Jongkook Hwang

Facile Synthesis of Nb2O5@Carbon Core–Shell Nanocrystals with Controlled Crystalline Structure for High-Power Anodes in Hybrid Supercapacitors

Hybrid supercapacitors (battery-supercapacitor hybrid devices, HSCs) deliver high energy within seconds (excellent rate capability) with stable cyclability. One of the key limitations in developing high-performance HSCs is imbalance in power capability between the sluggish Faradaic lithium-intercalation anode and rapid non-Faradaic capacitive cathode. To solve this problem, we synthesize Nb2O5@carbon core-shell nanocyrstals (Nb2O5@C NCs) as high-power anode materials with controlled crystalline phases (orthorhombic (T) and pseudohexagonal (TT)) via a facile one-pot synthesis method based on a water-in-oil microemulsion system. The synthesis of ideal T-Nb2O5 for fast Li(+) diffusion is simply achieved by controlling the microemulsion parameter (e.g., pH control). The T-Nb2O5@C NCs shows a reversible specific capacity of ∼180 mA h g(-1) at 0.05 A g(-1) (1.1-3.0 V vs Li/Li(+)) with rapid rate capability compared to that of TT-Nb2O5@C and carbon shell-free Nb2O5 NCs, mainly due to synergistic effects of (i) the structural merit of T-Nb2O5 and (ii) the conductive carbon shell for high electron mobility. The highest energy (∼63 W h kg(-1)) and power (16 528 W kg(-1) achieved at ∼5 W h kg(-1)) densities within the voltage range of 1.0-3.5 V of the HSC using T-Nb2O5@C anode and MSP-20 cathode are remarkable.

Mesoporous Ge/GeO2/Carbon Lithium-Ion Battery Anodes with High Capacity and High Reversibility.

We report mesoporous composite materials (m-GeO2, m-GeO2/C, and m-Ge-GeO2/C) with large pore size which are synthesized by a simple block copolymer directed self-assembly. m-Ge/GeO2/C shows greatly enhanced Coulombic efficiency, high reversible capacity (1631 mA h g(-1)), and stable cycle life compared with the other mesoporous and bulk GeO2 electrodes. m-Ge/GeO2/C exhibits one of the highest areal capacities (1.65 mA h cm(-2)) among previously reported Ge- and GeO2-based anodes. The superior electrochemical performance in m-Ge/GeO2/C arises from the highly improved kinetics of conversion reaction due to the synergistic effects of the mesoporous structures and the conductive carbon and metallic Ge.

Designing a Highly Active Metal‐Free Oxygen Reduction Catalyst in Membrane Electrode Assemblies for Alkaline Fuel Cells: Effects of Pore Size and Doping‐Site Position

To promote the oxygen reduction reaction of metal-free catalysts, the introduction of porous structure is considered as a desirable approach because the structure can enhance mass transport and host many catalytic active sites. However, most of the previous studies reported only half-cell characterization; therefore, studies on membrane electrode assembly (MEA) are still insufficient. Furthermore, the effect of doping-site position in the structure has not been investigated. Here, we report the synthesis of highly active metal-free catalysts in MEAs by controlling pore size and doping-site position. Both influence the accessibility of reactants to doping sites, which affects utilization of doping sites and mass-transport properties. Finally, an N,P-codoped ordered mesoporous carbon with a large pore size and precisely controlled doping-site position showed a remarkable on-set potential and produced 70% of the maximum power density obtained using Pt/C.

Direct access to hierarchically porous inorganic oxide materials with three-dimensionally interconnected networks.

