• 과학기술학연구
• /
• 제13권1호
• /
• pp.111-143
• /
• 2013

녹색 화학은 오염 물질의 배출을 피하면서도 동시에 공정 효율을 향상시키고자 하는 목적 하에 화학 공정의 설계, 운영에 대해 연구하는 새로운 과학 분야이다. 1991년에 처음으로 싹트기 시작한 녹색 화학은 오염물질을 청소하는데 집중했던 기존의 미국 환경 보호청의 정책에서 선회한 행보를 보였다. 이러한 녹색 화학의 형성 과정에 대해 연구한 선행 연구자들은 녹색 화학의 정치, 경제적인 동기에 대해서는 집중하지 않았다. 이 논문은 정부의 환경 정책, 산업계의 참여, 그리고 새로 출현한 녹색 화학자들의 학술 활동 사이의 관계를 보였으며, 이를 통해 녹색 화학의 형성 과정이 보여주는 함의를 알아내고자 하였다. 학계, 산업, 정부는 지속 가능한 발전이라는 폭넓은 정책 목표 아래에서, 녹색 화학을 형성했다. 녹색 화학자는 합성연구의 전통 안에서 합성효율을 높이는 반응 경로를 연구함으로써 오염물질 배출을 회피할 수 있는 지식을 만들어 내었고, 화학 산업계는 생산 효율성 증가를 통해 경제적인 이득을 얻고자 이것을 적극적으로 도입하였다. 이러한 새로운 형태의 동맹은 오염 회피, 자발적 규제 등의 방향을 선호하였던 미국 정부의 새로운 환경 정책의 흐름 안에서 지원받고, 유지될 수 있었다.

• Bulletin of the Korean Chemical Society
• /
• 제26권11호
• /
• pp.1743-1748
• /
• 2005

This work presents that carbon dioxide, which is a main contributor to the global warming effect, could be utilized as a selective oxidant in the oxidative dehydrogenation of ethylbenzene. The dehydrogenation of ethylbenzene over alumina-supported vanadium-antimony oxide catalyst has been studied under different atmospheres such as inert nitrogen, steam, oxygen or carbon dioxide as diluent or oxidant. Among them, the addition of carbon dioxide gave the highest styrene yield (up to 82%) and styrene selectivity (up to 97%) along with stable activity. Carbon dioxide could play a beneficial role of a selective oxidant in the improvement of the catalytic behavior through the oxidative pathway.

• Bulletin of the Korean Chemical Society
• /
• 제30권9호
• /
• pp.1956-1962
• /
• 2009

The binding abilities of two multidentate tripodal amine catechol ligands, cis,cis-1,3,5-tris[(2,3-dihydroxybenzylamino) aminomethyl]cyclohexane (TMACHCAT, $L^1)\;and\;N^1,N^3,N^5$-tris(2-(2,3-dihydroxybenzylamino) ethyl)cyclohexane-1,3,5-tricarboxamide (CYCOENCAT, $L^2$) with Ga(III) and In(III) have been investigated by potentiometric and spectrophotometric methods in an aqueous medium of 0.1 M KCl at 25 ${\pm}\;1\;{^{\circ}C}.$ The ligands $L^1\;and\;L^2$ formed various monomeric species $MLH_3,\;MLH_2$, MLH and ML (M = $Ga^{+3}\;and\;In^{+3}$) and showed potential to form strong encapsulated tris(catechol) type complexes. The coordination modes, binding ability and selectivity of the ligands towards Ga(III) and In(III) have been discussed with the help of experimental evidences, and supported with molecular modeling calculations.

• Bulletin of the Korean Chemical Society
• /
• 제32권8호
• /
• pp.2584-2592
• /
• 2011

Nickel nanoparticle-poly(N-vinyl-2-pyrrolidone)/$TiO_2-ZrO_2$ composite (Ni-PVP/$TiO_2-ZrO_2$) was prepared by in situ polymerization method. The physical and chemical properties of Ni-PVP/$TiO_2-ZrO_2$ were investigated by XRD, FT-IR, BET, TGA, SEM and TEM techniques. The catalytic performance of this novel heterogeneous catalyst was determined for the Suzuki-Miyaura cross-coupling reaction between aryl halides and phenylboronic acid in the presence of methanol-water mixture as solvent. The effects of reaction temperature, the amount of catalyst, amount of support, solvent, and amount of metal for the synthesis of Ni-PVP/$TiO_2-ZrO_2$, were investigated as well as recyclability of the heterogeneous composite. The catalyst used for this synthetically useful transformation showed considerable level of reusability besides very good activity.

