• Journal of the Korean Magnetic Resonance Society
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• v.11 no.2
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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.

• Journal of the Korean Chemical Society
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• v.46 no.1
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• pp.26-36
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• 2002

A solid-state reaction of $MoO_3$ with as-synthesized H-SAPO-34 generated paramagnetic Mo(V) species. The dehydration resulted in weak Mo(V) species, and subsequent activation resulted in the formation of Mo(V) species such as $Mo(V)_{5c}$ and $Mo(V)_{6c}$ that are characterized by ESR. The data of ESR and ESEM show the oxomolybdenum species, to be $(MoO_2)^+$ or $(MoO)^{3+}$. The $(MoO_2)^+$ species seems to be more probable. Since H-SAPO-34 has a low framework negative charge, $(MoO)^{3+}$ with a high positive charge can not be easily stabilized. A solution reaction between the solution of silico-molybdic acid and calcined H-SAPO-34 resulted in only $(MoO_2)^+$ species. A rhombic ESR signal is observed on adsorption of $D_2O$, $CD_3OH$, $CH_3Ch_2OD$ and $ND_3$. The Location and coordination structure of Mo(V) species has been determined by three-pulse electron spin-echo modulation data and their simulations. After the adsorption of methanol, ethylene, ammonia, and water for MoH-SAPO-34, three molecules, one molecule, one and one molecule, respectively, are directly coordinated to $(MoO_2)^+)$.

• Bulletin of the Korean Chemical Society
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• v.34 no.8
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• pp.2399-2402
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• 2013

The catalytic pyrolysis of cellulose was carried out over SAPO-11 for the first time. Pyrolyzer-gas chromatography/mass spectroscopy was used for the in-situ analysis of the pyrolysis products. The acid sites of SAPO-11 converted most levoglucosan produced from the non-catalytic pyrolysis of cellulose to furans. In particular, the selectivity toward light furans, such as furfural, furan and 2-methyl furan, was high. When the catalyst/cellulose ratio was increased from 1/1 to 3/1 and 5/1, the increase in the quantity of acid sites led to the promotion of deoxygenation and the resultant increase of the contents of light furan compounds. Because furans can be used as basic feedstock materials, the augmentation of the economical value of bio-oil through the catalytic upgrading over SAPO-11 is considerable.

• Korean Journal of Materials Research
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• v.9 no.8
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• pp.798-803
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• 1999

This study has been focused on the influence of Fe(III) incorporation into framework of SAPO-34(FeAPSO-34s;/su/Fe = 40,20 and 5) on the catalytic performance of methanol conversion. By rapid crystallization method, the XRD,SEM,ICP,TG-DTA, and BET sufrace areas. With an increase in the Fe content incorporated to the framework, the crystallinity identified from the intensity of XRD peaks slightly decreased and the particle size observed from SEM photographs decreased also. On the other hand, the acid sites in crystal decreased kin the Fe-incorporated samples, and the selectivity to ethylene for FeAPSO-34 catalyst on methanol conversion was enhanced compared with the nonmetal incorporated(SAPO-34)

• Journal of the Korean Chemical Society
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• v.38 no.1
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• pp.1-7
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• 1994

Semiempirical MNDO calculations are employed to study ionicity of OH groups and stability in $T_1-OH-T_2bridges(T_1$ = Al, B and $T_2$ = P, Si) such as found in aluminophosphate family($AlPO_4-5$, BAPO-5, and SAPO-5) molecular sieves. Dimeric model clusters of Al-OH-P, B-OH-P and Al-OH-Si bridges were considered. It is shown that the elongation of the T-O bond, upon replacement of Al by B, occurs preferentially by a local deformation of the Al-O-P bridge. But the elongation of the T-O bond occurs preferentially by a rotation of Al-O-Si bridge upon substitution P for Si. Also, the ionicity of OH groups and stability increase in order to B-OH-P < Al-OH-P < Al-OH-Si bridge.

• Journal of Environmental Science International
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• v.16 no.12
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• pp.1355-1367
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• 2007

This study summarizes the relations among $PM_{2.5}$ concentration, water-soluble ions concentration, metallic element Components characteristics and SPSS in negative ion and metallic element of $PM_{2.5}$ particle in Miryang.(By the urban area, the industrial complex area and the suburban area according to the season) $PM_{2.5}$ concentration of total 72 samples collected from 3 sites turned out to range from 3.47 to 34.7 ${\mu}g/m^3$, and the average concentration was the suburban area-the kin nup(16.00 ${\mu}g/m^3$) > the urban area-the roof of the old Miryang university(10.32 ${\mu}g/m^3$) > the industrial complex-Sapo industrial complex(10.29 ${\mu}g/m^3$). In particular, the suburban area had $PM_{2.5}$ concentration 1.5 times those of urban area, industrial complex. It was thought although the site was suburban and farm-side without pollutants around, it had a higher concentration value influenced by external factors including the brickyard, small-scale incinerator, driving range construction, construction on the Daegu-Busan express and the widening of the four-lane road between Miryang-Anyang nearby. As for water-soluble ions among $PM_{2.5}$ particle collected in Miryang area, $SO4_{2^-}$ accounted for 60% and $NO_{3^-}$, was 30% in spring and summer. And $NO_{3^-}$ accounted for 50% and $SO4_{2^-}$ was 35% in fall and winter. The AI value of metallic Components among $PM_{2.5}$ particle collected in Miryang area had a high value influenced by the apartment complex construction and the extension work of road. The industrial complex area had Zn concentration 3 times, and Fe concentration 2 times those of urban area and suburb area. When it comes to the relation with metallic elements in urban area, the highest coefficient of correlation was between Cr-Fe with 0.85, and Pb-Cd turned out in the reverse correlation. Among metallic elements, the coefficients of correlation between Zn and Cr, Mn, Fe, NI were high in industrial complex area. The highest coefficient of correlation was between Mn-Zn with 0.88, meanwhile Ni and Cu, Cd turned out in the reverse correlation in the suburb area. These coefficients of correlation are attributed to the difference in pollutant sources, rather than difference in pollutant and non-pollutant.