• 한국자기공명학회논문지
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• 제3권2호
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• pp.109-126
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• 1999

The location of Cu(II) exchanged into measoporous aluminosilicate MCM-41(AlMCM-41) material and its interaction with various adsorbate molecules were investigated by electron spin resonance and electron spin echo modulation spectroscopies. Cu(II) is fully coordinated to adsorbates in a wide open mesopore of AlMCM-41 for the formation of favorable complexes. It was found that in the fresh hydrated material, Cu(II) is octahedrally coordinated to six water molecules as evidenced by an isotropic room temperature ESR signal. This species is located in a cylindrical MCM-41 channel and rotates rapidly at room temperature. Evacuation at room temperature removes some of these water molecules, leaving the Cu(II) coordinated to less water molecules and anchored to oxygens in an MCM-41 channel wall. Dehydration at 450$^{\circ}C$ produces one Cu(II) species located on the internal wall of a channel, which is easily accessible to adsorbates. Adsorption of adsorbate molecules such as water, methanol, ammonia, pyridine, aniline, acetonitrile, benzene, and ethylene on a dehydrated Cu-AlMCM-41 material causes changes in the ESR spectrum of Cu(II), indicating the complex formation with these adsorbates. Cu(II) forms a complex with six molecules of methanol as evidenced by an isotropic room temperature ESR signal and ESEM analysis like upon water adsorption. Cu(II) also forms a square planar complex containing four molecules of N-containing adsorbates such as ammonia, pyridine and aniline based on resolved nitrogen superhyperfine interaction and their ESR parameters. However, Cu(II) forms a complex with six-molecules of acetonitrile based on ESR parameters. Only one molecule of benzene or ethylene is coordinated to Cu(II).

• 한국자기공명학회논문지
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• 제1권2호
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• pp.126-140
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• 1997

Mesoporous MCM-41 gallosilicate material was synthesized through shifting through shifting gallosilicate polymer equilibrium towards a MCM-41 phase by addition of acid. The location of Cu(II) exchanged into MCM-41 and its interaction with various adsorbate molecules were investigated by electron spin responance and electron spin echo modulation spectroscopies. It was found that in the fresh hydrated material, Cu(II) is octahedrally coordinated to six water molecules. This species is located in a cylindrical channel and rotates rapidly at room temperature. Evacuation at room temperature removes three of these water molecules, leaving the Cu (II) coordinated to three water molecules and anchored to oxygens in the channel wall. Dehydration at 45$0^{\circ}C$ produces one Cu (II) species located in the inner surface of a channel as evidenced by broadening of its ESR lines by oxygen. Adsorption of polar molecules such as water, methanol and ammonia on dehydrated CuNa-MCM-41 gallosilicate material causes changes in the ESR spectrum of Cu (II), indicating the complex formation with these adsorbates. Cu (II) forms a complex with six molecules of methanol as evidenced by an isotropic room temperature ESR signal and ESEM data like upon water adsorption. Cu(II) also forms a complex containing four molecules of ammonia based on resolved nitrogen superhyperfine interaction.

• 상하수도학회지
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• 제26권2호
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• pp.275-283
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• 2012

MCM-41(Mobil's Composition of Matter-41) and expanded graphite(EG) were investigated as potential adsorbents for heavy metal ions including Pb(II), Cu(II) and Ni(II) in various aqueous chemistries. MCM-41 showed shorter equilibrium times and higher adsorption capacities for all three heavy metal ions compared to expanded graphite. The adsorption of three heavy metal ions was significantly affected by the solution pH due to the competition with $H_{3}O^{+}$ at lower pH and precipitation at neutral or higher pH. Adsorptions of heavy metal ions onto MCM-41 and expanded graphite were successfully described with the pseudo-second-order model. During the competitive adsorption of three heavy metal ions, the selectivity of Pb(II) was highest and almost same selectivity was observed with Cu(II) and Ni(II) when MCM-41 was used as an adsorbent, while the expanded graphite exhibited the highest selectivity to Pb(II), followed by Ni(II) and Cu(II).

• Bulletin of the Korean Chemical Society
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• 제20권3호
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• pp.291-296
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• 1999

The immobilization of APTMS(3-(2-aminoethylamino)propyltrimethoxysilane) and AAPTMS(3-(2-(2-aminoethyl)aminoethylanino)propyltrimethoxysilane) on the surface of high quality mesoporous molecular sieves MCM-41 and MCM-48 have been confirmed by F.T.-IR spectroscopy, Raman spectroscopy, 29Si solid state NMR, and a surface polarity measurement using Reichardt's dye. The formation of metal (Co(Ⅱ), Ni(Ⅱ), and Cu(Ⅱ)) complexes by immobilized aminosilanes have been investigated by photoacoustic spectroscopy(PAS). The assignment of UV-Vis. PAS bands makes it possible to identify the structure of metal complexes within mesoporous molecular sieves. Co(Ⅱ) ion may be coordinated mainly in a tetrahedral symmetry by two APTMS onto MCM-41, and in an octahedral one by two AAPTMS. Both Ni(Ⅱ) and Cu(Ⅱ) coordinated by aminosilanes within MCM-41 form possibly the octahedral complexes such as [Ni(APTMS)2(H20)2]2+, [Ni(AAPTMS)2]2+, [Cu(APTMS)2(H2O)2]2+, and [Cu(AAPTMS)(H2O)3]2+, respectively. The PAS band shapes of complexes onto MCM-48 are similar to those of corresponding MCM-41 with the variation of PAS intensity. Most of metal ion(Ⅱ) within MCM-41 and MCM-48 are coordinated by aminosilanes without the impregnation on the surface.

• 공업화학
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• 제16권6호
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• pp.737-741
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• 2005

본 연구에서는 제조한 MCM-41에 Cu의 함량에 따른 NO의 전환율을 고찰하였다. MCM-41은 실리카 원으로 colloid silica를 사용하였고, template로 cetyltrimethylammonium chloride (CTMACl)를 사용하여 수열 합성하였으며, Cu/MCM-41은 Cu(II) acetylacetonate를 사용해서 Cu의 농도를 5, 10, 20 그리고 40%로 변화시켜 제조하였다. 표면 특성은 pH, FT-IR로 분석하였고, 육방배열의 1차원 기공 구조는 XRD로 고찰하였다. $N_2/77K$ 등온흡착 특성은 BET식과 t-plot을 이용하여 확인하였으며, NO 제거 효율은 가스크로마토그래프를 이용하여 측정하였다. 실험 결과, Si-OH와 Si-O-Si의 stretching vibration peak가 관찰되었으며, (100), (110), (200) 그리고 (210)의 육방배열의 1차원 구조를 확인하였다. Cu 금속이 도입된 MCM-41은 Cu 도입량이 증가할수록 비표면적과 미세기공부피는 감소한 반면에 NO 제거 효율은 증가하였다. 결과적으로 Cu/MCM-41의 Cu의 함량이 증가함에 따라 전체 촉매작용 반응과 NO 제거율이 증가하였다.

• Bulletin of the Korean Chemical Society
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• 제22권9호
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• pp.1045-1048
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• 2001