• Applied Chemistry for Engineering
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• v.8 no.4
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• pp.582-588
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• 1997

Synthetic reaction of TAME, ETBE, and MTBE compounds used largely for gasoline octane number enhancer to prevent air pollution was investigated using heteropolyacid catalyst in a fixed bed flow reactor. In the synthetic reaction of TAME, ETBE and MTBE, after hetero atom being replaced with poly atom, the activity of the catalyst, $H_4SiW_{12}O_{40}$ with coordinated bond with W and an hetero atom of Si was the highest among the catalysts tested. Also the activity depended upon the metals replaced which are related to the catalyst acidity. $FeHPW_{12}O_{40}$ and $K_3PM_{o12}O_{40}$ catalysts showed high activity in TAME synthesis, while they were not effective in ETBE and MTBE synthesis. In this study catalysts showing high activity were selected and mixed with equal weight combination of $H_4SiW_{12}O_{40}$ and $Sr_2SiW_{12}O_{40}$ ;$H_4SiW_{12}O_{40}$ and $NaH_2PW_{12}O_{40}$ ; $Fe_{1.5}PW_{12}O_{40}$ and $Mg_2SiW_{12}O_{40}$ ; $Mg_2SiW_{12}O_{40}$ and $Ba_2SiW_{12}O_{40}$. The mixed heteropolyacid catalysts showed higher TBA conversion rate and better selectivity of ETBE and MTBE than the single catalysts.

• Membrane Journal
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• v.19 no.2
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• pp.96-103
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• 2009

A series of organic-inorganic composite membranes from poly(vinyl chloride) (PVC) graft copolymer electrolyte and heteropolyacid (HPA) were prepared for proton conducting membranes. First, poly(vinyl chloride)-g-poly(styrene sulfonic acid) (PVC-g-PSSA) was synthesized by atom transfer radical polymerization (ATRP) using direct initiation of the secondary chlorines of PVC. HPA nanoparticles were then incorporated into the PVC-g-PSSA graft copolymer though the hydrogen bonding interactions, as confirmed by FT-IR spectroscopy. The proton conductivity of the composite membranes increased from 0.049 to 0.068 S/cm at room temperature with HPA contents up to 0.3 weight traction of HPA, presumably due to both the intrinsic conductivity of HPA particles and the enhanced acidity of the sulfonic acid of the graft copolymer. The water uptake decreased from 130 to 84% with the increase of HPA contents up to 0.45 of HPA weight traction, resulting from the decrease in number of water absorption sites due to hydrogen bonding interaction between the HPA particles and the polymer matrix. Thermal gravimetric analysis (TGA) demonstrated the enhancement of thermal stabilities of the composite membranes with increasing concentration of HPA.

• Proceedings of the Membrane Society of Korea Conference
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• 2008.05a
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• pp.147-150
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• 2008

• Transactions of the Korean hydrogen and new energy society
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• v.16 no.1
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• pp.40-48
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• 2005

Until recently, only perfluorinated ionomer membrane such as Nation and Aciflex practically could be successfully used in water splitting. However, these membrane are limited by high cost and loss of membrane performance such as proton conductivity at elevated temperature above 80$^{\circ}C$. The sulfonated aromatic polymers such as PEEK and PSf, polyimides, and polybenzimidazoles are expected to have lower production cost as well as satisfactory chemical and electrochemical properties. HPAs and sulfonated polymers could have a significant influence on water electrolysis performance at elevated temperatures above 80$^{\circ}C$, but these phenomena have received relatively little attention until now. Therefore, it would be desirable to investigate the interrelation between the HPA and sulfonated polymer, such as SPEEK. The SPEEK membrane were prepared by the sulfonation of PEEK, and HPA was blended with SPEEK to increase the mechanical strength and electrochemical characteristics. As a results, electrochemical characteristics such as proton conductivity and ion exchange capacity were improved with the addion of 0.5 g HPA. And the properties of polymer electrolyte, SPEEK/HPA were better than Nation membrane at elevated temperature above 80$^{\circ}C$.

