• Bulletin of the Korean Chemical Society
• /
• v.33 no.12
• /
• pp.4084-4092
• /
• 2012

Theoretical calculations based on density functional theory (DFT) were performed to study the substituent effect on the geometric and electronic structures as well as the biological behavior of technetium-99m-labeled diphosphonate complexes. Optimized structures of these complexes are surrounded by six ligands in an octahedral environment with three unpaired 4d electrons ($d^3$ state) and the optimized geometry of $^{99m}Tc$-MDP agrees with experimental data. With the increase of electron-donating substituent or tether between phosphate groups, the energy gap between frontier orbitals increases and the probability of non-radiative deactivation via d-d electron transfer decreases. The charge distribution reflects a significant ligand-to-metal electron donation. Based on the calculated geometric and electronic structures and biologic properties of $^{99m}Tc$-diphosphonate complexes, several structure-activity relationships (SARs) were established. These results may be instructive for the design and synthesis of novel $^{99m}Tc$-diphosphonate bone imaging agent and other $^{99m}Tc$-based radiopharmaceuticals.

• Journal of Electrochemical Science and Technology
• /
• v.13 no.3
• /
• pp.362-368
• /
• 2022

The application of polymer composite electrolyte in all-solid-state lithium-sulfur battery (ASSLSBs) can guarantee high energy density and improve the interface contact between electrolyte and electrode, which has a broader application prospect. However, the inherent insulation of the sulfur-cathode leads to a low electron/ion transfer rate. Carbon materials with high electronic conductivity and electrolyte materials with high ionic conductivity are usually selected to improve the electron/ion conduction of the composite cathode. In this work, PEO-LiTFSI-LLZO composite polymer electrolyte (CPE) with high ionic conductivity was prepared. The ionic conductivity was 1.16×10^-4 and 7.26×10^-4 S cm^-1 at 20 and 60℃, respectively. Meanwhile, the composite sulfur cathode was prepared with Sulfur, reduced graphene oxide and composite polymer electrolyte slurry (S-rGO-CPEs). In addition to improving the ion conductivity in the cathode, CPEs also replaces the role of binder. The influence of different contents of CPEs in the cathode material on the performance of the constructed battery was investigated. The results show that the electrochemical performance of the all-solid-state lithium-sulfur battery is the best when the content of the composite electrolyte in the cathode is 40%. Under the condition of 0.2C and 45℃, the charging and discharging capacity of the first cycle is 923 mAh g^-1, and the retention capacity is 653 mAh g^-1 after 50 cycles.

• Korean Chemical Engineering Research
• /
• v.61 no.1
• /
• pp.52-57
• /
• 2023

This study is a basic research for the development of high performance flexible electrode material. To enhance its electrochemical property, CuO nanoparticles (CuO NPs) were introduced and dispersed on surface of CNT fiber through electrochemical deposition method. The CNT fiber/CuO NPs electrode was fabricated and applied to electrochemical non-enzymatic glucose sensor. Surface morphology and elemental composition of the CNT fiber/CuO NPs electrode was characterized by scanning electron microscope (SEM) with energy dispersive X-ray spectrometry (EDS). And its electrochemical characteristics were investigated by cyclic voltammetry, electrochemical impedance spectroscopy and chronoamperometry. The CNT fiber/CuO NPs electrode exhibited the good sensing performance for glucose detection such as high sensitivity, wide linear range, low detection limit and good selectivity due to synergetic effect of CNT fiber and CuO NPs. Based on the unique property of CNT fiber, CuO NPs were provide large surface area, enhanced electrocatalytic activity, efficient electron transport property. Therefore, it is expected to develop high performance flexible electrode materials using various nanomaterials.

• Journal of the Korean Electrochemical Society
• /
• v.23 no.2
• /
• pp.47-55
• /
• 2020

Highly loaded LiCoO₂ positive electrodes are prepared to construct high-energy density lithium-ion batteries, their electrochemical performances are evaluated. For the standard electrode, a loading of about 2.2 mAh/㎠ is used, and for a high-loading electrode, an electrode is manufactured with a loading level of about 4.4 mAh/㎠. The content of carbon black as electronic conducting additive, and the porosity of the electrode are configured differently to compare the effects of electron conduction and ionic conduction in the highly loaded LiCoO₂ electrode. It is expected that the electrochemical performance is improved as the amount of the carbon black increases, but the specific capacity of the LiCoO₂ electrode containing 7.5 weight% carbon black is rather reduced. When the conductive material is excessively provided, an increase of electrode thickness by the low content of the LiCoO₂ active material in the same loading level of the electrode is predicted as a cause of polarization growth. When the electrode porosity increases, the path of ionic transport can be extended, but the electron conduction within the electrode is disadvantageous because the contact between the active material and the carbon black particles decreases. As the electrode porosity is lowered through the sufficient calendaring of the electrode, the electrochemical performance is improved because of the better contact between particles in the electrode and the reduced electrode thickness. In the electrode design for the high-loading, it is very important to construct the path of electron conduction as well as the ion transfer and to reduce the electrode thickness.

