• Journal of the Korean Chemical Society
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• v.52 no.1
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• pp.23-29
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• 2008

Simple Keggin type tungsten and molybdenum heteropoly acids, H3PW12O40 and H3PMo12O40, were usedas water-tolerant catalysts for the oxidation of alcohols with 34% hydrogen peroxide in normal drinking water. Accordingto our findings, H3PW12O40 may be used as a simple, effective, and cheap catalyst for this type of transformation in nor-mal drinking water with excelent yields. Efects of diferent solvents at 25-80oC and changing concentration of catalystand substrate on the reaction progress were also studied.

• Applied Chemistry for Engineering
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• v.4 no.3
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• pp.549-557
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• 1993

In the conversion of ethanol over heteropoly acids, we have studied catalytic reactivity, reaction mechanism, effect of organic bases added to reactant, and relation between acid strength of ion-exchanged catalysts and catalytic activities. The conversion of ethanol proceeded in the pseudoliquid phase of heteropoly acid. Due to this novel behavior, area increased by supporting with $SiO_2$. The reaction mechanism of ethylene production was different from that of ether production, and various partially substituted Al salts of 12-tungstophosphoric acid showed different catalytic activities.

• Journal of the Korean Chemical Society
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• v.52 no.1
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• pp.52-56
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• 2008

facile and efficient method for the preparation of Z-aldoximes is improved by means of H3PMo12O40 catalyst in solvent-free media. The major advantages of this method are: operational simplicity, low catalyst loading, selectivity, mild reaction conditions, short reaction times and excellent yields. The recovered catalyst could be used in new attempts without any purification.

• Applied Chemistry for Engineering
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• v.4 no.1
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• pp.162-170
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• 1993

Vapor-phase ETBE(ethyl tert-butyl ether) synthesis from TBA(tert-butyl alcohol) and ethanol was carried over solid acid catalysts such as heteropoly acids and proton type zeolites. Heteropoly acids were more active than proton type zeolites and $H_4SiW_{12}O_{40}$ catalyst showed about the same activity as Amberlyst-15 ion exchange resin catalyst used as an industrial catalyst in ETBE synthesis. The catalytic activity of transition metal exchanged heteropoly acids was greatly enhanced, because new acid site was generated with hydrogen reduction. This effect of hydrogen reduction was related to the reduction characteristics of catalysts and the order of reducibility was $Ag^+$>$Cu^{2+}$>$Fe^{2+}$.

• Applied Chemistry for Engineering
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• v.2 no.4
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• pp.363-371
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• 1991

The catalytic performance and availability of heteropoly compounds for the conversion of methanol to hydrocarbons have been studied. The effects of reaction conditions such as reaction temperature, methanol partial pressure and residence time and the effects of ion-exchange of the catalysts were examined for enhancing the yield of hydrocarbons and the selectivity of low olefins. Their acid strength depended on the kind of countercation, and the yield of hydrocarbons and the selectivity for propylene to propane were closely related to the electronegativity of the corresponding countercations. In contrast to the other heteropoly compounds, the ammonium salt showed a considerably high catalytic activity and a high selectivity for paraffins to low olefins.

• Applied Chemistry for Engineering
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• v.5 no.3
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• pp.431-437
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• 1994

The role and the formation of surface and bulk acid sites of heteropoly acids were studied by examining ethanol conversion and MTBE (methyl t-butyl ether) decomposition reaction. In ethanol dehydration diethylether was formed on the surface acid site of 12-tungstophosphoric acid, whereas ethylene was formed in the bulk acid site of the catalyst. It was revealed that water reinforced the bulk acid site of the catalyst, while organic base decreased the bulk acid function of the catalyst. The formation of acid sites of metal salts was due to hydrolysis of crystalline water and/or partial substitution of metal, and with hydrogen treatment, the acid site was reappeared. Also catalyst design as a selective oxidation catalyst was possible by controlling acid function of heteropoly acid catalyst.

• Applied Chemistry for Engineering
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• v.4 no.2
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• pp.335-341
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• 1993

In the conversion of methanol, the effect of acide property of heteropoly compounds on the catalytic activity was investigated. The pretreatment of Cu-exchanged 12-tungstophosphoric acid with hydrogen enhanced both the selectivity for propane and the conversion of methanol, and the pretreatment of Al-exchanged 12-tungstophosphoric acid with water enhanced the acid strength of the catalyst. The water added into the reactant decreased the conversion of methanol, while the pretreatment temperature did not affect it but the propylene/propane ratio. Various partially-substituted Al salts of 12-tungstophosphoric acid showed different catalytic activities depending on the degree of Al-substitution.