• Bulletin of the Korean Chemical Society
• /
• 제32권7호
• /
• pp.2377-2384
• /
• 2011

Azo-acenaphthylene oligomers with repeating acenaphthylene units "n" up to 4, 5, 7, 17 and 19 have been prepared successfully using nitroxide mediated Stable Free Radical Polymerization (SFRP). Azo-acenaphthylene oligomers, reversibly end-capped by the stable nitroxide 2,2,6,6-tetramethyl-1-piperidinoxyl (TEMPO), were further reacted via radical addition to 4-(naphthalenemethoxy)styrene monomer for diblock co-polymer formation. Characterization of the oligomers and diblock co-polymers was accomplished using MALDI-MS supported by GPC (Gel Permeation Chromatography) and $^1H$ NMR spectrometry. MALDI-MS afforded definitive results by providing an inter-peak interval of 152 (m/z), corresponding to acenaphthylene monomer, and inter-peak interval of 260 (m/z) for the naphthalenemethoxystyrene monomer unit in block copolymers. Our study opens the way to control the number of repeat units in the oligomers. Further these oligomers can be tailored with various monomers for the formation of block copolymers.

• 한국진공학회:학술대회논문집
• /
• 한국진공학회 2011년도 제41회 하계 정기 학술대회 초록집
• /
• pp.160-160
• /
• 2011

In the present work, $TiO_2$ fiilms supported by porous silica gel with high surface area synthesized by atomic layer deposition(ALD). Porous structure of silica substrate could be maintained even after deposit large amount of $TiO_2$ (500 cycles of ALD process), suggesting the differential growth mode of $TiO_2$ on top surface and inside the pore. All the $TiO_2$-covered silica samples showed improved MB adsorption abilities, comparing to bare one. In addition, when silica surface was covered with $TiO_2$ films, MB adsorption capacity was almost fully recovered by re-annealing process (500$^{\circ}C$, for 1 hr, in ambient pressure), whereas MB adsorption capacity of bare silica was decreased after re-heaing process. FT-IR study demonstrated that $TiO_2$ film could prevent deposition of surface-bound intermediate species during thermal decomposition of adsorbed MB molecules. Photocatalytic activity of $TiO_2$/silica sample was also investigated.

• Bulletin of the Korean Chemical Society
• /
• 제15권6호
• /
• pp.473-477
• /
• 1994

Second-order rate constants have been measured spectrophotometrically for the nucleophilic substitution reactions of aryl substituted benzenesulfonates $(1,\;X-C_6H_4SO_2-OC_6H_4-Y)$ with aryloxides $(Z-C_6H_4O^{-})$ and ethoxide $(EtO^-)$ in absolute ethanol at $25^{circ}C$. The nucleophilicity of aryloxides increases with increasing electron donating ability of the substituent (Z) on aryloxides, and results in a good Hammett correlation with $\sigma^{-}$ constant. The reactivity of 1 toward aryloxides and ethoxide shows also significant dependence on the electronic nature of the substituent X and Y. Large positive ${\sigma}_{acyl}$ values have been obtained for the reaction of 1 with phenoxide and ethoxide, indicating that the leaving group departure is little advanced at the transition-state of the rate-determining step. This has been further supported from the fact that ${\sigma}^-$ constant gives extremely poor Hammett correlation, while ${\sigma}^0$ does reasonably good correlation for the reaction of 1 with ethoxide. Thus, the present sulfonyl-transfer reaction is proposed to proceed via a ratedetermining attack of nucleophile to the sulfur atom of 1 followed by a fast leaving group departure.

