• Bulletin of the Korean Chemical Society
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• 제28권8호
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• pp.1305-1310
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• 2007

A conjugated spirocyclic polymer was synthesized via the cyclopolymerization of 1,1-dipropargyl-1- silacyclohexane with various transition metal catalysts. The monomer, 1,1-dipropargyl-1-silacyclohexane was synthesized by Grignard reaction of 1,1-dichloro-1-silacyclohexane with propargyl magnesium bromide. This polymerization proceeded well to give the corresponding poly(1,1-dipropargyl-1-silacyclohexane). The catalytic activity of WCl6 was found to be similar with that of MoCl5. The structure of polymer having the conjugated backbone with silacyclohexane moieties was characterized by such instrumental methods as NMR (1H-, 13C-), IR, and UV-visible spectroscopies. The resulting polymers were mostly yellow or light-brown powders, depending on the catalyst systems used. This polymer was completely soluble in halogenated and aromatic hydrocarbons such as chloroform, 1,2-dichloromethane, benzene, toluene, and chlorobenzene, etc. The thermal and oxidative stabilities of polymer were also studied and discussed.

• Environmental Engineering Research
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• 제19권3호
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• pp.205-214
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• 2014

Petroleum a vital commodity affecting every aspect of 21st century. Toxicity and adverse effects of sulphur as catalyst in petroleum products is of great concern required development of techniques for desulphurization in compliance with the International standards. Installation of desulphurizing units costs over $200 million per unit placing economic burden on developing countries like Pakistan. Present study analysis of commercial fuels (station petrol and jet fuel JP8) on gas chromatography-mass spectrometry (GC-MS) identified sulphur concentration of 19.94 mg/L and 21.75 mg/L, respectively. This scenario urged the researcher to attempt synthesis of material that is likely to offer good adsorption capacity for sulphur. Following protocol of sol-gel method, transition metals (Ni, Cu, Zn) solution is gelated with tetraethoxysilane (TEOS; silica precursor) using glycerol. Fourier transform infrared spectroscopy (FTIR) spectra revealed bonding of Zn-O, Cu-O, and Ni-O by stretching vibrations at $468cm^{-1}$, $617cm^{-1}$, and $468cm^{-1}$, respectively. Thiophene and Benzothiophene mixed in n-heptane and benzene (4:1) for preparation of Model Fuels I and II, respectively. Each of silica based metal was applied as adsorbent in batch mode to assess the removal efficiency. Results demonstrated optimal desulphurization of more than 90% following efficacy order as Si-Ni > Si-Zn > Si-Cu based adsorbents. Proposed multilayered (Freundlich) adsorption mechanism follows ${\pi}$-complexation with pseudo secnd order kinetics.

• 세라미스트
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• 제23권2호
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• pp.211-230
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• 2020

Perovskite-type oxides with the nominal composition of ABO₃ can exsolve the B-site transition metal upon the controlled reduction. In this exsolution process, the transition metal emerges from the oxide lattice and migrates to the surface at which it forms catalytically active nanoparticles. The exsolved nanoparticles can recover back to the bulk lattice under oxidation treatment. This unique regeneration character by the redox treatment provides uniformly dispersed noble metal nanoparticles. Therefore, the conventional problem of traditional impregnated metal/support, i.e., sintering during reaction, can be effectively avoided by using the exsolution phenomenon. In this regard, the catalysts using the exsolution strategy have been well studied for a wide range of applications in energy conversion and storage devices such as solid oxide fuel cells and electrolysis cells (SOFCs and SOECs) because of its high thermal and chemical stability. On the other hand, although this exsolution strategy can also be applied to gas phase reaction catalysts, it has seldomly been reviewed. Here, we thus review recent applications of the exsolution catalysts to the gas phase reactions from the aspects of experimental measurements, where various functions of the exsolved particles were utilized. We also review non-perovskite type metal oxides that might have exolution phenomenon to provide more possibilities to develop higher efficient catalysts.

• Bulletin of the Korean Chemical Society
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• 제35권8호
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• pp.2438-2442
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• 2014

