• Bulletin of the Korean Chemical Society
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• v.28 no.8
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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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• v.19 no.3
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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.

• Ceramist
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• v.23 no.2
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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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• v.35 no.8
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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.

• Applied Chemistry for Engineering
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• v.26 no.4
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• pp.394-399
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• 2015

In this study, the Cu catalyst decorated with activated carbon fibers were prepared for improving $SO_2$ adsorption properties. Flame retardant and heat treatments of Lyocell fibers were carried out to obtain carbon fibers with high yield. The prepared carbon fibers were activated by KOH solution for the high specific surface area and controlled pore size to improve $SO_2$ adsorption properties. Copper nitrate was also used to introduce the Cu catalyst on the activated carbon fibers (ACFs), which can induce various reactions in the process; i) copper nitrate promotes the decomposition reaction of oxygen group on the carbon fiber and ii) oxygen radical is generated by the decomposition of copper oxide and nitrates to promote the activation reaction of carbon fibers. As a result, the micro and meso pores were formed and Cu catalysts evenly distributed on ACFs. By Cu-impregnation process, both the specific surface area and micropore volume of carbon fibers increased over 10% compared to those of ACFs only. Also, this resulted in an increase in $SO_2$ adsorption capacity over 149% than that of using the raw ACF. The improvement in $SO_2$ adsorption properties may be originated from the synergy effect of two properties; (i) the physical adsorption from micro, meso and specific surface area due to the transition metal catalyst effect appeared during Cu-impregnation process and ii) the chemical adsorption of $SO_2$ gas promoted by the Cu catalyst on ACFs.

• Advances in materials Research
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• v.6 no.2
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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.

• Transactions of the Korean hydrogen and new energy society
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• v.26 no.1
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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.

• Applied Chemistry for Engineering
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• v.32 no.4
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• pp.409-416
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• 2021

Dimensionally stable electrodes are one of the important components in electrochemical water treatment processes. In the manufacturing of the dimensionally stable electrodes, the type of metal catalyst coated on the surface of the metal substrate, the coating and sintering methods substantially influence their performance and durability. In this study, using Ir-Ru-Ta ternary metal coating, various electrodes were prepared depending on the coating method under the same pre-treatment and sintering conditions, and its performance and durability were studied. As a coating method, brush and spray coating were used. As a result, the reduction in the amount of catalyst ink was achieved because more amount of metal could be coated for the electrode using spraying with the same amount of catalyst ink. In addition, the spray_2.0_3.0 electrode prepared by a specific spray coating method shows the phenomenon of cracking and the uniform coating of the ternary metal on the surface of the coating layer, and results in a high electrochemically active specific surface area, and the decomposition performance of 4-chlorophenol was superior to the other electrodes. However, it was found that there was no significant difference in durability depending on the coating method.

• Bulletin of the Korean Chemical Society
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• v.33 no.2
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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.

• Applied Chemistry for Engineering
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• v.20 no.1
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• pp.28-33
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• 2009

Carbon nanotube supported molybdenum carbide catalysts were prepared as a function of various preparation conditions and characterized, and their catalytic activities were compared through electrochemical oxidation of methanol. To overcome the low activity of a transition metal catalyst, carbon nanotube was used as a support, and the amount and the kind of precursors, acid treatment method, and carburization temperature were varied for the catalyst preparation. ICP-AES, XRD and TEM were used for the catalyst characterization. Based on the various preparation methods of carbon nanotube supported molybdenum carbide catalysts ($Mo_2C/CNT$), the size and the amount of supported catalysts could be controlled, and their effects on the electrochemical oxidation could be explained.