• 한국자기공명학회논문지
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• 제6권1호
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• pp.20-37
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• 2002

MnAPSO-34 and Mn-impregnated SAPO-34(Mn-SAPO-34) sample were prepared with various manganese contents and studied by electron spin resonance(ESR) and electron spin echo modulation(ESEM). Electron spin echo modulation analysis of 0.07mo1 ％ Mn(relative to p) in MnAPSO-34 with adsorbed D$_{2}$O shows two deuteriums at 0.26 nm and two at 0.36 nm from Mn. This suggests that two waters hydrate an MnO$_{4}$ configuration with a D-O bond orientation for the waters as expect for a negatively charged site at low manganese content (0.1 mol％), the ESR spectra of MnAPSO-34 and MnH-SAPO-34 exhibit the same parameters(g 2.01 and A 89 G), but the spectra obtained from MnAPSO-34 samples are better resolved. The decomposition temperature of as-synthesized MnAPSO-34 were in the range of 200-600 $^{\circ}C$ of the morpholine which is 12 $^{\circ}C$ higher than that in as-synthesized MnH-SAPO-34. Infrared spectra showed that the position of a band at 3450 $cm^{-1}$ / shifted about 15 $cm^{-1}$ / toward higher energy in MnAPSO-34 versus MnH-SAPO-34. The modulation depth of the two-pulse ESE of MnAPSO-34 with adsorbed D$_{2}$O is deeper than that of MnH-SAPO-34 with adsorbed D$_{2}$O. Three-pulse ESEM of MnAPSO-34 and MnH-SAPO-34 with adsorbed deuterium oxide shows that the local environments of manganese in the hydrated samples are different, suggesting that Mn(II) is framework substituted in MnAPSO-34 since it obviously occupies an extraframework position in MnH-SAPO-34.

• 한국자기공명학회:학술대회논문집
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• 한국자기공명학회 2002년도 International Symposium on Magnetic Resonance
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• pp.80-80
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• 2002

MnPSO-34 and Mn-impregnated SAPO-34 (Mn-SAPO-34) sample were prepared with various manganese contents and studied by electron spin resonance (ESR) and electron spin-echo modulation (ESEM). Electron spin-echo modulation analysis of 0.07mol ％ Mn(relative to p) in MnAPSO-34 with adsorbed D$_2$O shows two deuteriums at 0.25 nm and two at 0.36 nm from Mn. This suggests that two waters hydrate an MnO4 configuration with a D-O bond orientation for the waters as expect for a negatively charged site at low manganese content (0.07 mol％), the ESR spectra of MnAPSO-34 and MnH-SAPO-34 exhibit the same parameters (g 2.02 and A 87 G), but the spectra obtained from MnAPSO-34 samples are better resolved. TGA of as-synthesized MnAPSO-34 shows that the decomposition temperature in the range 200-$600^{\circ}C$ of the morpholine is 12$^{\circ}C$ higher than that in as-synthesized MnH-SAPO-34. Infrared spectra shows that the position of a band at about 15 cm-1 toward higher energy in MnAPSO-34 versus MnH-SAPO-34. The modulation depth of the two-pulse ESE of MnAPSO-34 with absorbed D$_2$O is deeper than that of MnH-SAPO-34 with absorbed D$_2$O. Three-pulse ESEM of MnAPSO-34 and MnH-SAPO-34 with absorbed deuterium oxide shows that the local environments of manganese in the hydrated samples are different, suggesting that Mn(II) is framework substituted in MnAPSO-34 since it obviously occupies an extra-framework position in MnH-SAPO-34

• 한국자기공명학회논문지
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• 제5권1호
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• pp.1-12
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• 2001

