• Proceedings of the Membrane Society of Korea Conference
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• 2003.07a
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• pp.37-40
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• 2003

Mesoporous zeolite - heteropolyacid-polymer hybrid membrane was prepared by sol-gel processes to make a proton conducting membrane. The crystallinity of mesoporous zeolite in composite membrane was increased with contents of heteropolyacid. Proton conductivity obtained from impedance measurements increases with contents of heteropolyacid, about 10$^{-3}$ S/cm in ca. 1.5 Wt% heteropolyacid.

• Korean Chemical Engineering Research
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• v.47 no.2
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• pp.163-168
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• 2009

Negative differential resistance(NDR) behaviors of Keggin-type and Wells-Dawson-type heteropolyacids with cation, heteroatom, and polyatom substitutions were investigated by scanning tunneling microscopy. A reliable correlation between NDR peak voltage and reduction potential of heteropolyacid catalysts was established. It was found that more reducible heteropolyacid catalyst showed NDR behavior at less negative voltage, regardless of the structural difference. Thus, NDR peak voltage of heteropolyacid catalyst could be utilized as a single correlating parameter for the reduction potential of heteropolyacid catalyst.

• Applied Chemistry for Engineering
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• v.18 no.1
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• pp.36-40
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• 2007

The study on the isomerization reaction of endo-tetrahydrodicyclopentadiene and endo-tetrahydrodi(methylcyclopentadiene) using heteropolyacid catalyst was carried out. Exo compound was prepared from endo compound through isomerization reaction. To improve the problem of aluminum chloride as an isomerization catalyst, application of heteropolyacid was attempted. In use of Keggin type heteropolyacid, catalytic activity was extremely high at cesium substitution instead of 2.5 hydrogen atoms of $H_3PW_{12}O_{40}$. Using the cesium substituted heteropolyacid, isomerization reaction rate was faster than aluminum chloride and the effect of reaction temperature and times on reactivities were compared in isomerization of tetrahydrodicyclopentadiene and tetrahydrodi(methylcyclopentadiene).

• Korean Chemical Engineering Research
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• v.50 no.2
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• pp.251-256
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• 2012

Etherification of n-butanol to di-n-Butyl Ether was carried out over Keggin $H_{3+x}PW_{12-x}Nb_xO_{40}$ (x=0, 1, 2, 3) and $H_{6+x}P_2W_{18-x}Nb_xO_{62}$ (x=0, 1, 2, 3) Wells-Dawson heteropolyacid catalysts. Niobium-substituted Keggin and Wells-Dawson heteropolyacid catalysts with different niobium content were prepared. Successful preparation of the catalysts was confirmed by FT-IR, ICP-AES, and $^{31}P$ NMR analyses. Their acid properties were determined by $NH_3$-TPD (Temperature-Programmed Desorption) measurements. Heteropolyacid catalysts showed different acid properties depending on niobium content in both series. The correlation between acid properties of heteropolyacid catalysts and catalytic activity was then established. Acidity of Keggin and Wells-Dawson heteropolyacid catalysts decreased with increasing niobium content, and conversion of n-butanol and yield for di-n-butyl ether increased with increasing acidity of the catalysts, regardless of the identity of heteropolyacid catalysts (without heteropolyacid structural sensitivity). Thus, acidity of heteropolyacid catalysts served as an important factor determining the catalytic performance in the etherification of n-butanol to di-n-Butyl Ether.

• Proceedings of the Membrane Society of Korea Conference
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• 2005.05a
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• pp.100-103
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• 2005

• Proceedings of the Membrane Society of Korea Conference
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• 2008.05a
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• pp.51-57
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• 2008

Mixed matrix membranes of poly(vinyl alcohol) (PVA), loaded with phosphomolybdic heteropolyacid (HPA) and crosslinked with glutaraldehyde have been prepared by the solution casting technique. Pervaporation (PV) experiments have been performed at $30^{\circ}C$ to separate water-isopropanol feed mixtures containing 10 to 40 wt.% of water. The membranes were characterized by DSC and DMTA to understand their thermal behavior and mechanical strength properties. At high content (i.e. 7 wt.% with respect to weight of PVA) of HPA, the mixed matrix membranes could extract water efficiently on the permeate side with a selectivity of 90,000 and a flux of 0.032 $kg/m^2h$ for 10 wt.% of water containing feed mixture (the lowest feed composition of water studied). Flux of the mixed matrix membranes decreased with increasing concentrations of HPA.

• Korean Membrane Journal
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• v.10 no.1
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• pp.20-25
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• 2008

Proton conducting composite membranes were prepared by solution blending of poly(vinylidene fluoride-co-chlorotrifluoroethylene)-graft-poly(sulfopropyl methacrylate) (P(VDF-CTFE)-g-PSPMA) graft copolymer and heteropolyacid (HPA). The P(VDF-CTFE)-g-PSPMA graft copolymer was synthesized by atom transfer radical polymerization (ATRP) using direct initiation of the secondary chlorines of P(VDF-CTFE). FT-IR spectroscopy revealed that HPA nanoparticles were incorporated into the graft copolymer via hydrogen bonding interactions. The water uptake of membranes continuously decreased with increasing HP A concentration up to 45wt%, after which it slightly increased. It is presumably due to the decrease in number of water absorption sites due to hydrogen bonding interaction between the HP A particles and the polymer matrix. The proton conductivity of membranes increased with increasing HPA concentration up to 45wt%, resulting from both the intrinsic conductivity of HP A particles and the enhanced acidity of the sulfonic acid of the graft copolymer.

• Bulletin of the Korean Chemical Society
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• v.32 no.11
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• pp.3963-3966
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• 2011

A series of pyranopyrazoles, was efficiently synthesized via one-pot, four component reaction of ethyl acetoacetate, hydrazine hydrate, aldehydes and malononitrile in the presence of catalytic amount silicotungstic acid under solvent free condition. NOE experiments confirmed that the product exist exclusively in the 2H form. The present protocol offers the advantages of clean reaction, short reaction time, high yield, easy purification and economic availability of the catalyst.

• Proceedings of the Korean Fiber Society Conference
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• 2002.04a
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• pp.459-461
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• 2002

A new class of materials based on organic and inorganic species combined at a molecule level has obtained more attention recently[1]. HPA(heteropolyacid) shows unmatched applied perspective in terms of synthesis chemistry, analysis chemistry, biology, medicine and materials science[2]. As a potential photochemical material, the hybrid system of HPA and polymer has been investigated. However, the design and synthesis of heteropolyacid-based hybrids, which are at the forefront of the materials chemistry research, is still in its infancy. (omitted)

• Journal of the Korean Chemical Society
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• v.55 no.1
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• pp.14-18
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• 2011

Esterification of methacrylic acid with ethylene glycol was carried out over Heteropolyacids [HPA: $H_4SiW_{12}O_{40}$ (STA) and $H_3PW_{12}O_{40}$ (PTA)] supported on ZSM-5. For comparison, the same reaction was carried out over unsupported HPA, $H_2SO_4$, $BF_3$ and PTSA. Among the catalysts studied, HPA showed better activity compared to $H_2SO_4$, $BF_3$ and PTSA. Catalytic activity was compared with HPA supported ZSM-5 catalysts. Typical results indicated that 30 wt% PTA supported on ZSM-5 showed nearly the same activity as that of bulk PTA. It was found that the reaction follows first order kinetics with respect to methacrylic acid. The reaction products were identified by $^1H$-NMR and FT-IR.