• Title/Summary/Keyword: Heteropolyacids

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Dehydration Reaction of Fructose to 5-Hydroxymethylfurfural over Various Keggin-type Heteropolyacids (Keggin형 헤테로폴리산에 의한 과당의 5-하이드록시메틸퍼퓨랄로의 전환을 위한 탈수반응)

  • Baek, Ja-Yeon;Yun, Hyeong-Jin;Kim, Nam-Dong;Choi, Young-Bo;Yi, Jong-Heop
    • Clean Technology
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    • v.16 no.3
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    • pp.220-228
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    • 2010
  • Four Keggin-type heteropolyacids, $H_nXM_{12}O_{40}$(X = P and Si, M = W and Mo) that were substituted with heteroatom and polyatom were applied to the dehydration reaction of fructose to 5-hydroxymethylfurfural (HMF). The results showed that the acid became stronger when the heteroatom and polyatom were substituted with P and W than the cases of Si and Mo, respectively. However, the amount of acidic sites increased with the decrease in the acid strength, resulting in the change of the catalytic activity of heteropolyacids in the dehydration reaction. The experimental results revealed that four different heteropolyacids produced similar amounts of HMF via the dehydration reaction of fructose due to the counterbalancing effect between the amount of active sites, which is related to the catalytic activity of heteropolyacids, and the softness of polyanion. In addition, it was observed that the prepared heteropolyacids showed good structural stability after heat treatment at $200^{\circ}C$.

STM Studies of Keggin-type and Wells-Dawson-type Heteropolyacid Catalysts (Keggin 형 및 Wells-Dawson 형 헤테로폴리산 촉매의 STM 연구)

  • Park, Gyo Ik;Barteau, Mark A.;Jung, Ji Chul;Song, In Kyu
    • 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.

The Electrochemical Characteristics of MEA with Pt/Cross-Linked SPEEK-HPA Composite Membranes/Pt-Ru for Water Electrolysis (수전해용 Pt/공유가교 SPEEK-HPA 복합막/Pt-Ru MEA의 전기화학적 특성)

  • Hwang, Yong-Koo;Woo, Je-Young;Lee, Kwang-Mun;Chung, Jang-Hoon;Moon, Sang-Bong;Kang, An-Soo
    • Transactions of the Korean hydrogen and new energy society
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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.

Esterification of Methacrylic acid with Ethylene glycol over Heteropolyacid supported on ZSM-5 (ZSM-5 위에 지지된 Heteropolyacid 하에서 Methacrylic acid와 Ethylene glycol의 에스테르화 반응)

  • Prabhakarn, A.;Fereiro, J.A.;Subrahmanyam, Ch.
    • 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.

Characteristics and Catalytic Activities of 12-Molybdophosphoricacid Modified by Ring Opening Polymerization of Tetrahydrofuran (테트라하이드로퓨란의 개환 중합반응에 의해 변형된 12-몰리브도인산의 특성 및 촉매 반응성)

  • Park, Gyo Ik;Lee, Wha Young;Song, In Kyu
    • Applied Chemistry for Engineering
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    • v.9 no.7
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    • pp.1018-1022
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    • 1998
  • Characteristics and catalytic activities of 12-molybdophosphoricacid catalysts modified by ring opening polymerization of tetrahydrofuran (THF) were studied in this work. 12-Molybdophosphoricacid catalysts modified by THF showed higher conversions and product yields than the mother acid in the vapor-phase ethanol conversion. It was believed that the enhanced catalytic activities of modified 12-molybdophosphoricacids were due to structural flexibility of heteropolyanions and weakened hydrogen bond around heteropolyanions. THF interacted with protons and crystalline water molecules of heteropolyacids. The interaction between THF and heteropolyanoins, which crystalline water molecules act as intermediary, was the dominant factor deciding the catalytic activities of modified 12-molybophosphoricacids.

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Antifungal Activity of Silver Salts of Keggin-Type Heteropolyacids Against Sporothrix spp.

