Dimeric assemblies of lanthanide-stabilised dilacunary Keggin tungstogermanates: A new class of catalysts for the selective oxidation of aniline

Trautwein, Guido; Bakkali, Bouchra El; Alcañiz-Monge, Juan; Artetxe, Beñat; Reinoso, Santiago; Gutiérrez‐Zorrilla, Juan M.

doi:10.1016/j.jcat.2015.09.004

Cited by 24 publications

(13 citation statements)

References 45 publications

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“…Polioxometalatoak bezalako makroanioi eta makrokatioi molekularren arteko kristal ionikoek, hutsune asko uzten dituzte eskuragarri, beraien tamaina eta forma bereziek paketatze eraginkorra zailtzen baitute. Hurbilketa sintetiko hau jarraituz, Keggin motako [XW 12 Beñat Artetxe, Santiago Reinoso, Juan M. Gutiérrez-Zorrilla rako molekula polarrak (alkohol, nitrilo eta esterrak) era eraginkorrean banatzeko absortzio selektiboaren bidez. Gainera, formiatoaren ( -OOCH) ordez talde handiagoak dituzten karboxilatoen erabilerak (adibidez, propanoatoa -OOCC 2 H 5 edo butanoatoa -OOCC 3 H 7 ) bahe molekular gisa jokatzeko ahalmena alkeno edo haloalkanoak bezalako konposatu apolarragoetara heda dezake [8].…”

Section: Gasen Harrapaketa Eta Hondakin-uren Tratamenduaunclassified

“…Prozesua guztiz selektiboa da, % 100ean nitrosobentzenoa lortzen baita produktu gisa. Bide berde (H 2 O 2 bidezko oxidazio katalitikoan ura da sortzen den azpiproduktu bakarra), garbi eta merke honetan, kutsatzaile bat eliminatzen da eta industria ezberdinetarako baliagarria den lehengaia lortzen da [12]. Ildo beretik jarraituz, kutsatzaileak desagerraraztea baino are garrantzitsuago da hauen erabilera ekiditea.…”

Section: Gasen Harrapaketa Eta Hondakin-uren Tratamenduaunclassified

“…J. Berzelius izan zela esan ohi den arren, Elhuyar anaiek ia 40 urte lehenago prestatua zuten wolframioan oinarritutako (NH 4 ) 10 [H 2 W 12 O 42 ] · 10H 2 O gatza, «hori koloreko konposatu mingots eta mina» bezala deskribatu zutena [3]. Ordutik, nahiz eta 1933. urtean J. F. Keggin-ek H 3 [PMo 12 O 40 ] azidoaren egitura kristalinoa ebatzi, XX. mendearen bukaera arte POMen kimika ez zen mundura zabaldu.…”

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Polioxometalatoak: Elhuyar anaien ametsak bizirik dirau!

Artetxe

Reinoso

Gutiérrez‐Zorrilla

2017

EKAIA

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Laburpena: Polioxometalatoak (POMak) kimika ez-organikoaren munduan ezagunak diren metalez eta oxigenoz osatutako kluster anionikoak dira. Azaldu ohi duten forma, konposizio eta propietate aniztasunaren ondorioz, POMek aplikazio ugari dituzte teknologiari, ekonomiari edo ingurugiroari lotutako arlo ezberdinetan. Nahiz eta aspaldidanik aplikazio katalitikoetan erabili, gaur egun etorkizunerako garrantzitsuak izango diren esparru oso ezberdinetarako ikertzen ari dira, besteak beste, hondakin-uren tratamenduan, medikuntzan, konputazio kuantikoan, energia-iturri berriztagarrietan edota sentsore kimiko lumineszenteetan. Horrengatik guztiagatik, polioxometalatoen kimika, etorkizun handiko kimika ezorganikoaren alorreko esparru dinamikoenetariko bat dela baiezta genezake.Hitz gakoak: polioxometalatoak, materialen zientzia, katalisia, nanozientzia, sentsore lumineszenteak, medikuntza.Abstract: Polyoxometalates (POMs) are a well known class of anionic metal-oxygen clusters within the area of inorganic chemistry, with a large variety of shapes, compositions and structures. These features make POMs unique compounds with a wide range of applications in current fields of interest related to technology, economy and environment. In spite of their traditional use as catalysts, they are nowadays being explored for very different issues such as wastewater treatment, medicine, quantum computing, renewable energies or luminescent sensors. Therefore, POM chemistry can be considered as one of the most dynamic fields of the inorganic chemistry, as well as one of the fields with the greatest future.