A kinetic study is reported for $S_NAr$ reaction of 1-fluoro-2,4-dinitrobenzene (5a) and 1-chloro-2,4-dinitrobenzene (5b) with alkali-metal ethoxides (EtOM, M = Li, Na, K and 18-crown-6-ether complexed K) in anhydrous ethanol. The second-order rate constant increases in the order $k_{EtOLi}$ < $k_{EtO^-}$ < $k_{EtONa}$ < $k_{EtOK}$ < $k_{EtOK/18C6}$ for the reaction of 5a and $k_{EtOLi}$ < $k_{EtONa}$ < $k_{EtO^-$ < $k_{EtOK}$ < $k_{EtOK/18C6}$ for that of 5b. This indicates that $M^+$ ion behaves as a catalyst or an inhibitor depending on the size of $M^+$ ion and the nature of the leaving group ($F^-$ vs. $Cl^-$). Substrate 5a is more reactive than 5b, although the $F^-$ in 5a is ca. $10pK_a$ units more basic than the $Cl^-$ in 5b, indicating that the reaction proceeds through a Meisenheimer complex in which expulsion of the leaving group occurs after the rate-determining step (RDS). $M^+$ ion would catalyze the reaction by increasing either the nucleofugality of the leaving group through a four-membered cyclic transition state or the electrophilicity of the reaction center through a ${\pi}$-complex. However, the enhanced nucleofugality would be ineffective for the current reaction, since expulsion of the leaving group occurs after the RDS. Thus, it has been concluded that $M^+$ ion catalyzes the reaction by increasing the electrophilicity of the reaction center through a ${\pi}$-complex between $M^+$ ion and the ${\pi}$-electrons in the benzene ring.

• 공업화학
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• 제26권4호
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• pp.394-399
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• 2015

본 연구에서는 Cu 촉매가 도입된 활성탄소섬유를 제조하여 고효율 $SO_2$ 흡착재를 제조하였다. 라이오셀 섬유를 내염화 및 탄화공정을 통해 탄소섬유를 얻었으며, $SO_2$ 흡착능을 향상시키기 위해 KOH 활성화를 사용하여 높은 비표면적 및 균일한 미세기공구조를 부여하였다. 활성탄소섬유에 Cu 촉매를 도입하기 위하여 $Cu(NO_3)_2{\cdot}3H_2O$ 수용액을 사용하였으며, 공정 시 i) 탄소섬유 내 산소 관능기의 분해반응을 촉진하고, ii) 산화구리 및 질산염의 분해로 oxygen radical이 생성되어 탄소섬유의 활성화 반응을 촉진시켰다. 이로 인해 활성탄소섬유의 미세공과 중기공 형성효과 및 탄소섬유 표면에 고르게 분산된 Cu 촉매를 확인하였다. Cu 촉매 도입 후, 활성탄소섬유에 비해 비표면적 및 미세공의 비율이 약 10% 이상 증가되었고, $SO_2$ 흡착능이 149% 이상 향상된 결과를 얻을 수 있었다. Cu 촉매도입공정 시, 전이금속 촉매효과에 의하여 발달된 미세공, 중기공 및 비표면적에 의한 물리적 흡착과 도입된 Cu 촉매에 의한 $SO_2$ 가스의 화학적 흡착반응의 시너지 효과에 기인하여 $SO_2$ 흡착능이 향상된 것으로 사료된다.

• Advances in materials Research
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• 제6권2호
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• pp.129-153
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• 2017

Platinum is a transition metal that is very resistant to corrosion. It is used as catalyst for converting methyl alcohol to formaldehyde, as catalytic converter in cars, for hydrocracking of heavy oils, in Fuel Cell devices etc. Moreover, Platinum compounds are important ingredient for cancer chemotherapy drugs. The nano forms of Platinum due to its unique physico-chemical properties that are not found in its bulk counterpart, has been found to be of great importance in electronics, optoelectronics, enzyme immobilization etc. The stability of Platinum nanoparticles has supported its use for the development of efficient and durable proton exchange membrane Fuel Cells. The present review concentrates on the use of Platinum conjugated with various metal or compounds, to fabricate nanocomposites, to enhance the efficiency of Platinum nanoparticles. The recent advances in the synthesis methods of different Platinum-based nanocomposites and their applications in Fuel Cell, sensors, bioimaging, light emitting diode, dye sensitized solar cell, hydrogen generation and in biosystems has also been discussed.

• 한국수소및신에너지학회논문집
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• 제26권1호
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• pp.8-14
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• 2015

In this study, the model biomass was used for hydrogen production by supercritical water gasification (SCWG). Model biomasses were glycerol, glycine, lignin and cellulose. The feed concentration was set to 1 wt%. Experiments were conducted in a reactor at $440^{\circ}C$ and above 26.3 MPa for 30 min. The effects of catalysts such as alkali metal salt ($K_2CO_3$ and $Na_2CO_3$) and transition metal salts ($Ni(NO_3)_2$, $Fe(NO_3)_3$ and $Mn(NO_3)_2$) on the gasification were systematically investigated. No tar or coke was observed in all experiments. The results showed that the gasification efficiency increased with various catalysts. For the cellulose and glycerol, all catalysts were effective for the promoted $H_2$ production compared with no catalyst. The significant decrease of $H_2$ production compared with no catalyst was observed with $Na_2CO_3$ and $Fe(NO_3)_3$ for glycine and lignin. respectively. The highest H2 production, 1.24 mmol was obtained for glycerol-SCWG with $Mn(NO_3)_2$. Conclusively, the addition of $Mn(NO_3)_2$ enhanced all model biomass gasification efficiency and increased the hydrogen production promoting the supercritical water reaction.