  • Mathias, Luciana Da Silva;Almeida, Joao Carlos De Aquino;Passoni, Luis Cesar;Gossani, Cristiani Miranda David;Taveira, Gabriel Bonan;Gomes, Valdirene Moreira;Vieira-Da-Motta, Olney
    • Journal of Microbiology and Biotechnology
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    • v.30 no.4
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    • pp.540-551
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    • 2020
  • Sporotrichosis is a chronic and subacute mycosis causing epidemiological outbreaks involving sick cats and humans in southeastern Brazil. The systemic disease prevails in cats and in humans, with the symptoms restricted to the skin of immunocompetent individuals. Under these conditions, the prolonged treatment of animals and cases of recurrence justify the discovery of new treatments for sporotrichosis. This work addresses the antifungal activity of silver salts of Keggin-type heteropolyacid salts (Ag-HPA salts) such as Ag3[PW12O40], Ag6[SiW10V2O40], Ag4[SiW12O40] and Ag3[PMo12O40] and interactions with the antifungal drugs itraconazole (ITC), terbinafine (TBF) and amphotericin B (AMB) on the yeast and mycelia forms of Sporothrix spp. Sporothrix spp. yeast cells were susceptible to Ag-HPA salts at minimum inhibitory concentration (MIC) values ranging from 8 to 128 ㎍/ml. Interactions between Ag3[PW12O40] and Ag3[PMo12O40] with itraconazole and amphotericin B resulted in higher antifungal activity with a reduction in growth and melanization. Treated cells showed changes in cell membrane integrity, vacuolization, cytoplasm disorder, and membrane detachment. Promising antifungal activity for treating sporotrichosis was observed for the Ag-HPA salts Ag3[PMo12O40] and Ag3[PW12O40], which have a low cost, high yield and activity at low concentrations. However, further evaluation of in vivo tests is still required.

Characteristics of CL-SPEEK/HPA Membrane Electrodes with Pt-Ni and Pt-Co Electrocatalysts for Water Electrolysis (전극 촉매 Pt-Ni 및 Pt-Co를 이용한 수전해용 공유가교 CL-SPEEK/HPA 막전극의 특성)

  • Woo, Je-Young;Lee, Kwang-Mun;Jee, Bong-Chul;Chung, Jang-Hoon;Moon, Sang-Bong;Kang, An-Soo
    • Transactions of the Korean hydrogen and new energy society
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    • v.21 no.1
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    • pp.26-34
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    • 2010
  • The electrocatalystic prperties of Pt-Co and Pt-Ni with heteropolyacids (HPAs) entrapped in covalently cross-linked sulfonated poly(ether ether ketone) (CL-SPEEK)/HPA membranes were investigated for water electrolysis. The HP As, including molybdophosphoric acid (MoPA), and tungstophosphoric acid (TPA) were both used as membrane additives and electrocatalysts. The membrane electrode assembly (MEA) was prepared by a nonequilibrium impregnation-reduction (I-R) method. $Pt(NH_3)_4Cl_2$, $NiCl_2$ and $CoCl_2$ as electrocatalytic materials and $NaBH_4$ as reducing agent were used. I order to enhance electrocatalytic activity, the catalyst layer prepared above was electrodeposited (Dep) with HP A. Surface morphologies and physico-chemical properties of MEA were investigated by means of SEM, EDX and XRD. The electrocatalytic properties of composite membranes such as the cell voltage and coulombic charge in CV were in the order of magnitude: CL-SPEEK/MoPA40 (wt%) > CL-SPEEK/TPA30 > Nafion117. In the optimum cell applications for water electrolysis, the cell voltage of Pt/CL-SPEEK-MoPA40/Pt-Co (Dep-MoPA) and Pt/CL-SPEEK-TPA30/Pt-Co (Dep-TPA) was 1.75 Vat $80^{\circ}C$ and $1\;A/cm^2$ and voltage efficiency was 87.1%. Also, the observed activity of Pt-Co (84:16 atomic ratio by EDX) is a little higher than that of Pt-Ni (86: 14). The current density peak of electrodeposited electrodes were better a little than those of unactivated electrodes based on the same membranes.