionalization of CNTs as well as provided CNTs with outstanding dispersion stability, manipulation of solubility, and hybridization with Ag nanoparticles (NPs). With regard to the dispersion properties, superior records in maximum concentration (2.88-3.10 mg/mL in chloroform), and mass ratio of the compatibilizer for good CNT dispersion (36 wt %) were achieved by MWCNTs functionalized with a multiamphiphilic block copolymer compatibilizer. In particular, the solubility limitations of MWCNT dispersion in solvents ranging from toluene (nonpolar) to aqueous solution (polar) are surprisingly resolved by introducing this multiamphiphilic polymer compatibilizer. Furthermore, this polymer compatibilizer allowed the synthesis of the hybrid CNT nanocomposites with Ag nanoparticles by an in situ nucleation process. As such, the multiamphiphilic compatibilizer candidate as a new concept for the noncovalent functionalization of CNTs can extend their use for a wide range of applications.

Ionic block copolymer doped reduced graphene oxide supports with ultra-fine Pd nanoparticles: strategic realization of ultra-accelerated nanocatalysis

We synthesized an ultra-fine Pd nanocatalyst supported by ionic block copolymer doped reduced graphene oxide (Pd-PIBrGO) for ultra-accelerated nanocatalysis. This hybrid catalyst exhibited exceptionally advanced catalytic performance for the reduction of methylene blue using miniscule quantities of Pd-PIBrGO due to facilitated diffusion of reagents, resulting in full reduction within a few seconds and showing a 280-fold increase of the rate constant over Pd-rGO without ionic block copolymers.

Molybdenum-Doped PdPt@Pt Core-Shell Octahedra Supported by Ionic Block Copolymer-Functionalized Graphene as a Highly Active and Durable Oxygen Reduction Electrocatalyst.

Development of highly active and durable electrocatalysts that can effectively electrocatalyze oxygen reduction reactions (ORR) still remains one important challenge for high-performance electrochemical conversion and storage applications such as fuel cells and metal-air batteries. Herein, we propose the combination of molybdenum-doped PdPt@Pt core-shell octahedra and the pyrene-functionalized poly(dimethylaminoethyl methacrylate)-b-poly[(ethylene glycol) methyl ether methacrylate] ionic block copolymer-functionalized reduced graphene oxide (Mo-PdPt@Pt/IG) to effectively augment the interfacial cohesion of both components using a tunable ex situ mixing strategy. The rationally designed Mo-PdPt@Pt core-shell octahedra have unique compositional benefits, including segregation of Mo atoms on the vertexes and edges of the octahedron and 2-3 shell layers of Pt atoms on a PdPt alloy core, which can provide highly active sites to the catalyst for ORR along with enhanced electrochemical stability. In addition, the ionic block copolymer functionalized graphene can facilitate intermolecular charge transfer and good stability of metal NPs, which arises from the ionic block copolymer interfacial layer. When the beneficial features of the Mo-PdPt@Pt and IG are combined, the Mo-PdPt@Pt/IG exhibits substantially enhanced activity and durability for ORR relative to those of commercial Pt/C. Notably, the Mo-PdPt@Pt/IG shows mass activity 31-fold higher than that of Pt/C and substantially maintains high activities after 10 000 cycles of intensive durability testing. The current study highlights the crucial strategies in designing the highly active and durable Pt-based octahedra and effective combination with functional graphene supports toward the synergetic effects on ORR.