• Bulletin of the Korean Chemical Society
• /
• 제13권5호
• /
• pp.498-503
• /
• 1992

The protonation of RuH(NO)(Cyttp) resulted in the formation of $[RuH_2(NO)(Cyttp)]^+$ which is characterized as a classical cis-dihydried complex. This complex is fluxional and the intramolecular process involving a molecular hydrogen complex is proposed. This mechanism was further supported by the reactivity of this complex toward neutral 2-electron ligands. On the other hand, it failed to detect the existence of $[RuH_2(NO)(etp)]^+$ probably due to instability of the complex but the crystal structure of $[Ru(PMe_3)(NO)(etp)]^+$ formed by the protonation of RuH(NO)(etp) followed by the addition of $PMe_3$ was determined to have a trigonal bipyramidal structure with a linear NO in the equatorial plane and a facial etp ligand. The crystals are monoclinic, space group P21/n, with unit cell dimensions a = 14.130(2), b = 21.026 (3), c = 14.760 (1) ${\AA}$, ${\beta}$ = 97.88 $(l)^{\circ}$ V = 4344 ${\AA}^3$, Z = 4, R = 0.046 and $R_w$ = 0.056 for the 4779 intensities with $F_o^2 > 3{\sigma}(F_0^2)$ and the 440 variables.

• Advances in nano research
• /
• 제13권6호
• /
• pp.527-543
• /
• 2022

A novel, green, versatile and magnetically retrievable BiFeO₃/CDR (Bismuth ferrite/coriander) nanocomposites were fabricated via simple wet chemical method utilizing in situ functionalized, cheap coriander seed powder (CDR 5%, 10%, 15% and 20 wt%) as a fuel to enhance the efficiency of pristine BiFeO₃. A comparative study was performed between BiFeO₃/CDR and BiFeO₃/CNT (Bismuth ferrite/carbon nanotubes) nanocomposites for the removal of various hazardous pollutants from waste water. The successful synthesis of the fabricated nanomaterials was monitored via FT-IR, Powder XRD, FE-SEM, CV, VSM, CHNS/O and XPS studies. The synthesized nanomaterials were employed for the oxidative degradation of Carbol fuchsin, Reactive black 5, Ciprofloxacin and Doxorubicin; adsorption of a pesticide malathion; and reduction studies for Para-nitrophenol (PNP). The fabricated nanomaterials (BiFeO₃/CDR) showcased excellent efficiency and comparable results with (BiFeO₃/CNT) for the removal of model pollutants. Moreover, synthesized green heterojunction was also testified for mixture of textile and pharmaceutical waste. Hence CDR can be utilized as a better alternative of CNTs.

• Bulletin of the Korean Chemical Society
• /
• 제28권12호
• /
• pp.2377-2381
• /
• 2007

Solvolyses of 3,4-dimethoxybenzenesulfonyl chloride (DSC) in water, D2O, CH3OD, and in aqueous binary mixtures of acetone, acetonitrile, 1,4-dioxane, ethanol, methanol, and 2,2,2-trifluoroethanol (TFE) have been investigated at 25.0 oC. Kinetic solvent isotope effects (KSIE) in water and in methanol and product selectivities in alcohol-water mixtures are also reported. The Grunwald-Winstein plot of first-order rate constants for the solvolyic reaction of DSC with YCl shows marked dispersions into separated lines for various aqueous mixtures. With use of the extended Grunwald-Winstein equation, the l and m values obtained are 1.12 and 0.58 respectively for the solvolyses of DSC. The relatively large magnitude of l is consistent with substantial nucleophilic solvent assistance. From Grunwald-Winstein plots the rate data are dissected approximately into contributions from two competing reaction channels. This interpretation is supported for alcohol-water mixtures by the trends of product selectivities, which show a maximum for ethanol-water mixtures. From the KSIE of 1.45 in methanol, it is proposed that the reaction channel favored in methanolwater mixtures and in all less polar media is general-base catalysed and/or is possibly (but less likely) an addition-elimination pathway. Also, the KISE value of 1.35 for DSC in water is expected for SN2-SN1 processes, with minimal general base catalysis, and this mechanism is proposed for solvolyses in the most polar media.