• 공업화학
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• 제32권4호
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• pp.409-416
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• 2021

불용성 산화 전극은 전기화학적 수처리 공정에 있어 가장 핵심적인 소재이며, 이를 이용하여 난분해성 유기물질을 분해하는 방법으로 많은 연구가 진행되어 왔다. 이러한 불용성 산화 전극 제조에 있어 금속 기판 표면에 코팅하는 금속 촉매의 종류, 코팅 방식, 소결 방법 등의 다양한 제조 변수가 불용성 산화 전극의 성능 및 내구성에 영향을 미친다. 본 연구에서는 Ir-Ru-Ta 삼원 금속 코팅을 활용하여 동일한 전 처리 및 소결 조건에서 코팅 방법에 따라 불용성 산화 전극을 제조하고 이의 성능과 내구성을 연구하였다. 코팅 방식은 브러쉬 및 스프레이 코팅법을 활용하였으며, 그 결과 최적화된 스프레이 코팅 조건에서 동일한 촉매 잉크양으로 더 많은 금속을 Ti 기판 표면에 코팅이 가능하여 촉매 잉크 저감이 가능한 것을 확인하였다. 또한, 전극 표면의 갈라짐 현상 및 삼원 금속의 균일한 도포에 의해 스프레이 코팅법으로 제조한 Spray_2.0_3.0 전극이 가장 높은 전기화학적 활성 비표면적을 보여주었으며, 4-chlorophenol의 분해 성능이 타 전극에 비해 우수한 것으로 나타났다. 하지만, 불용성 산화전극의 내구성은 전극의 코팅방법에 따라 큰 차이가 없는 것으로 나타났다.

• Bulletin of the Korean Chemical Society
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• 제33권2호
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• pp.519-523
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• 2012

A kinetic study is reported on nucleophilic displacement reactions of benzyl 2-pyridyl carbonate 6 with alkalimetal ethoxides, EtOM (M = Li, Na, and K), in anhydrous ethanol at $25.0{\pm}0.1^{\circ}C$. The plots of pseudo-firstorder rate constant $k_{obsd}$ vs. [EtOM] curve upward, a typical phenomenon reported previously for alkaline ethanolysis of esters in which alkali-metal ions behave as a Lewis-acid catalyst. The kobsd value for the reaction of 6 with a fixed EtOK concentration decreases rapidly upon addition of 18-crown-6-ether (18C6), a complexing agent for $K^+$ ion up to [18C6]/[EtOK] = 1.0 and then remains constant thereafter, indicating that the catalytic effect exerted by K+ ion disappears in the presence of excess 18C6. The reactivity of EtOM towards 6 increases in the order $EtO^-$ < EtOLi < EtONa < EtOK, which is contrasting to the reactivity order reported for the corresponding reactions of 2-pyridyl benzoate 4, i.e., $EtO^-$ < EtOK < EtONa < EtOLi. Besides, 6 is 1.7 and 3.5 times more reactive than 4 towards dissociated $EtO^-$ and ion-paired EtOK, respectively. The reactivity difference and the contrasting metal-ion selectivity are discussed in terms of electronic effects and transition-state structures.

• 공업화학
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• 제20권1호
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• pp.28-33
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• 2009

카본나노튜브에 담지된 몰리브데늄 카바이드 촉매를 다양한 제조 조건을 통해 제조하여 촉매특성을 분석하였고, 메탄올의 전기화학적 산화반응을 통해 촉매의 활성을 비교하였다. 촉매로써 전이금속의 낮은 활성을 극복하기 위한 방안으로 카본나노튜브를 지지체로 사용하였으며 전구체의 양 및 종류, 지지체의 산처리 방법, 탄화공정 온도조건 등을 변화하여 촉매를 제조하였다. 제조된 촉매는 ICP-AES, XRD, TEM을 통하여 촉매의 특성을 분석하였고, 메탄올의 전기화학적 산화반응을 통해 촉매의 활성을 비교하였다. 몰리브데늄 카바이드 촉매($Mo_2C/CNT$)의 다양한 제조방법으로 입자크기와 담지량을 변화시킬 수 있었으며, 입자의 크기와 담지량의 변화에 따른 전기화학적 산화반응의 특성을 설명할 수 있었다.