• Journal of the Korean Chemical Society
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• v.19 no.1
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• pp.16-20
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• 1975

3-Molybdo-9-tungstophosphoric acid, 6-molybdo-6-tungstophosphoric acid and their one-electron and two-electron reduction products have been synthesized. Infrared spectra show that all of them have Keggin structure. Polarograms and optical spectra of the reduced species are reported. Both data indicate that each additional electron is localized on a molybdenum atom.

• Bulletin of the Korean Chemical Society
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• v.27 no.8
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• pp.1246-1248
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• 2006

• 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.

• Proceedings of the Membrane Society of Korea Conference
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• 1992.10a
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• pp.43-44
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• 1992

촉매막반응기란 반응기와 분리막이 동시에 하나의 과정으로 결합된 unit로, 촉매막반응기를 사용할 경우 가역 반응에서 막을 통한 생성물의 선택적 제거는 화학 평형이동을 유발시켜 열역학적으로 얻을수 있는 평형 전환율보다 높은 전환유을 얻을 수 있다. 본 연구는 이러한 촉매막반응기의 성능에 대한 실험적 연구로, 산 촉매하에서 일어나는 MTBE 분해반응을 12-텅스토인산 촉매상에서 수행하였다.

• Membrane Journal
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• v.21 no.2
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• pp.141-147
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• 2011

The cation exchange membrane using TPA (tungstophosphoric acid) and the block co-polymer of polysulfone and polyphenylenesulfidesulfone was prepared for a separator of all-vanadium redox flow battery. The membrane resistance of the prepared cation exchange membrane in 1mol/L $H_2SO_4$ aqueous solution was measured. The membrane resistance of the prepared Psf-PPSS and Psf-TPA-PPSS cation exchange membrane was about $0.94{\Omega}{\cdot}cm^2$. Electrochemical property of all-vanadium redox flow battery using the prepared cation exchange membrane was measured. The measured charge-discharge cell resistance of V-RFB at 4 A decreased in the order; Nafion117 < Psf-TPA-PPSS < Psf-PPSS. The durability of membrane was earried out by soaking it in $VO_2{^+}$ solution and evaluated by measuring the charge-discharge cell resistance of V-RFB with an increase of soaking time. The prepared Psf-PPSS cation exchange membrane had high durability and Psf-TPA-PPSS cation exchange membrane had almost same durability compared with Nafion117.

• 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.

• 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.

• Journal of Hydrogen and New Energy
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• v.20 no.3
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• pp.194-201
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• 2009

The e1ectrocatalytic properties of heteropolyacids(HPAs) entrapped in covalently cross-linked sulfonated polyetheretherketone(CL-SPEEK/HPA) membranes have been studied for water electrolysis. The HPAs, including tungstophosphoric acid(TPA), molybdophosphoric acid(MoPA), and tungstosilicic acid(TSiA) were used as additives in the composite membranes. The MEA was prepared by a non-equilibrium impregnation-reduction(I-R) method, using reducing agent, sodium borohydride(NaBH4) and tetraamineplatinum(II) chloride(pt(NH$_3$)$_4$Cl$_2$). The electrocatalytic properties of composite membranes such as the cell voltage were in the order of magnitude CL-SPEEKlMoPA40 (wt%) > /TPA30 > /TSiA40. In the optimum cell applications for water electrolysis, the cell voltage of PtlPEM/Pt-Ru MEA with CL-SPEEKlTPA30 membrane was 1.75 V at 80$^{\circ}$C and I A/cm$^2$ and this voltage carried lower than that of 1.81 V of Nafion 117. Consequently, in regards of electrochemical and mechanical characteristics and oxidation durability, the newly developed CL-SPEEKITPA30 composite membrane exhibited a better performance than the others, but CLSPEEKlMoPA40 showed the best electrocatalytic activity (1.71 Vat 80$^{\circ}$C and 1 A/cm$^2$) among the composite membranes.

• Journal of Hydrogen and New Energy
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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.

• Journal of Hydrogen and New Energy
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• v.28 no.1
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• pp.17-23
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• 2017

Polyether ether ketone (PEEK) composite including tungstophosphoric acid(TPA) membranes have been intensively investigated for polymer electrolyte membrane water electrolysis (PEMWE) and thus covalently linked sulfonated polyether ether ketone (CL-SPEEK) with captured TPA composite membranes were prepared and characterized. Sulfonated polyether ether ketone (SPEEK) was prepared in sulfonation of PEEK and was cross-linked with 1,4 diiodobutane. The carbonyl group of SPEEK was reduced with $NaBH_4$ and 3-isocyanatepropyltriethoxysilane (ICPTES) was added. The TPA captured composite was prepared in reaction of TPA with 3-mercaptopropyltrime thoxysilane (MPTMS). The polymer composite membranes showed better thermostability and electrochemical properties than SPEEK. The membranes were prepared by sol-gel casting method. The polymer composite membrane featured 0.1285 S/cm of proton conductivity at $80^{\circ}C$ and outstanding durability.