A facile synthetic route for highly durable mesoporous platinum thin film electrocatalysts based on graphene: morphological and support effects on the oxygen reduction reaction

Porous-structured noble metal electrocatalysts offer activity and durability benefits based on a high surface area and interconnected nanostructure, respectively. However, conventional technical methods used for synthesizing a porous structure are still difficult as well as resulting in defects in the structure. Here we report a facile route for the synthesis of uniform, large-area mesoporous platinum thin films based on ionic polymer doped graphene, which exhibit substantially enhanced activity and durability for oxygen reduction relative to commercial Pt/C. Notably, a remarkable durability (≥95% retention of electrochemical activities after 30 000 cycles of intensive accelerated durability tests) is acquired which is ascribed to the synergistic effects derived from the interconnected Pt structure (morphology) and ionic polymer-doped graphene (support). The suggested robust concept for a controlled mesoporous-structured platinum thin film on graphene could be a great breakthrough for obtaining a highly durable electrocatalyst.

An asymmetric electrically conducting self-aligned graphene/polymer composite thin film for efficient electromagnetic interference shielding

Here, we study the self-aligned asymmetric electrically conductive composite thin film prepared via casting of graphene oxide (GO)/poly (vinylidene-hexafluoropropylene) (PVDF-HFP) dispersion, followed by low temperature hydriodic acid reduction. The results showed that composite thin film revealed the high orientation of graphene sheets along the direction of film surface. However, graphene sheets are asymmetrically distributed along the film thickness direction in the composite film. Both sides of as prepared composite film showed different surface characteristics. The asymmetric surface properties of composite film induced distinction of surface resistivity response; top surface resistivity (21 Ohm) is ∼ 4 times higher than bottom surface resistivity (5 Ohm). This asymmetric highly electrically conducting composite film revealed efficient electromagnetic interference (EMI) shielding effectiveness of ∼ 30 dB. This study could be crucial for achieving aligned asymmetric composite thin film for high-perfor...

Recyclable palladium–graphene nanocomposite catalysts containing ionic polymers: efficient Suzuki coupling reactions

Palladium nanoparticles on ionic polymer-doped graphene (Pd–IPG) nanocomposite catalysts have been investigated for efficient Suzuki coupling reactions. This combination effected highly accelerated Suzuki coupling reactions due to several advantageous features associated with the flanking ionic polymer part of the catalyst system. These include a high level of Pd incorporation, excellent dispersion stability, and increased accessibility and diffusion of the substrates onto the surface of Pd NPs. The enhanced availability of the Pd catalyst to the reacting substrates is believed to allow for ca. 16-fold higher catalytic activity than that of Pd–graphene without the ionic polymer. Moreover, high recycling capability of the catalyst (10 times) in combination with excellent product yields (>96%) and no significant leaching of the catalyst upon hot-filtration test suggest that the Pd–IPG nanocomposite catalysts have high reusability with significant retention (>95%) of the Pd species.

Control of hard block segments of methacrylate-based triblock copolymers for enhanced electromechanical performance

A series of well-defined hard–soft–hard triblock copolymers were synthesized by Ru-based atom transfer radical polymerization (ATRP) (MWD < 1.26) in order to examine their electromechanical properties under electric fields. The obtained methacrylate based triblock copolymers consisted of poly(dodecyl methacrylate) (PDMA) soft middle block segments and three different hard block segments with poly(methyl methacrylate) (PMMA), poly(tert-butyl methacrylate) (PtBMA), and their random copolymers (PMTDTMTs). Polar acidified triblock copolymers were also prepared by deprotecting tert-butyl groups in tBMA-incorporating hard block segments through simple thermal treatment at 200 °C for 120 min, which in situ gave poly(methacrylic acid) (PMAA) and its random copolymers (PAMDMA) in the hard block segments. SAXS and AFM studies indicated that these triblock copolymers showed well-organized phase separations with different domain sizes, which were strongly dependent on the amount of bulky PtBMA or polar PMAA in the hard block segments. In addition, these triblock copolymers had a variety of morphologies affecting their mechanical (elastic modulus) and electrical (dielectric constant) properties, leading to a tuning of their electromechanical properties. The transverse strains of these triblock random copolymers as a function of an applied electric field indicated that the PTMDMT series possessed the best electromechanical properties, exhibiting an 11-fold enhancement relative to the corresponding acidified polymer PAMDMA at 50 Vpp μm−1 due to a dramatic decrease of the elastic modulus from 4.04 to 0.05 MPa in spite of an increase of the dielectric constant from 3.6 to 5.1. In situ SAXS analysis under an electric field showed that these bulk strains originated from nano-structured microdomain changes.