• Korean Chemical Engineering Research
• /
• v.46 no.4
• /
• pp.727-731
• /
• 2008

Mesoporous Pt-Au alloy films were successfully fabricated on ITO-coated glass by electrodeposition method using tri-blockcopolymer (P123) as a templating agent. The electrolyte consisted of 10 mM hydrogen hexachloroplatinate ($H_2PtCl_6$), 10 mM hydrogen tetrachloroaurate ($HAuCl_4$), and proper amount of P123. For comparison, control samples were electrodeposited without $HAuCl_4$ and P123. Film composition was determined by EDS(Energy Dispersive X-ray Spectroscopy), and the mesoporous structure was confirmed by TEM(Transmission Electron Microscopy). SEM(Scanning Electron Microscopy) was utilized to examine surface morphology, and it was observed that the addition of P123 affected the particle growth, resulting in the significant change of surface morphology. Methanol oxidation and CO oxidation were carried out to investigate electrocatalytic activities of synthesized samples. It was observed that the catalytic activity was strongly dependent on the film compositions. Compared with nonporous electrode prepared without P123 templating, mesoporous films prepared with P123 templating showed much higher catalytic activities and stability for both methanol oxidation and CO oxidation. These enhanced electrocatalytic activities were due to the high surface area and facilitated charge transfer of mesoporous films.

• Proceedings of the Korean Vacuum Society Conference
• /
• 1994.02a
• /
• pp.50-50
• /
• 1994

Half-metallic Heusler alloys (NiMnSb, ppdMnSb, pptMnSb) have attracted much attention due to their unique electronic and magnetic structures. Sppin-ppolarized band structure calculation ppredicts metallic behavior for the majority sppin states and semiconductor behavior for the minority sppin states. We have studied the electronic structures of these half-metallic Heusler alloys by core-level pphotoemission sppectroscoppy of Mn 2pp and 3s XppS sppectra. We found large intensities of Mn 2pp satellites and 3s exchange spplitting comppared with other metal Mn-alloys. These satellite structure can be understood by applying Anderson imppurity model. This fact supports the calculated sppin pprojected ppartial density of states which suggests that the valence electrons be highly sppin ppolarized near Fermi level and that the electrons involved with charge-transfer be mainly minority sppin ones which have semiconducting band structure. The trend of charge transfer energies Δ from ligands (Sb 5pp) to Mn 3d, obtained from our model fitting, is consistent with that calculated from sppin pprojected ppartial density of state. Also the trend of d-d electron correlation energies U calculated from Mn Auger line L3 VV by Mg $K\alpha$ source is comppatible with that resulted from our model fitting. We fitted the Mn 3s curve in the same way as for insulating Mn comppounds by using the same pparameters calculated from Mn 2pp curve fitting exceppt for the Coulomb interaction energy Q between core hole and d-electrons. The 3s sppectra were analyzed by combing the charge transfer model and a simpple model taking into account the configuration mixing effect due to the intra-shell correlation. We found that the exchange interaction between 3s hole and 3d electrons is mainly respponsible for the satellite of Mn 3s sppectra. This is consistent with the neutron scattering data, which suggests local 3d magnetic moment. We find that the XppS analysis results of Mn 2pp and 3s satellite structures of half-metallic Heusler alloys are very similar to those of insulating transition metal comppounds.

• Proceedings of the Korean Vacuum Society Conference
• /
• 2011.08a
• /
• pp.68-69
• /
• 2011

The process of charge transfer at the interface between two semiconductors or between a metal and a semiconductor plays an important role in many areas of technology. The optimization of such devices requires a good theoretical description of the interfaces involved. This, in turn, has motivated detailed mechanistic studies of interfacial charge-transfer reactions at metal/organic, organic/organic, and organic/inorganic semiconductor heterojunctions. Charge recombination of photo-induced electron with redox species such as oxidized dyes or triiodide or cationic HTM (hole transporting materials) at the heterogeneous interface of $TiO_2$ is one of main loss factors in liquid junction DSSCs or solid-state DSSCs, respectively. Among the attempts to prevent recombination reactions such as insulating thin layer and lithium ions-doped hole transport materials and introduction of co-adsorbents, although co-adsorbents retard the recombination reactions as hydrophobic energy barriers, little attention has been focused on the anchoring processes. Molecular engineering of heterogeneous interfaces by employing several co-adsorbents with different properties altered the surface properties of $TiO_2$ electrodes, resulting to the improved power conversion efficiency and long-term stability of the DSSCs. In this talk, advantages of the coadsorbent-assisted sensitization of N719 in preparation of DSSCs will be discussed.

