Yonghyun Kwon

Lanthanum-catalysed synthesis of microporous 3D graphene-like carbons in a zeolite template

Three-dimensional graphene architectures with periodic nanopores—reminiscent of zeolite frameworks—are of topical interest because of the possibility of combining the characteristics of graphene with a three-dimensional porous structure. Lately, the synthesis of such carbons has been approached by using zeolites as templates and small hydrocarbon molecules that can enter the narrow pore apertures. However, pyrolytic carbonization of the hydrocarbons (a necessary step in generating pure carbon) requires high temperatures and results in non-selective carbon deposition outside the pores. Here, we demonstrate that lanthanum ions embedded in zeolite pores can lower the temperature required for the carbonization of ethylene or acetylene. In this way, a graphene-like carbon structure can be selectively formed inside the zeolite template, without carbon being deposited at the external surfaces. X-ray diffraction data from zeolite single crystals after carbonization indicate that electron densities corresponding to carbon atoms are generated along the walls of the zeolite pores. After the zeolite template is removed, the carbon framework exhibits an electrical conductivity that is two orders of magnitude higher than that of amorphous mesoporous carbon. Lanthanum catalysis allows a carbon framework to form in zeolite pores with diameters of less than 1 nanometre; as such, microporous carbon nanostructures can be reproduced with various topologies corresponding to different zeolite pore sizes and shapes. We demonstrate carbon synthesis for large-pore zeolites (FAU, EMT and beta), a one-dimensional medium-pore zeolite (LTL), and even small-pore zeolites (MFI and LTA). The catalytic effect is a common feature of lanthanum, yttrium and calcium, which are all carbide-forming metal elements. We also show that the synthesis can be readily scaled up, which will be important for practical applications such as the production of lithium-ion batteries and zeolite-like catalyst supports.

N-doped zeolite-templated carbon as a metal-free electrocatalyst for oxygen reduction

Nitrogen-doped, zeolite-templated carbon was synthesized using aqueous acetonitrile as a nitrogen-containing carbon source, and beta zeolite as a template. The carbon had a three-dimensionally ordered microporous structure with a large surface area, which consisted of sp2-carbon. The nitrogen content was approximately 4 wt%. In the electrocatalytic oxygen reduction reaction, the nitrogen-doped zeolite-templated carbon showed a notably high current density and a positive onset potential as compared to nitrogen-doped reduced graphene oxide. The surface of this carbon also had a lower work function than that of planar graphene. The high catalytic performance with the low work function of this carbon seems to come from a curved graphene-like framework structure containing nitrogen.

Extremely high electrical conductance of microporous 3D graphene-like zeolite-templated carbon framework

We report the remarkably high electrical conductance of microporous 3D graphene-like carbons that were formed using lanthanum (La)-catalyzed synthesis in a Y zeolite (LaY) template investigated using conductive atomic force microscopy (C-AFM) and theoretical calculations. To uncover the relation between local electrical conductance and the microporous structures, we tuned the crystallographic ordering of LaY-templated carbon systems by changing the heating temperature. The structure of the LaY-templated carbon prepared at the higher temperature has graphene-like sp2 hybridized bonds, which was confirmed using high-resolution transmission electron microscopy and X-ray diffraction measurements. C-AFM current–voltage spectroscopy revealed that the local current flow in the LaY-templated carbon depends on the quantity of C–C bonds within the narrow neck between the closed supercages (i.e. there are three types of carbon: carbon with heat treatment, carbon without heat treatment, and carbon synthesized at low temperature). The difference in electrical conductance on the LaY-templated carbon was also confirmed via theoretical computation using the Boltzmann transport theory and the deformation potential theory based on the density functional theory. These results suggest that the degree of order of the pores in the 3D zeolite-templated carbon structures is directly related to electrical conductance.

Nanocage-Confined Synthesis of Fluorescent Polycyclic Aromatic Hydrocarbons in Zeolite

Polycyclic aromatic hydrocarbons (PAHs) attract much attention for applications to organic light-emitting diodes, field-effect transistors, and photovoltaic cells. The current synthetic approaches to PAHs involve high-temperature flash pyrolysis or complicated step-by-step organic reactions, which lead to low yields of PAHs. Herein, we report a facile and scalable synthesis of PAHs, which is carried out simply by flowing acetylene gas into zeolite under mild heating, typically at 400 °C and generates the products of 0.30 g g-1 zeolite. PAHs are synthesized via acetylene polymerization inside Ca2+-ion-exchanged Linde type A (LTA) zeolite, of which the α-cage puts a limit on the product molecular size as a confined-space nanoreactor. The resultant product after the removal of the zeolite framework exhibits brilliant white fluorescence emission in N-methylpyrrolidone solution. The product is separated into four different color emitters (violet, blue, green, and orange) by column chromatography. Detailed characterizations of the products by means of various spectroscopic methods and mainly mass spectrometric analyses indicate that coronene (C24H12) is the main component of the blue emitter, while the green emitter is a mixture of planar and curved PAHs. The orange can be attributed to curved PAHs larger than ovalene, and the violet to smaller molecules than coronene. The PAH growth mechanism inside Ca2+-exchanged LTA zeolite is proposed on the basis of mass spectral analyses and density functional theory calculations.

The Knock-On Effect in Business Group: Evidence from Korean Chaebols Credit Rating Changes

We examine the knock-on effect of credit rating changes in Korean Chaebol. We show that credit rating changes of chaebol-affiliated firm share the effect of credit rating change with related affiliates because: (1) chaebol affiliates share their internal capital markets and (2) chaebol affiliates are bounded together by cross-holdings. We conclude that impact of credit rating change of chaebol-affiliated firm spills over to other affiliates included in the same chaebols, and cross-holdings may determine the extent of the knock-on effect.