Controlled synthesis of multi-armed P3HT star polymers with gold nanoparticle core

Well-defined multi-armed P3HT star polymers with a gold nanoparticle (NP) core were synthesized by an arm-first method based on a ligand exchange reaction between linear end-functionalized P3HT (P3HT-SH) and gold NPs. A high loading amount of gold NPs to P3HT-SH with a relatively lower molecular weight gave a higher yield of star polymers (∼70%) with a high molecular weight (Mw = 2867k, PDI = 2.1), and the number of P3HT arm chains on one gold NP was 119. The P3HT star polymer with a gold NP core was well-dispersed both in solution and in solid, which was interestingly not crystalline because of the unique 3-dimenstional structure. In addition, surface plasmon resonance (SPR) absorption from the gold NP, as the core of the star polymer, was more enhanced both in solution and in solid, in comparison to those with non end-functionalized P3HT arm chains (P3HT-allyl); however, PL emission was more diminished because of the molecularly contacted P3HT arm chain and gold NP core. This was then introduced in an active layer consisting of P3HT:PCBM in an organic solar cell to increase optical absorption by the SPR effect from the gold NP, however, the device efficiency was rather decreased compared to that of the reference device without gold NPs, which was probably due to direct electron transfer between the gold NP and P3HT.

Enhanced Electrical Properties of PVDF-TrFE Nanocomposite for Actuator Application

Carbon nanotubes (CNTs) coated by compatibilizer (P3HT-PMMA) imparted sta-ble dispersion in organic solvents and polymer matrix (P(VDF-TrFE)). The compatibility be-tween CNTs with P3HT-PMMA was con rmed by measuring Raman spectroscopy. CoatedCNTs were then blended with P(VDF-TrFE) (70:30 mol%) to obtain polymer nanocompositesby solution- casting process. Polymer nanocomposites showed enhanced electrical characteris-tics, as nanocomposites near the threshold of the transition between P(VDF-TrFE) insulatorand CNT conductor revealed great improvement of electrical conductivity up to 10-6 S/cmat 1 KHz. Electromechanical properties of the polymer nanocomposite were examined as afunction of electric eld.

Synthesis of amine-functionalized ZIF-8 with 3-amino-1,2,4-triazole by postsynthetic modification for efficient CO2-selective adsorbents and beyond

The facile tuning of the gate size and the chemical functionalization of zeolitic imidazolate frameworks (ZIFs) have been considered efficient strategies for various potential applications including gas membranes, sensors, and catalysts. Herein, we demonstrate the synthesis of amine-functionalized ZIF-8 (ZIF8-A) with 3-amino-1,2,4-triazole (Atz) by postsynthetic modification (PSM) towards two objectives: (1) CO2 selective adsorption by a combination of chemical interactions and controlled gate sizes and (2) potential for further chemical modifications. The acquired ZIF8-A substantially enhanced CO2/N2 and CO2/CH4 selectivity at 35 °C compared to ZIF-8 since the Atz conversion enhanced chemical interactions with CO2 due to the introduction of amine moieties while reducing both the surface area and pore volume. The gate size control of ZIF-8 by the replacement of Atz was thoroughly investigated by extensive transport experiments and density functional theory (DFT)-based computational simulations. In addition, the vinyl-functionalized ZIF-8, another versatile starting material, was successfully prepared by further chemical modifications of ZIF8-A with either methacrylic anhydride or glycidyl methacrylate through nucleophilic substitution reactions. As such, we believe that our current work can provide promising platforms for designing ZIF-based materials with versatile properties including precise control of the gate size and the incorporation of various functional groups.