ZSM-5 gallosilicate molecular sieves was synthesized and cupric ion was ion-exchanged into the gallosilicate. The locations of Cu(ll) species in the framework and their interactions with various adsorbates were characterized by combined electron spin resonance(ESR) and electron spin echo modulation(ESEM) methods. It was found that in a fresh hydrated material, Cu(II) is octahedrally coordinated to six water molecules. This species is located in the channel intersections of two sinusoidal channels and rotates rapidly at room temperature. Evacuation removes some of these water molecules, leaving the Cu(II) coordinated to less water molecules and anchored to of oxygens in the channel wall. Dehydration produces two Cu(II) species, both of which are located in sites inaccessible to oxygen as evidenced by non-broadening of its ESR lines by oxygen. Adsorption of adsorbate molecules such as water, alcohols, ammonia, acetonitrile and ethylene on dehydrated CuNaH-ZSM-5 gallosilicate materials causes changes in the ESR spectrum of Cu(II), indicating the migration of Cu(II) into main channels to form complexes with these adsorbates there. Cu(II) forms a complex with two molecules of methanol, ethanol and propanol, respectively as evidenced by ESR parameters and ESEM data. Cu(II) also forms a square planar complex with four molecules of ammonia, based on the resolved nitrogen superhyperfine interactions and their ESEM parameters. Cu(II) forms a complex with two molecules of acetonitrile based on the ESR parameters and ESEM data. Interestingly, however, only part of Cu(II) interacts indirectly with one molecule of nonpolar ethylene based on ESR and ESEM analyses.

• 대한화학회지
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• 제46권1호
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• pp.26-36
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• 2002

$MoO_3$와 H-SAPO-34의 고체상 반응은 상자기성의 Mo(V) 화학종을 띤다. 탈수하면 Mo(V) 화학 종이 약하게 나타나지만 계속적으로 활성화 시키면 ESR로 규명할 수 있는 $Mo(V)_{5c}$와 $Mo(V)_{6c}$와 같은 Mo(V) 화학종이 생성된다. ESR과 ESEM 자료들은 $(MoO_2)^+$나 $(MoO)^{3+}$ 같은 옥소-몰리브덴 화학 종을 보여준다. $(MoO_2)^+$ 화학 종이 다음과 같이 더 합리적인 것 같이 보여진다. H-SAPO-34는 낮은 골격전하를 갖기 때문에 높은 양전하를 갖는 $(MoO)^{3+}$는 쉽게 안정화 되지 못한다. 소성된 H-SAPO-34와 도데카몰리브덴 규산 용액 사이의 용액 상태 반응은 단지 $MoO^{2+}$ 화학 종만을 발생한다. 마름모형 ESR 신호는 $D_2O$, $CD_3OH$, $CH_3CH_2OD$와 $ND_3$를 흡착할 때 관측되었다. Mo(V) 화학 종의 배위구조와 위치는 트리 펄스 전자 스핀반향 자료로 측정하였다. MoH-SAPO-34에 메탄올, 에틸렌 암모니아와 물이 흡착될 때 3분자, 1분자, 1분자와 1분자가 $(MoO_2)^+$에 각각 직접 배위하였다.

• 한국자기공명학회논문지
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• 제6권2호
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• pp.118-131
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• 2002

Manganese-doped H-SAPO-34 samples were prepared by an ion-exchanged reaction between H-SAPO-34 and paramagnetic Mn(II) species in methanol media and characterized by ESR and Electron Spin-Echo Modulation(ESEM) studies. In the hydrated (W)MnH-SAPO-34 measured in water, the Mn(II) ion was octahedrally coordinated with four framework oxygens and two water molecules at a displaced site IV of the eight membered ring window in the ellipsoidal cavity, while the Mn(II) ion was octahedrally coordinated to three framework oxygens and three water molecules at a displaced site I' of the six membered ring window in the ellipsoidal cavity in hydrated(M)MnH-SAPO-34 measured in methanol. The similar result was found in the experiments with methanol adsorbents except ethanol.

• 한국자기공명학회논문지
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• 제9권2호
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• pp.138-154
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• 2005