Hierarchically porous oxide materials have immense potential for applications in catalysis, separation, and energy devices, but the synthesis of these materials is hampered by the need to use multiple templates and the associated complicated steps and uncontrollable mixing behavior. Here we report a simple one-pot strategy for the synthesis of inorganic oxide materials with multiscale porosity. The inorganic precursor and block copolymer are coassembled into an ordered mesostructure (microphase separation), while the in situ-polymerized organic precursor forms organic-rich macrodomains (macrophase separation) around which the mesostructure grows. Calcination generates hierarchical meso/macroporous SiO2 and TiO2 with three-dimensionally interconnected pore networks. The continuous 3D macrostructures were clearly visualized by nanoscale X-ray computed tomography. The resulting TiO2 was used as the anode in a lithium ion battery and showed excellent rate capability compared with mesoporous TiO2. This work is of particular importance because it (i) expands the base of BCP self-assembly from mesostructures to complex porous structures, (ii) shows that the interplay of micro- and macrophase separation can be fully exploited for the design of hierarchically porous inorganic materials, and therefore (iii) provides strategies for researchers in materials science and polymer science.

One-Pot Synthesis of Intermetallic Electrocatalysts in Ordered, Large-Pore Mesoporous Carbon/Silica toward Formic Acid Oxidation

This study describes the one-pot synthesis and single-cell characterization of ordered, large-pore (>30 nm) mesoporous carbon/silica (OMCS) composites with well-dispersed intermetallic PtPb nanoparticles on pore wall surfaces as anode catalysts for direct formic acid fuel cells (DFAFCs). Lab-synthesized amphiphilic diblock copolymers coassemble hydrophobic metal precursors as well as hydrophilic carbon and silica precursors. The final materials have a two-dimensional hexagonal-type structure. Uniform and large pores, in which intermetallic PtPb nanocrystals are significantly smaller than the pore size and highly dispersed, enable pore backfilling with ionomers and formation of the desired triple-phase boundary in single cells. The materials show more than 10 times higher mass activity and significantly lower onset potential for formic acid oxidation as compared with commercial Pt/C, as well as high stability due to better resistivity toward CO poisoning. In single cells, the maximum power density was higher than that of commercial Pt/C, and the stability highly improved, compared with commercial Pd/C. The results suggest that PtPb-based catalysts on large-pore OMCSs may be practically applied as real fuel cell catalysts for DFAFC.

Ordered mesoporous tungsten suboxide counter electrode for highly efficient iodine-free electrolyte-based dye-sensitized solar cells.

A disulfide/thiolate (T(2)/T(-)) redox-couple electrolyte, which is a promising iodine-free electrolyte owing to its transparent and noncorrosive properties, requires alternative counter-electrode materials because conventional Pt shows poor catalytic activity in such an electrolyte. Herein, ordered mesoporous tungsten suboxide (m-WO(3-x)), synthesized by using KIT-6 silica as a hard template followed by a partial reduction, is used as a catalyst for a counter electrode in T(2)/T(-)-electrolyte-based dye-sensitized solar cells (DSCs). The mesoporous tungsten suboxide, which possesses interconnected pores of 4 and 20 nm, provides a large surface area and efficient electrolyte penetration into the m-WO(3-x) pores. In addition to the advantages conferred by the mesoporous structure, partial reduction of tungsten oxide creates oxygen vacancies that can function as active catalytic sites, which causes a high electrical conductivity because of intervalence charge transfer between the W(5+) and W(6+) ions. m-WO(3-x) shows a superior photovoltaic performance (79 % improvement in the power conversion efficiency) over Pt in the T(2)/T(-) electrolyte. The superior catalytic activity of m-WO(3-x) is investigated by using cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and Tafel polarization curve analysis.

Ammonium Fluoride Mediated Synthesis of Anhydrous Metal Fluoride–Mesoporous Carbon Nanocomposites for High-Performance Lithium Ion Battery Cathodes