• Applied Chemistry for Engineering
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• v.8 no.2
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• pp.211-219
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• 1997

Liquid or gas phase alkylation of isobutane with 1-butene for i-octane production was carried out over Cs- or $NH_4$-exchanged $H_3PW_{12}O_{40}$. Pretreatment temperature of the catalyst played an important role on the catalytic activity of heteropoly acids in the liquid phase alkylation. Cation-exchanged $H_3PW_{12}O_{40}$ showed a better total yield and i-octane selectivity than the mother acid in the liquid phase alkylation, and $(NH_4)_{2.5}H_{0.5}PW_{12}O_{40}$ was more efficient than $Cs_{2.5}H_{0.5}PW_{12}O_{40}$ in terms of i-octane selectivity. It was found that the acidic property (deactivation of acid sites) of the catalyst was closely related to the catalytic activity of Cs- or $NH_4$-exchanged $H_3PW_{12}O_{40}$ in the gas phase alkylation. $C_5-C_7$ were mainly formed in the early stage of gas phase alkylation due to the strong acidic property of the catalyst, whereas $C_8$ and $+C_9$ were mainly produced as the reaction proceeded due to the deactivation of acid sites. $Cs_{2.5}H_{0.5}PW_{12}O_{40}$ showed the highest total yield in the gas phase alkylation among the catalysts examined.

• Clean Technology
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• v.19 no.1
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• pp.13-21
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• 2013

The hydrogenolysis of cellulose into polyols was examined over Pt/$Cs_xH_{3-x}PW_{12}O_{40}$ catalysts containing different Cs fractions. The surface area and Pt dispersion of Pt/$Cs_xH_{3-x}PW_{12}O_{40}$ catalysts were found to increase with Cs content. Similar polyol yields were obtained over Pt/$Cs_xH_{3-x}PW_{12}O_{40}$ catalysts irrespective of their Cs content. The catalytic activity of Pt/$Cs_xH_{3-x}PW_{12}O_{40}$ was comparable to that of Ni/W/SBA-15 and combined catalytic systems such as Pt/AC+$H_3PW_{12}O_{40}$ and Pt/AC + $Cs_{3.0}PW_{12}O_{40}$. Some polyanion species were found to leach from the Pt/$Cs_xH_{3-x}PW_{12}O_{40}$ catalyst during the course of the reaction.

• Transactions of the Korean hydrogen and new energy society
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• v.20 no.2
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• pp.95-103
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• 2009

In order to improve the electrochemical, mechanical and electrocatalytic characteristics, engineering plastic of polyether ether ketone (PEEK) as polymer matrix was sulfonated (SPEEK) and the organic-inorganic blend composite membranes has been prepared by loading heteropoly acids (HPAs), including tungstophosphoric acid (TPA), molybdophosphoric acid (MoPA), and tungstosilicic acid (TSiA). And then these were covalently cross-linked (CL-SPEEK/HPA) as the electrolyte and MEA of polymer electrolyte membrane electrolysis (PEME). As a result, the optimum reaction conditions of CL-SPEEK/HPA was established and the electrochemical characteristics such as ion conductivity ($\sigma$) were in the order of magnitude: CL-SPEEK /TPA30 (${\sigma}=0.128\;S/cm^{-1}$) < /MoPA40 (${\sigma}=0.14\;S/cm^{-1})$ < /TSiA30 (${\sigma}=0.22\;S/cm^{-1}$) at $80^{\circ}C$, and mechanical characteristics such as tensile strength: CL-SPEEK /TSiA30 $\fallingdotseq$ /MoPA40 < /TPA30. Consequently, in regards of above characterisitics and oxidation durability, the CL-SPEEK/TPA30 exhibited a better performance in PEME than the others, but CL-SPEEK/MoPA40 showed the best electrocatalytic activity of cell voltage 1.71 V among the composite membranes. The dual effect of higher proton conductivity and electrocatalytic activity with the addition of HPAs, causes a synergy effect.