Vanadium-incorporated aluminophosphate molecular sieve $VO^{2+}-SAPO-5$ was studied by electron spin resonance (ESR) and electron spin echo modulation (ESEM) spectroscopies to determine the vanadium structure and interaction with various adsorbate molecules. It was found that the main species at low concentration of vanadium is a monomeric vanadium units in square pyramidal or distorted octahedral coordination, both in oxidation state (IV) for the calcined hydrated material and in oxidation state (V) for the calcined material. After calcinations in $O_2$ and exposure to moisture, only species A is observed with reduced intensities. It is suggested as a $VO(H_2O)_3^{2+}$ complex coordinated to two framework oxygen bonded aluminum. When calcined, hydrated $VO^{2+}-}SAPO-5$ is dehydrated at elevated temperature, a species loses its water ligands and transforms to $VO^{2+}$ ions coordinated to two framework oxygens (species B). Species B reduces its intensity, significantly after treatment with $O_2\;at\;600^{\circ}C$ for 5 h, thus suggesting oxidation of $V^{4+}\;to\;V^{5+}$. When dehydrated $VO^{2+}-SAPO-5$ contacts with $D_2O$ at room temperature, the EPR signal of species A is observed. Thus species assumed as a $VO^{2+}(O_f)_2(D_2O)_3$, by considering two framework oxygens. Adsorption of deuterated ethanol, propanol on dehydrated $VO^{2+}_{-}SAPO-5$ result in another new vanadium species E and F, respectively, which are identified as a $VO^{2+}-(CH_3CH_2OD)_3,\;VO^{2+}-(CH_3CH_2CH_2OD)_2$ complex. When deuterated benzene is adsorbed on dehydrated $VO^{2+}-SAPO-5$, another new vanadium species G, identified as a $VO^{2+}-(C_6D_6)$ is observed. Possible coordination geometries of these various complexes are discussed.

• 한국자기공명학회논문지
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• 제5권2호
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• pp.73-90
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• 2001

Vanadium-doped H-SAPO-34 samples were prepared by a high-temperature solid-state reaction between SAPO-34 and the paramagnetic V(Ⅳ) species and characterized carefully by EPR and Electron Spin-Echo Modulation(ESEM) studies. The paramagnetic vanadium species generated in both V$_2$O$\_$5/ and VOSO$\_$4/ of SAPO-34 have the same narrow range of g value fur vanadium species assigned to VO$\^$2+/ inferred from the isotropic EPR spectrum at 293 K. The EPR and ESEM data indicate that the V(Ⅳ) species exist as a vanadyl ion either as [V(Ⅳ)]O$\^$2+/ or V$\^$4+/. The [V(Ⅳ)]O$\^$2+/ species seems to be more probable because SAPO-34 having a low negative framework charged and more positively charged species like V$\^$4+/can not be easily stabilized. Tetravalent vanadium ion in vadium-doped H- SAPO-34 can only be observed at the temperature lower than 77 K, while the vanadyl ion, VO$\^$2+/in the activated sample of VH-SAPO-34 can produce the ion even at room temperature. After the adsorption of methanol, ethanol, propanol or ethene to the VH-SAPO-34, only one molecule coordinate to [V(Ⅳ)]O$\^$2+/ was observed in EPR and ESEM spectra.

• 한국자기공명학회논문지
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• 제11권2호
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• pp.95-109
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• 2007

Vanadium-incorporated aluminophosphate microporous molecular sieve VH-SAPO-42 has been studied by electron spin resonance(ESR) and electron spin-echo modulation (ESEM) spectroscopies to determine the vanadium location and interaction with various adsorbate molecules. The results are interpreted in terms of V(IV) ion location and coordination geometry. Assynthesized VH-SAPO-42 contains only vanadyl species with distorted octahedral or trigonal bipyramidal coordination. Vanadium incorporated into H-SAPO-42 occupied extra-framework site. After calcinations in $O_2$ and exposure to moisture, only species A is observed with reduced intensities. Species A is identified as a $VO(H_2O)_2^{2+}$ complex coordinated to three framework oxygen atoms bonded to aluminum. When hydrated VH-SAPO-42 is dehydrated at elevated temperature by calcination, species A loses its water ligand and transforms to $VO^{2+}$ ions coordinated to three framework oxygens (species B). Species B reduces its intensities significantly after treatment with $O_2$ at high temperature, thus suggesting oxidation of $V^{4+}$ to $V^{5+}$. When dehydrated VH-SAPO-42 makes contact with $D_2O$ at room temperature, the ESR signal of species A is regained. The species is assumed as a $VO(O_f)_3(D_2O)_2$ by considering three framework oxygens. Adsorption of deuterated methanol on dehydrated VH-SAPO-42 results in another new vanadium species D, which is identified as a $VO(CD_3OH)_2$ complex. When deuterated ethylene is adsorbed on dehydrated VH-SAPO-42, another new vanadium species E identified as a $VO(C_2D_4)^{2+}$, is observed. Possible coordination geometries of these various complexes are discussed.

• 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.