Metal fluorides (MFx) are one of the most attractive cathode candidates for Li ion batteries (LIBs) due to their high conversion potentials with large capacities. However, only a limited number of synthetic methods, generally involving highly toxic or inaccessible reagents, currently exist, which has made it difficult to produce well-designed nanostructures suitable for cathodes; consequently, harnessing their potential cathodic properties has been a challenge. Herein, we report a new bottom-up synthetic method utilizing ammonium fluoride (NH4F) for the preparation of anhydrous MFx (CuF2, FeF3, and CoF2)/mesoporous carbon (MSU-F-C) nanocomposites, whereby a series of metal precursor nanoparticles preconfined in mesoporous carbon were readily converted to anhydrous MFx through simple heat treatment with NH4F under solventless conditions. We demonstrate the versatility, lower toxicity, and efficiency of this synthetic method and, using XRD analysis, propose a mechanism for the reaction. All MFx/MSU-F-C prepared in this study exhibited superior electrochemical performances, through conversion reactions, as the cathode for LIBs. In particular, FeF3/MSU-F-C maintained a capacity of 650 mAh g-1FeF3 across 50 cycles, which is ∼90% of its initial capacity. We expect that this facile synthesis method will trigger further research into the development of various nanostructured MFx for use in energy storage and other applications.

Multiscale Phase Separations for Hierarchically Ordered Macro/Mesostructured Metal Oxides

Porous architectures play an important role in various applications of inorganic materials. Several attempts to develop mesoporous materials with controlled macrostructures have been reported, but they usually require complicated multiple-step procedures, which limits their versatility and suitability for mass production. Here, a simple approach for controlling the macrostructures of mesoporous materials, without templates for the macropores, is reported. The controlled solvent evaporation induces both macrophase separation via spinodal decomposition and mesophase separation via block copolymer self-assembly, leading to the formation of hierarchically porous metal oxides with periodic macro/mesostructures. In addition, using this method, macrostructures of mesoporous metal oxides are controlled into spheres and mesoporous powders containing isolated macropores. Nanocomputed tomography, focused ion beam milling, and electron microscopy confirm well-defined macrostructures containing mesopores. Among the various porous structures, hierarchically macro/mesoporous metal oxide is employed as an anode material in lithium-ion batteries. The present approach could provide a broad and easily accessible platform for the manufacturing of mesoporous inorganic materials with different macrostructures.

One pot synthesis of mesoporous boron nitride using polystyrene-b-poly(ethylene oxide) block copolymer

We report a successful synthesis of Mesoporous BN (MBN) powder through a facile one-pot synthesis strategy. In this respect, laboratory made block copolymer, polystyrene-b-poly(ethylene oxide) (PS-b-PEO) was used as structure directing agent and ammonia borane was used as BN precursor, respectively. Various characterization techniques such as X-ray photoelectron spectroscopy, Fourier-transform infrared spectroscopy, X-ray diffraction (XRD), scanning electron microscopy, transmission electron microscopy (TEM) and N2 sorption analysis were used to characterize different properties of the synthesized MBN powder. The formation of turbostratic boron nitride with wormlike pores (20 nm) was confirmed by XRD and TEM results. N2 sorption analysis of the obtained MBN sample exhibited a high specific surface area of 326 m2 g−1 and a pore volume of 0.5 m3 g−1.

Direct access to aggregation-free and small intermetallic nanoparticles in ordered, large-pore mesoporous carbon for an electrocatalyst

An intermetallic catalyst with ordered atomic arrays has a higher electrocatalytic activity than alloy, but the high temperature required for the formation makes the particles large, resulting in low mass activity. We report the simple synthesis of small Pt-based intermetallic nanoparticles on a carbon-based ordered mesoporous support by combining block copolymer-assisted evaporation-induced self-assembly and strong metal-support interaction (SMSI). Aluminosilicate in the mesostructured wall is an SMSI agent and charge transfer from Pt to the aluminosilicate suppresses the sintering of intermetallic nanoparticles. Intermetallic PtPb and Pt3Co on carbon-based mesoporous supports are synthesized, and their particle sizes are below 5 nm even at high loading. The PtPb catalyst shows 15 times higher mass activity for formic acid oxidation than Pt/C, and the Pt3Co catalyst shows 3.25 times higher mass activity for oxygen reduction than Pt/C. This procedure can be extended to synthesize various heterogenous catalysts that require high temperature for synthesis or to operate.