• 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.

• Transactions of the Korean hydrogen and new energy society
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• v.28 no.5
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• pp.433-439
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• 2017

The high temperature performance of PEM type electrolyser at $120^{\circ}C$ based on covalently cross-linked sulfonated poly ether ether ketone (SPEEK) composie membrane was investigated. Ion conductivity and other properties of SPEEK membrane were improved by adding heteropoly acid and Ceria. The membrane electrode assemblies were prepared using commercial PtC and nano-sized $IrRuO_2$ catalyst by electro-spraying and decal process. Voltage efficiency of MEA equipped with SPEEK membrane was slightly better than that of $Nafion^{(R)}$ membrane, due to its higher proton conductivity at high temperature. The cell performance of MEA with CL-SPEEK/Cs-TSiA/Ceria is 1.71 V at $1A/cm^2$ and $120^{\circ}C$.

• Macromolecular Research
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• v.12 no.1
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• pp.22-25
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• 2004

We have synthesized aniline oligomer composites by using heteropoly acid (H$_4$SiW$_{12}$O$_{40}$ ) as a dopant. The doping and dedoping processes of the aniline oligomer composites were investigated with the aid of UV- Vis spectra. The bands of the aniline oligomer at 572 nm weakened or disappeared, and the bands at 268, 412, and 771 nm appeared, after the aniline oligomer was doped. When the solution of the aniline oligomer doped with H$_4$SiW$_{12}$O$_{40}$ was kept at lower values of pH, the aniline oligomer could not be dedoped by dilution. The turning point of doping and dedoping occurred at pH 5.5. The band at 771 nm shifted towards longer wavelengths when the aniline oligomer composites were synthesized using acetone as the solvent. This observation indicates that the molecular chain became stretched. In addition, we also investigated the change of the electronic absorption spectra of the composites with respect to the time laid up.id up.

• Proceedings of the Membrane Society of Korea Conference
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• 1992.04a
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• pp.35-36
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• 1992

화학반응이 주로 고온에서 일어나기 때문에 polymer membrane의 화학반응에의 적용은 거의 없었으며, 연구의 대부분은 열적 안정성이 좋은 inorganic membrane reactor에 대하여 이루어져 왔다. 산 및 산화환원 촉매로써의 12-텅스토인산은 반응물의 종류에 따라 특이한 흡착 특성을 보이며, 헤테로폴리산만이 지니는 특징적인 surface, bulk 특성 때문에 바능물의 종류에 따라 반응은 촉매의 surface and/or bulk에서 일어난다. 무기 축합산인 12-텅스토인산이 지니는 또 하나의 특징은 물, 알콜, ether 같이 산소를 포함하는 organic solvent에 매우 잘 녹는다는 사실이다.

• Clean Technology
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• v.25 no.1
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• pp.91-97
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• 2019

Oxidative desulfurization (ODS) has received much attention in recent years because refractory sulfur compounds such as dibenzothiophenes can be oxidized selectively to their corresponding sulfoxides and sulfones, and these products can be removed by extraction and adsorption. In this work, The oxidative desulfurization of marine diesel fuel was performed in a batch reactor with hydrogen peroxide ($H_2O_2$) in the presence of various supported heteropoly acid catalysts. The catalysts were characterized by XRD, XRF, XPS and nitrogen adsorption isotherm techniques. Based on the sulfur removal efficiency of promising silica supported heteropoly acid catalysts, the ranking of catalytic activity was: $30\;H_3PW_{12}/SiO_2$ > $30\;H_3PMo_{12}/SiO_2$ > $30\;H_4SiW_{12}/SiO_2$, which appears to be related with their intrinsic acid strength. The $30\;H_3PW_{12}/SiO_2$ catalyst showed the highest initial sulfur removal efficiency of about 66% under reaction conditions of $30^{\circ}C$, $0.025g\;mL^{-1}$ (cat./oil), 1 h reaction time. However, through the recycle test of the $H_3PW_{12}/SiO_2$ catalyst, significant deactivation was observed, which was attributed to the elution of the active component $H_3PW_{12}$. By introducing cesium cation ($Cs^+$) into the $H_3PW_{12}/SiO_2$ catalyst, the stability of the catalyst was improved with changing the solubility, and the $Cs^+$ ion exchanged catalyst could be recycled for at least five times without severe elution.

