Microporous Acidic Cesium Salt of 12-Tungstosilicic Acid Cs3HSiW12O40 as a Size-selective Solid Acid Catalyst

Kamiya, Yuichi; Sano, Shogo; Miura, Yuki; Uchida, Y.; Ogawa, Yuki; Iwase, Yukari; Okuhara, Toshio

doi:10.1246/cl.2010.881

Cited by 16 publications

(25 citation statements)

References 20 publications

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“…In accordance with the literature, phosphotungstic acid is the most acidic and widely used Keggin HPA in acid‐catalyzed reactions . Several works have described the partial exchange of their protons by cesium, resulting in solid catalysts with a higher activity than their soluble parent acids …”

Section: Introductionsupporting

confidence: 64%

Cesium‐Exchanged Lacunar Keggin Heteropolyacid Salts: Efficient Solid Catalysts for the Green Oxidation of Terpenic Alcohols with Hydrogen Peroxide

2020

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In this work, an innovative and green oxidative process to convert renewable and abundant raw material to more value‐added fine chemicals was developed. Hydrogen peroxide, an environmentally benign oxidant, was used in Cs–exchanged lacunar Keggin heteropolyacid salts‐catalyzed oxidation reactions of the terpenic alcohols (i. e., nerol was the model molecule). The activity of most outstanding catalyst (Cs8SiW11O39) was compared with various catalysts. Epoxides and aldehydes, which are an attractive feedstock for fragrance and pharmaceutical industries were selectively obtained. Lacunar Keggin heteropolyacid salts containing cesium as the counter ion (i. e., Cs7PW11O39, Cs7PMo11O39 and Cs8SiW11O39) were easily synthesized and characterized by infrared spectroscopy, powdered X‐rays diffraction, X‐rays dispersive spectroscopy, scanning electronic microscopy, thermal analysis, porosimetry analyses, diameter and pores distribution. The influences of the main reaction variables such as catalyst concentration, the stoichiometry of the reactants and reaction temperature were evaluated. The reaction scope was successfully extended to the other terpenic alcohols. The Cs8SiW11O39 was the most active and selective lacunar salt. After five cycles of successive reuse, no loss of catalytic activity or selectivity was observed.

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Section: Introductionsupporting

confidence: 64%

Cesium‐Exchanged Lacunar Keggin Heteropolyacid Salts: Efficient Solid Catalysts for the Green Oxidation of Terpenic Alcohols with Hydrogen Peroxide

2020

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“…The solid acid can be simply separated from the liquid-phase system by filtration or decantation, and it also can be readily recovered for utilization (Dhepe & Sahu, 2010;Sebah et al, 2013;Testa, La Parola, Liotta, & Venezia, 2013). Currently, some solid acids such as amorphous carbon material bearing SO 3 H and OH groups, microporous crystalline material (zeolites), and sulfated zirconia have been proposed as potential catalysts for lignocellulosic material hydrolysis (Arichi, Ivanova, & Louis, 2009;Kamiya et al, 2010;Nakajima & Hara, 2012;Teimouri & Chermahini, 2012).…”

Section: Introductionmentioning

confidence: 99%

Selective hydrolysis of hemicellulose from wheat straw by a nanoscale solid acid catalyst

Zhong

Wang

Huang

et al. 2015

Carbohydrate Polymers

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“…In our previous communication [39] O 39 (Sn-n-C 4 H 9 )] 4-, and [PW 11 O 39 (Sn-OH)] 4-. In addition, the pore size distributions, which ranged from the microporous to mesoporous, and the external surface areas were determined by combining Ar porosimetry with conventional mesopore analysis using N 2 adsorption-desorption isotherms.…”

Section: Introductionmentioning

confidence: 99%

Microporous cesium salts of tetravalent Keggin-type polyoxotungstates Cs4[SiW12O40], Cs4[PW11O39(Sn-n-C4H9)], and Cs4[PW11O39(Sn-OH)] and their adsorption properties

Miura

Imai

Yokoi

et al. 2013

Microporous and Mesoporous Materials

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ABSTRACTwere synthesized. The crystalline structures, which had body-centered cubic (bcc) arrangements, the lattice constants, and the pore-size distributions of the three Cs salts were similar, regardless of the presence or absence and types of functional groups introduced. The Cs salts had only micropores and no mesopores. The micropore size distributions were determined from adsorption isotherms of Ar, which showed a sharp peak at 0.59 nm and a shoulder at 0.62 nm. The fractions of the external surface areas to the total surface areas of the Cs salts were less than 6%. It is plausible that the micropores originate from the heteropoly anion defects in the crystallite, which form to avoid mismatches in the Cs + /(heteropoly anion) ratio required for charge balance (= 4) and for a bcc structure (= 3). The surface of the Cs salt introduced with n-butyl groups was hydrophobic, although the surface density of the n-butyl groups was low. On the other hand, the hydroxyl groups present on the surface of Cs 4 [PW 11 O 39 (Sn-OH)] had little effect on the adsorption of water, methanol, ethanol, and hexane but a great impact on that for benzene due to the interactions between the -OH groups and the aromatic rings (-OH···π).3

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Microporous Acidic Cesium Salt of 12-Tungstosilicic Acid Cs3HSiW12O40 as a Size-selective Solid Acid Catalyst

Abstract: Figure Figure S1. Catalytic reactions in a liquid-solid reaction system conducted in the present study.

Cited by 16 publications

References 20 publications

Cesium‐Exchanged Lacunar Keggin Heteropolyacid Salts: Efficient Solid Catalysts for the Green Oxidation of Terpenic Alcohols with Hydrogen Peroxide

Cesium‐Exchanged Lacunar Keggin Heteropolyacid Salts: Efficient Solid Catalysts for the Green Oxidation of Terpenic Alcohols with Hydrogen Peroxide

Selective hydrolysis of hemicellulose from wheat straw by a nanoscale solid acid catalyst

Microporous cesium salts of tetravalent Keggin-type polyoxotungstates Cs4[SiW12O40], Cs4[PW11O39(Sn-n-C4H9)], and Cs4[PW11O39(Sn-OH)] and their adsorption properties

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