• Bulletin of the Korean Chemical Society
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• 제19권5호
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• pp.527-530
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• 1998

This paper presents the electrochemistry and molecular orbital (MO) picture of a series of conformationally-restricted thioxantone derivatives. A series of $C_2-substituted$ thioxanthones were examined to probe the electronic influence of the substituent on the electrooxidation and electroreduction sites (i.e., on the electron densities at the 10-and 9-positions), respectively. In the presence of "electrophoric" groups such as C=O and S, characteristic electrochemical reduction and oxidation responses are observed. The electrochemical reaction was diffusion-controlled, because the $I_p/{\upsilon}^{1/2}$ ratio was constant for the anodic and cathodic wave of thioxantone derivatives. These substituent effects are presented in terms of correlations of oxidation (or reduction) potentials with the highest occupied molecular orbital (HOMO), or lowest unoccupied molecular orbital (LUMO) energies, respectively. There is good correlation between energies of the HOMO vs. $E_{pa}^{(+)}$ and energies of the LUMO vs. $E_{pc}^{(-)}$. Frontier Molecular Orbital (FMO) is changed by the functional group of thioxanthones. FMO energy level was offered us the information about the electron transfer direction, and the coefficient of FMO was offered the information about the electron transfer position. Sulfur atom has an important effect on oxidation potential, $E_{pa}^{(+)}$ and the carbonyl carbon has an important effect on reduction potential, $E_{pc}^{(-)}$. Therefore we were appreciated that the contribution of sulfur atom for the $E_{pa}^{(+)}$ and HOMO energies is larger than the contribution of carbonyl group for the $E_{pc}^{(-)}$ and LUMO energies.

• Bulletin of the Korean Chemical Society
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• 제20권10호
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• pp.1177-1180
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• 1999

The ab initio SCF MO and density functional theory (DFT) studies are carried out on the electrophilic (1a) and electron transfer (1b) addition reactions to the vinyl double bond of aryl vinyl sulfides and ethers. In the electrophilic addition processes, a double bond shift from C3 = C4 to X = C3 occurs with occupation number (1.97) close to the normal two. Due to this shift direct conjugation between the cationic center, X = S or O, and the para electron-donor substituent becomes impossible so that the reaction energies (or log K) are correlated with σ rather than σ+. By contrast, radical cation formation leads to delocalization of the SOMO, a lone-pair πorbital on X, with four major resonance structures in which cationic charge as well as spin density is delocalized over C4 , X and C7 atoms. As a result, partial πbonds are formed over C1 -X and C3 - C4 with occupation numbers (0.82) lower than one. In two of the cannonical structures, III(Ⅹ) and III(X+), direct conjugation between the cationic center, X, and the para substituent is achieved so that a better correlation with σ+ rather than σis obtained. The SCF MO energies at the HF/3-21G* and HF/6-31G* levels lead to very much inferior Hammett correlations in the σ/ σ+ diagnostic criterion. In contrast, the ρvalues evaluated with the DFT energies can give reliable diagnostic distinction between the two addition mechanisms.

• Nano
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• 제13권10호
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• pp.1850116.1-1850116.14
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• 2018

In this study, we report the mercury ions ($Hg^{2+}$) mediated phosphorus-containing carbon dots (PCDs) as a selective "off-on" fluorescence probe for glutathione (GSH), cysteine (Cys) and homocysteine (Hcys). PCDs obtained by hydrothermal reaction are sensitive to $Hg^{2+}$ ions and its fluorescence can be significantly quenched owing to the electron transfer from the lowest unoccupied molecular orbital (LUMO) of PCDs to $Hg^{2+}$. Interestingly, the weak fluorescence of $Hg^{2+}$-mediated PCDs could be gradually recovered with the addition of GSH, Cys and Hcys. This can be attributed to the formation of $Hg^{2+}-S$ complex due to the super affinity of $Hg^{2+}$-sulfydryl bond. The formation of $Hg^{2+}-S$ complex extremely reduces the oxidation ability of $Hg^{2+}$ that inhibits the electron transfer from LUMO of PCDs to $Hg^{2+}$ and re-opens the native electron transition from LUMO to the highest occupied molecular orbital (HOMO) of PCDs. Thus, the green fluorescence of PCDs is switched on. Furthermore, the present $Hg^{2+}$-mediated PCDs assay exhibits a high selectivity for GSH, Cys and Hcy and has been successfully used to detect the total biothiols content in human urine samples.

