• Bulletin of the Korean Chemical Society
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• 제31권9호
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• pp.2483-2487
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• 2010

Pseudo-first-order rate constants ($k_{obsd}$) were measured spectrophotometrically for nucleophilic substitution reactions of 4-nitrophenyl picolinate (6) with alkali metal ethoxides (EtOM, $M^+\;=\;K^+$, $Na^+$ and $Li^+$) in anhydrous ethanol at $25.0{\pm}0.1^{\circ}C$. The plot of $k_{obsd}$ vs. [EtOM] exhibits upward curvature regardless of the nature of $M^+$ ions. However, the plot for the reaction of 6 with EtOK is linear with significantly decreased $k_{obsd}$ values when 18-crown-6-ether (18C6, a complexing agent for $K^+$ ion) is added in the reaction medium. Dissection of $k_{obsd}$ into $k_{EtO^-}$ and $k_{EtOM}$ (i.e., the second-order rate constant for the reaction with dissociated $EtO^-$ and ion-paired EtOM, respectively) has revealed that ion-paired EtOM is 3~17 times more reactive than dissociated $EtO^-$. The reaction has been proposed to proceed through a 5-membered cyclic transition state, in which $M^+$ ion increases the electrophilicity of the reaction site. Interestingly, $Na^+$ ion exhibits the largest catalytic effect. The presence of a nitrogen atom in the pyridine moiety of 6 has been suggested to be responsible for the high $Na^+$ ion selectivity.

• 한국세라믹학회지
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• 제54권1호
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• pp.1-8
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• 2017

Electrochemical water splitting to produce hydrogen energy is regarded as a promising energy conversion process for its environmentally friendly nature. To improve cell efficiency, the development of efficient water oxidation catalysts is essentially demanded. For several decades, 3d transition metal oxides have been intensively investigated for their high activity, good durability and low-cost. This review covers i) recent progress on 3d transition metal oxide electrocatalysts and ii) the reaction mechanism of oxygen evolving catalysis, specifically focused on the proposed pathways for the O-O bond formation step.

• 공업화학
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• 제10권5호
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• pp.804-807
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• 1999

페로센 카르복시알데히드와 1,2-diaminocyclohexane을 2:1로 반응시켜 키랄 리간드 L(L=N,N'-cyclohexane bis(ferrocenylmethylene)amine)을 합성하고 이를 구리와 반응시켜 새로운 구리 착물을 합성하였다. 이 착물들을 확인하고 비대칭 유기 합성반응에 촉매로 사용하였다. 구리(II) 착물들은 스티렌과 에틸디아조아세테이트와의 시클로프로판화 반응에서 촉매작용을 하지 않았으나 구리(I)화합물, Cu(I)LOTf (OTf=trifluoromethanesulfonate)는 시클로프로판 생성물 trans:cis의 비율에 있어 80:20 이상의 높은 regioselectivity를 보였다.

• 한국환경과학회지
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• 제3권4호
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• pp.439-443
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• 1994

In aqueous acid solution ${[Cr(CN)_6]}^{3-}$ aquates via a series of stepwise stereospecific reactions to give ${[Cr{(H_2O)}_6]}^{3+}$as the final product.Some of the intermediate cyanoaquo complexes in the sequence have been isolated.These complexes aquate by both acid independent and acid denpendent pathways, the latter involving protonation of the cyano ligands followed by aquation of the singly protonated species. The kinetic data for the aquation of {[CrCN{(H_2O)}_5]}^{2+}$ are consistent with the transition state structure ${[{(H_2O)}_4Cr(CN)-OH-Cr{(H_2O)}_5]}^{3+}$. Addition of $Cr^{2+}$ to solutions of cyanocobalt(III) complexes produces the metastable intermediate${[CrNC{(H_2O)}_5]}^{2+}$ This isomerizes to in a $Cr^{2+}$-catalyzed reaction which occurs by a ligand-bridged electron-change mechnism. From acid catalysis on these aquation reactions, it product HCN. Especially, $HSO_3$-ions do the role of catalyst in the formation of HCN from $CrCN^{3-}$

• 대한방사성의약품학회지
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• 제4권1호
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• pp.11-15
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• 2018

Electrophilic fluorinating reagents are typically efficient for carbon-fluorine (C-F) bonds formation due to their higher reactivity even under mild condition. Thus, they have been playing an important role to improve C-F bonds formation reactions via direct fluorination reaction with electrophilic fluorinating reagents or transition metal catalysis. Advances on the recent fluorination methods are mainly results of $Selectfluor^{TM}$'s capability on facile fluorination. In this mini-review, we describe synthesis and application of four old yet popular electrophilic fluorinating reagents such as N-fluorobenzenesulfonimide (NFSI), N-fluoropyridinium salts, $Selectfluor^{TM}$, and N-fluorosultam.