• Bulletin of the Korean Chemical Society
• /
• v.32 no.8
• /
• pp.2743-2750
• /
• 2011

Lanthanide(III)-cored complex as a wavelength conversion material has been successfully designed and synthesized for highly efficient dye-sensitized solar cells, for the first time, since light with a short wavelength has not been effectively used for generating electric power owing to the limited absorption of these DSSCs in the UV region. A black dye (BD) was chosen and used as a sensitizer, because BD has a relatively weak light absorption at shorter wavelengths. The overall conversion efficiency of the BD/WCM device was remarkably increased, even with the relatively small amount of WCM added to the device. The enhancement in $V_{oc}$ by WCM, like DCA, could be correlated with the suppression of electron recombination between the injected electrons and $I_3{^-}$ ions. Furthermore, the short-circuit current density was significantly increased by WCM with a strong UV light-harvesting effect. The energy transfer from the Eu(III)-cored complex to the $TiO_2$ film occurred via the dye, so the number of electrons injected into the $TiO_2$ surface increased, i.e., the short-circuit current density was increased. As a result, BD/WCM-sensitized solar cells exhibit superior device performance with the enhanced conversion efficiency by a factor of 1.22 under AM 1.5 sunlight: The photovoltaic performance of the BD/WCM-based DSSC exhibited remarkably high values, $J_{sc}$ of 17.72 mA/$cm^2$, $V_{oc}$ of 720 mV, and a conversion efficiency of 9.28% at 100 mW $cm^{-2}$, compared to a standard DSSC with $J_{sc}$ of 15.53 mA/$cm^2$, $V_{oc}$ of 689 mV, and a conversion efficiency of 7.58% at 100 mW $cm^{-2}$. Therefore, the Eu(III)-cored complex is a promising candidate as a new wavelength conversion coadsorbent for highly efficient dye-sensitized solar cells to improve UV light harvesting through energy transfer processes. The abstract should be a single paragraph which summaries the content of the article.

• Journal of the Korean Magnetics Society
• /
• v.21 no.2
• /
• pp.56-60
• /
• 2011

Optical properties of $T_{0.2}Fe_{2.8}O_4$ (T = V, Cr, Mn) thin films derived from ferrimagnetic $Fe_3O_4$ were investigated by spectroscopic ellipsometry in the 1~8 eV photon-energy range. The difference in optical-absorption spectrum between the ternary compounds and $Fe_3O_4$ was analyzed based on preferable sites in spinel structure and iconicity of the doped V, Cr, and Mn ions. The observed absorption spectra from $Fe_3O_4$ and the ternary compounds can be interpreted as mainly due to charge-transfer transitions of Fe d electrons characterized by absorption structures with wide energy width. Also, the observed absorption structures with narrow energy width can be interpreted as due to crystal-field transitions between different d electron configurations of tetrahedral $Fe^{3+}(d^5)$ ion. The transitions were described in terms of spin-polarized electronic states of $Fe_3O_4$.

• Korean Chemical Engineering Research
• /
• v.61 no.2
• /
• pp.196-201
• /
• 2023

In this study, a CNT fiber flexible electrode grafted with CuO nanoparticles (CuO NPs) and polyaniline (PANI) was developed and applied to a nonenzymatic electrochemical sensor for H₂O₂ detection. CuO NPs/PANI/CNT fiber electrode was fabricated through the synthesis and deposition of PANI and CuO NPs on the CNT fiber surface using an electrochemical method. Surface morphology and elemental composition of the CuO NPs/PANI/CNT fiber electrode were characterized by scanning electron microscope with energy dispersive X-ray spectrometry. And its electrochemical characteristics were investigated by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and chronoamperometry (CA). Compared with a bare CNT fiber as a control group, the CuO NPs/PANI/CNT fiber electrode showed a 4.78-fold increase in effective surface area and a 8.33-fold decrease in electron transfer resistance, which leads to excellent electrochemical properties such as a good electrical conductivity and an efficient electron transfer. These improved characteristics were due to the synergistic effect through the grafting of CNT fiber, PANI and CuO NPs. As a result, this electrode enhanced the H₂O₂ sensing performance.