• Bulletin of the Korean Chemical Society
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• 제19권6호
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• pp.661-666
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• 1998

Active reaction sites and electrochemical O2 reduction kinetics on La_{1-x}Sr_xMnO_{3+{\delta}} (x=0.1-0.4)/YSZ (yttria-stabilized zirconia) electrodes are investigated in the temperature range of 700-900 ℃ at $Po_2=10^{-3}$-0.21 atm. Results of the steady-state polarization measurements, which are formulated into the Butler-Volmer formalism to extract transfer coefficient values, lead us to conclude that the two-electron charge transfer step to atomically adsorbed oxygen is rate-limiting. The same conclusion is drawn from the $Po_2$-dependent ac impedance measurements, where the exponent m in the relationship of $I_o$ (exchange current density) ∝ $P_{o_{2}}^m$ is analyzed. Chemical analysis is performed on the quenched Mn perovskites to estimate their oxygen stoichiometry factors (δ) at the operating temperature (700-900 ℃). Here, the observed δ turns out to become smaller as both the Sr-doping contents (x) and the measured temperature increase. A comparison between the 8 values and cathodic activity of Mn perovskites reveals that the cathodic transfer coefficients $({\alpha}_c)$ for oxygen reduction reaction are inversely proportional to δ whereas the anodic ones $({\alpha}_a)$ show the opposite trend, reflecting that the surface oxygen vacancies on Mn perovskites actively participate in the $O_2$ reduction reaction. Among the samples of x= 0.1-0.4, the manganite with x=0.4 exhibits the smallest 8 value (even negative), and consistently this electrode shows the highest ${\alpha}_c$ and the best cathodic activity for the oxygen reduction reaction.

• 대한금속재료학회지
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• 제48권7호
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• pp.674-682
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• 2010

Fe-fullerene/$TiO_2$ composite photocatalysts were prepared with titanium (IV) n-butoxide (TNB) by a sol-gel method. The samples were characterized by scanning electron microscopy (SEM), Transmission electron microscope (TEM), specific surface area (BET), X-ray diffraction analysis (XRD) and energy dispersive X-ray spectroscopy (EDX). The photocatalytic activities were evaluated by the photocatalytic degradation of methylene blue (MB) solution. XRD patterns of the composites showed that the Fe-fullerene/$TiO_2$ composite contained a typical single and clear anatase phase. The surface properties shown by SEM present a characterization of the texture on Fe-fullerene/$TiO_2$ composites and showed a homogenous composition in the particles for the titanium sources used. The EDX spectra for the elemental identification showed the presence of C and Ti with strong Fe peaks for the Fe-fullerene/$TiO_2$ composite. From the photocatalytic results, the excellent activity of the Fe-fullerene/$TiO_2$ composites for degradation of methylene blue under UV light irradiation could be attributed to both the effects between photocatalytic reaction of the supported $TiO_2$, decomposition of the organometallic reaction by the Fe compound and energy transfer effects such as electron and light of the fullerene.

• 열처리공학회지
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• 제15권1호
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• pp.16-20
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• 2002

In conventional metallothermic reduction(MR) for obtaining tantalum powder in batch-type operation, it is difficult to control morphology and location of deposits because the reaction occurs by direct physical contact between reductants and feed materials. On the other hand, a electronically mediated reaction(EMR) is capable to overcome these difficulties through the reaction by electron transfer and have a merit of continuous process. In this study an MR and EMR method has been applied to the production of a tantalum powder by sodium reduction of $K_2TaF_7$. As the reduction temperature increases, the particle size and yield of tantalum powder obtained by MR and EMR method is increased.

• 한국표면공학회지
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• 제51권3호
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• pp.179-184
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• 2018

In this study, Ni and tungsten carbide (WC) nanoparticles are simultaneously synthesized with the mesoporous carbon nanoparticles (CNP) using a solution plasma processing (SPP) in the benzene. The Ni and WC nanoparticles were formed through the sputtering effect of electrodes during discharge, and mean time CNP were formed through reduction reaction. TEM observation showed that loaded Ni and WC nanoparticles were evenly dispersed on the CNP. The results of electrochemical analysis demonstrated that an introduction of Ni nanoparticles promoted to improve catalytic activity for oxygen reduction reaction (ORR). Moreover, Ni-WC/CNP lead to fast electron transfer process compared to that of WC/CNP. Therefore, the inexpensive Ni-WC/CNP might be a promising as catalytic material for cathodes in fuel cell applications.