• Journal of Pharmaceutical Investigation
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• 제20권3호
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• pp.145-152
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• 1990

Zirconium pyrithione complex was prepared by reaction of sodium-pyrithione solution and zirconyl chloride solution. The physico-chemical properties of the complex was examined by means of IR, XRD, DSC and NMR. And the stability of Zr-complex was investigated on the basis of accelerated stability analysis under conditions of temp. elevation, UV radiation and pH dependence. The result indicates that the ratio of the ligand to metal in Zr-pyrithione complex was determined 4:1, and its stability constant was $4.643{\times}10^4$. The rate order of decomposition of the complex was apparent first-order reaction of which rate constant and the decomposition rate was not only accelerated by effect of heat and UV radiation but was catalyzed by specific acid-base catalysis considered the pH dependence for the hydrolysis of the complex and the suspension was most stable over the range pH 4-8 indicating that solvent catalysis is the primary made of reaction in this region.

• Advances in materials Research
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• 제3권4호
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• pp.199-216
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• 2014

Noble metal nanoparticles (mainly Au, Ag, Pt and Pd) have received enormous attention owing to their unique and fascinating properties. In the past decades, many researchers have reported methods to control the shape and the size of these noble metal nanoparticles. They have consequently demonstrated outstanding and tunable properties and thus enabled a variety of applications such as surface plasmonics, photonics, diagnostics, sensing, energy storage and catalysis. This paper focuses on the recent advances in the solution-phase synthesis of shape- and size-controlled noble metal nanoparticles. The strategies and protocols for the synthesis of the noble metal nanoparticles are introduced with discussion of growth mechanisms and important parameters, to present the general criteria needed for producing desirable shapes and sizes. This paper reviews their remarkable properties as well as their shape- and size- dependence providing insights on the manipulation of shape and size of metal nanoparticles, necessary for appropriate applications. Finally, several applications using the shape- and size-controlled noble metal nanoparticles are highlighted.

• Bulletin of the Korean Chemical Society
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• 제22권7호
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• pp.673-677
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• 2001

Pseudo-first-order rate constants have been measured spectrophotometrically for the reactions of 8-(5-nitroquinolyl) 3-furoate with alkali metal ethoxides in anhydrous ethanol. The plot of kobs vs the concentration of alkali metal ethox ides is linear for the reactions performed in the presence of a complexing agent, 18-crown-6 ether, but exhibits upward curvatures for the corresponding reactions performed in the absence of the complexing agent, indicating that the alkali metal ions in this study behave as catalysts. Second-order rate constants were determined for the reactions with dissociated free ethoxide (kEtO-) and with ion paired alkali metal ethoxides (kEtO-M + ) from ion pairing treatments. The magnitude of catalytic effect (kEtO-M + /kEtO-) was found to be 1.7, 3.4 and 2.5 for the reaction of 8-(5-nitroquinolyl) 3-furoate, while 1.4, 3.6 and 4.2 for that of 4-nitrophenyl 2-furoate, 1.8, 3.7 and 2.4 for that of 8-(5-nitroquinolyl) benzoate, and 2.0, 9.8 and 9.3 for that of 8-(5-nitroquinolyl) 2-furoate with EtO- Li+ , EtO- Na+ and EtO- K+ , respectively. A 5-membered chelation at the leaving group is suggested to be responsible for the catalytic effect shown by alkali metal ions.

• Bulletin of the Korean Chemical Society
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• 제22권7호
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• pp.669-672
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• 2001

Pseudo-first-order rate constants have been measured spectrophotometrically for the title reactions. The plot of kobs vs the concentration of alkali metal ethoxides is linear for the reactions performed in the presence of complexing age nt, 18-crown-6 ether, but curved upwardly for the corresponding reactions performed in the absence of the complexing agent, indicating that the alkali metal ions studied in this study behave as a catalyst. The catalytic effect was found to increase in the order Li+ << K+ ${\leq}$ Na+. Second-order rate constants were determined for the reactions with dissociated free ethoxide (kEtO-) and with ion paired alkali metal ethoxides (kEtO-M+ ) from ion pairing treatments. The magnitude of catalytic effect (kEtO-M+/kEtO-) was found to be 2.3, 9.5 and 8.7 for the reaction of 8-(5-nitroquinolyl) 2-furoate, while 1.4, 3.6 and 4.2 for that of 4-nitrophenyl 2-furoate, indicating that the catalytic effect is larger in the reaction of the former substrate than in that of the latter one. The larger catalytic effect was attributed to two possible complexing sites with alkali metal ions in the former substrate.

• 한국재료학회지
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• 제31권9호
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• pp.525-531
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• 2021

Carbon-encapsulated Ni catalysts are synthesized by an electrical explosion of wires (EEW) method and applied for CO₂ methanation. We find that the presence of carbon shell on Ni nanoparticles as catalyst can positively affect CO₂ methanation reaction. Ni@5C that is produced under 5 % CH₄ partial pressure in Ar gas has highest conversions of 68 % at 350 ℃ and 70 % at 400 ℃, which are 73 and 75 % of the thermodynamic equilibrium conversion, respectively. The catalyst of Ni@10C with thicker carbon layer shows much reduced activity. The EEW-produced Ni catalysts with low specific surface area outperform Ni catalysts with high surface area synthesized by solution-based precipitation methods. Our finding in this study shows the possibility of utilizing carbon-encapsulated metal catalysts for heterogeneous catalysis reaction including CO₂ methanation. Furthermore, EEW, which is a highly promising method for massive production of metal nanoparticles, can be applied for various catalysis system, requiring scaled-up synthesis of catalysts.