• Transactions of the Korean hydrogen and new energy society
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• v.22 no.5
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• pp.569-578
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• 2011

The $SiO_2$ membranes for polymer electrolyte membrane fuel cell (PEMFC) are preapared by electrospinning method. It leads to high porosity and surface area of membrane to accommodate the proton conducting materials. The composite membrane was prepared by impregnating of Nafion ionomer into the pores of electrospun $SiO_2$ membranes. The $SiO_2$:heteropolyacid (HPA) nano-particles as a inorganic proton conductor were prepared by microemulsion process and the particles are added to the Nafion ionomer. The characterization of the membranes was confirmed by field emission scanning electron microscope (FE-SEM), thermogravimetry analysis (TGA), and single cell performance test for PEMFC. The Nafion impregnated electrospun $SiO_2$ membrane showed good thermal stability, satisfactory mechanical properties and high proton conductivity. The addition of the $SiO_2$:HPA nano-particle improved proton conductivity of the composite membrane, which allow further extension for operation temperature in low humidity environments. The composite membrane exhibited a promising properties for the application in high temperature PEMFC.

• Journal of Photoscience
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• v.10 no.3
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• pp.231-236
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• 2003

TiO$_2$ has been used as photocatalyst since two and half decades ago. The efficiency in its photocatalytic reactions has been improved by increasing the surface area of the photocatalyst by supporting fine TiO$_2$ particles on some porous materials. In this work, heteropolytungstic acid (HPA) - encapsulated into the titanium exchanged SBA-15 mesoporous materials (TiSBA-15) were prepared and characterized. Also their photocatalytic effects on decomposition of phenol were investigated and the photodecomposition rates of the phenol were observed to be increased by 2.5 8 fold, as compared to those observed in the presence of HPA-encapsulated SBA-15 or TiSBA-15 without HPA.

• Proceedings of the Korean Society of Propulsion Engineers Conference
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• 2005.11a
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• pp.229-232
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• 2005

The study on the improvement of manufacturing process of RJ-4 liquid fuel that have high flash point, was carried out. In preparing of RJ-4 using commercially available MCPD, 1st, 2nd hydrogenation and isomerization reaction were enabled 1 step continuous process by combined use of heteropoly phosphoroustungstic cesium salt catalyst and 2nd stage-heat-controllable reactor. Also when heteropolyacid cesium salt was used as a isomerization catalyst instead of aluminum chloride, formation rate of exe-THDMCPD was higher, the catalyst could be easily separable from product and there was no production of waste acid, so this new reaction condition was confirmed as the environment friendly process.

• 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.

• Membrane Journal
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• v.16 no.1
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• pp.9-15
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• 2006

PVA/SSA/HPA composite membranes were prepared by the addition of SSA as a crosslinking agent and HPA such as PWA or SiWA. The water uptake decreased and the IEC increased as the HPA contents increased in PVA/SSA/HPA composite membranes. XRD results showed that HPA distributed well into the composite membranes as the HPA concentration increased, and SiWA dispersed better than PWA in the composite membranes. TGA results showed that PVA/SSA composite membranes were more heat-resistant than PVA due to the crosslinking of PVA, and the heat stability of the composite membranes improved much more as the concentration of HPA increased. The methanol barrier property of PVA/SSA/HPA composite membranes was superior to Nafion, and the methanol permeability of the composite membranes decreased as the concentration of HPA increased.

• Transactions of the Korean hydrogen and new energy society
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• v.17 no.2
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• pp.149-157
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• 2006

Hydrogen as new energy sources is highly efficient and have very low environmental emissions. The proton exchange membrane fuel cell (PEMFC) is an emerging technology that can meet these demands. Therefore, the preparation of stable polymeric membranes with good proton conductivity and durability are very important for hydrogen production via water electrolysis with PEM at medium temperature above $80^{\circ}C$. Currently Nafion of Dupont and Aciflex of Asahi, etc., solid polymer electrolytes of perfluorosulfonic acid membrane, are the best performing commercially available polymer electrolytes. However, these membrane have several flaws including its high cost, and its limited operational temperature above $80^{\circ}C$. Because of this, significant research efforts have been devoted to the development of newer and cheaper membranes. In order to make up for the weak points and to improve the mechanical characteristics with cross -linking, acid-base complexes were prepared by the combination PSf-co-PPSS-$NH_2$ with PEEK-$SO_3H$. The results showed that the proton conductivity decreased in 17.6% and 40% but tensile strength increased in 78% and 98%, about $20.65\;{\times}\;10^6N/m^2$, in comparison with SBPSf/HPA and SPEEK/HPA complex membrane.