• Journal of Electrochemical Science and Technology
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• 제14권3호
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• pp.243-251
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• 2023

Developing oxygen evolution reaction (OER) electrocatalysts is essential to accomplish viable CO₂ and water electrolysis. Herein, we report the fabrication and OER performance of Ni-foam (NF)-immobilized Ni₆ nanoclusters (NCs) (Ni₆/NF) prepared by a dip-coating process. The Ni₆/NF electrode exhibited a high current density of 500 mA/cm² for the OER at an overpotential as low as 0.39 V. Ni₆/NF exhibited high durability in an alkaline solution without corrosion. Electrokinetic studies revealed that OER can be easily initiated on Ni6 NC with fast electron-transfer rates. Finally, we demonstrated stable CO₂-to-CO electroreduction using an NC-based zero-gap CO₂ electrolyzer operated at a current density of 100 mA/cm² and a full-cell potential of 2.0 V for 12 h.

• 대한화학회지
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• 제37권1호
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• pp.83-91
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• 1993

염기성 용액에서 가벼운 란탄족 원소 착물의 전기화학적 거동을 직류(DC), 펄스차이 폴라로그래피(DPP), 순환전압전류법(CV) 및 정전위 전기분해법으로 조사하였다. 란탄이온들은 NaCl 지지전해질에서 o-cresolphthalexon(OCP)과 1:1로 배위하였으며, 전극반응은 2단계 1전자 환원반응이었다. 착물의 반파전위는 pH에 따라 변화하였으며 환원전류는 흡착성을 나타냈다. DC 및 CV에서 첫번째 1전자 환원반응은 유사가역적 거동을 나타냈으며, 환원 뒤에 형성된 음이온 라디칼은 이합체와 반응을 하였다. 두번째 환원파는 전자전이 반응에 이어 생성된 카르보 음이온의 빠른 양성자 첨가반응으로 비가역적 거동을 나타냈다. -1.80V에서 정전위 전해시간이 증가함에 따라 착물의 질은 청색은 점점 옅어져서 무색이 되었으며, 최종생성물은 전기적으로 비활성이었다. 따라서 Ln-OCP 착물의 단계적인 전극반응은 ECEC 메카니즘으로 제안되었다.

• Bulletin of the Korean Chemical Society
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• 제35권2호
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• pp.587-596
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• 2014

A new ${\pi}$-stacked donor-acceptor (D-A) system, [Ru(1-([2,2'-bipyridine]-6-yl-methyl)-3-(2-cyclohexa-2',5'-diene-1,4-dionyl)-1H-imidazole)(2,2':6',2"-terpyridine)]$[PF_6]_2$ (ImQ_T), has been synthesized and characterized. Similar to its precedent, [Ru(6-(2-cyclohexa-2',5'-diene-1,4-dione)-2,2':6',2"-terpyridine)(2,2':6',2"-terpyridine)]$[PF_6]_2$ (TQ_T), this system has a cofacial alignment of terpyridine (tpy) ligand and quinonyl (Q) group, which facilitates an electron transfer through ${\pi}$-stacked manifold. Despite the presence of lowest-energy charge transfer transition from the Ru-based-HOMO-to-Q-based-LUMO (MQCT) predicted by theoretical calculations by using time-dependent density functional theory (TD-DFT), the experimental steady-state absorption spectrum does not exhibit such a band. The selective excitation to the Ru-based occupied orbitals-to-tpy-based virtual orbital MLCT state was thus possible, from which charge separation (CS) reaction occurred. The photo-induced CS and thermal charge recombination (CR) reactions were probed by using ultrafast visible-pump/mid-IR-probe (TrIR) spectroscopic method. Analysis of decay kinetics of Q and $Q^-$ state CO stretching modes as well as aromatic C=C stretching mode of tpy ligand gave time constants of <1 ps for CS, 1-3 ps for CR, and 10-20 ps for vibrational cooling processes. The electron transfer pathway was revealed to be Ru-tpy-Q rather than Ru-bpy-imidazol-Q.