• Journal of the Korean Chemical Society
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• v.54 no.4
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• pp.411-413
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• 2010

A simple, efficient and an environmental friendly method have been developed for the synthesis of substituted indole from aryl hydrazines and aldehydes/ketones with HPA-phosphomolybdic acid as a heterogeneous catalyst. The catalyst is nontoxic and recyclable.

• Korean Chemical Engineering Research
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• v.57 no.6
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• pp.891-897
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• 2019

In this study, heteropoly acid PVMo catalysts were supported on activated carbon with various composition of phosphoric acid ($H_3PO_4$), vanadium (V) pentoxide ($V_2O_5$) and molybdenum (VI) trioxide ($MoO_3$). Catalytic performance was examined at $140^{\circ}C$ for 1hour in vapor formaldehyde. XRD and BET analyses were carried with the catalysts before and after the reaction. Formaldehyde conversion was increased with decreasing Mo and $H_3PO_4$ content and increasing $V_2O_5$ content. Acidity of the catalysts was investigated with $NH_3-TPD$. Crystallinity of the catalysts was relatively low, and surface area was decreased after the reaction. In $NH_3-TPD$ result, the ratio of strong acid site corresponding to $NH_3$ desorption between $400^{\circ}C$ and $500^{\circ}C$ was increased by decreasing $MoO_3$ and $H_3PO_4$ content and increasing $V_2O_5$ content. Therefore, it was found that the strong acid site could affect the catalytic reactivity in vapor formaldehyde conversion.

• Applied Chemistry for Engineering
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• v.5 no.5
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• pp.819-824
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• 1994

A membrane-like $H_3PMo_{12}O_{40}$-polysulfone film was prepared by blending $H_3PMo_{12}O_{40}$ with polysulfone using dimethylformamide as a common solvent. SEM and EDX analysis showed that $H_3PMo_{12}O_{40}$ was uniformly and finely distributed in the film catalyst. The ESCA measurement also revealed that the oxidation state of Mo was not changed. The $H_3PMo_{12}O_{40}$-polysulfone catalyst showed lower activity for acid-catalyzed reaction and higher activity for oxidation reaction than $H_3PMo_{12}O_{40}$ in ethanol conversion reaction. The oxidation activity of the film catalyst was about 10 times higher than $H_3PMo_{12}O_{40}$. The decrease of acidic activity was due to DMF strongly adsorbed in acid sites of $H_3PMo_{12}O_{40}$, whereas the increase of oxidation activity was mainly due to uniform distribution of $H_3PMo_{12}O_{40}$. Adsorption results showed that the surface character of $H_3PMo_{12}O_{40}$ was drastically increased, while the bulk property of that was almost same after blending. It is suggested that the control of surface/bulk property as well as acid/redox property of heteropoly acid would be possible by blending it with a polymer.

• 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.

• 한국신재생에너지학회:학술대회논문집
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• 2010.11a
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• pp.85.2-85.2
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• 2010

There is widespread effort to develop polymer membranes in place of Nafion for high temperature polymer electrolyte membrane fuel cell(PEMFC). In our study, SiO2 membranes are arranged by electrospinning method. For impregnation solution, the modified sulfonated poly(ether ether ketone)(SPEEK) polymer is prepared from sulfonation, sulfochlorination, partial reduction and lithiation reaction. The modified polymer is cross-linked with 1,4-diiodobetane in NMP solvent and then blended with Heteropoly acid(HPA). The characterization of membranes is confimed by FT-IR, Thermogravimetry(TGA), water uptake test and single cell performance test for PEMFC, etc. The composite membrane shows satisfactory thermal and mechanical properties. Beside, The membrane exhibits good ion exchange capacity and high proton conductivity. As a result, The composite membrane is promising as an alternative membrane in high temperature PEMFC.