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Section: Gasen Harrapaketa Eta Hondakin-uren Tratamenduaunclassified

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Polioxometalatoak: Elhuyar anaien ametsak bizirik dirau!

Artetxe

Reinoso

Gutiérrez‐Zorrilla

2017

EKAIA

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“…[10,11] Polyoxometalates (POMs), as abundant molecular-basedi norganic materials, are potentially interesting catalysts for the epoxidation of olefins. Particular attention has been paid to transition-metal-substituted polyoxotungstates,w hich have showns ignificant catalytic activity and selectivity,s uch as Venturello-type anions, {PO 4 [WO(O 2 ) 2 ] 4 } 3À , [15][16][17] Keggin-type [18][19][20][21][22][23][24][25][26][27][28][29] and To urnØ sandwich-typepolyoxotungstates. [30][31][32][33][34][35][36][37][38][39][40] In the literature, the low-valent noble transition-metal-substituted sandwich-typep olyoxotungstates, {[WZnTM 2 (H 2 O) 2 ](ZnW 9 O 34 ) 2 } nÀ (TM=Rh III ,P d II ,a nd Pt II ), referredt oa s1Rh, 1Pd,a nd 1Pt (Figure 1), have been reported to be highly active and selective catalysts with ag ood solvolytic stability for olefin epoxidation with H 2 O 2 .…”

Section: Introductionmentioning

confidence: 99%

Mechanistic Investigation into Olefin Epoxidation with H₂O₂ Catalyzed by Aqua‐Coordinated Sandwich‐Type Polyoxometalates: Role of the Noble Metal and Active Oxygen Position

Liu

Yan

et al. 2016

ChemistryOpen

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Aqua‐coordinated sandwich‐type polyoxometalates (POMs), {[WZnTM2(H2O)2](ZnW9O34)2}n− (TM=RhIII, PdII, and PtII), catalyze olefin epoxidation with hydrogen peroxide and have been well established, and they present an advance toward the utilization of olefins. To elucidate the epoxidation mechanism, we systematically performed density functional calculations. The reaction proceeds through a two‐step mechanism: activation of H2O2 and oxygen transfer. The aqua‐coordinated complexes show two distinct H2O2 activation pathways: “two‐step” and “concerted”. The concerted processes are more facile and proceed with similar and rate‐determining energy barriers at the Rh‐, Pd‐, and Pt‐containing transition states, which agrees well with the experimental results. Next, the resulting TM−OH−(μ‐OOH) intermediate transfers an O atom to olefin to form an epoxide. The higher reactivity of the Rh‐containing POM is attributed to more interactions between the Rh and hydroperoxo unit. We also calculated all active oxygen positions to locate the most favorable pathway. The higher reactivity of the two‐metal‐bonded oxygen position is predominantly ascribed to its lower stereoscopic hindrance. Furthermore, the presence of one and two explicit water solvent molecules significantly reduces the energy barriers, making these sandwich POMs very efficient for the olefin epoxidation with H2O2.

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“…Heteropoly compounds (HPCs) have attracted great attention as effective catalysts for redox and acid-catalyzed reactions, especially in the production processes of petroleum and coal downstream products, such as the oxidative dehydrogenation of alkanes [1,2], the oxidation of propylene/propane to acrolein/acrylic acid [3,4], the oxidation of iso-butane/methacrolein (MAL) to methacrylic acid (MAA) [5,6], and an increasing number of newly emerging fields [7][8][9][10].…”

Section: Introductionmentioning

confidence: 99%

Composition, Structural Evolution and the Related Property Variations in Preparation of Mixed Cesium/Ammonium Acidic Salts of Heteropolyacids

Zhang

Wang

et al. 2016

Catalysts

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Abstract:The composition, structural evolution and the related property variations of mixed cesium/ammonium acidic salts of heteropolyacids were investigated in detail by tracking and analyzing the initial precipitates, evaporation residues and the calcined products in their preparation process. Results show that V cannot completely enter the heteropolyanions in the initial precipitates when the Cs + added amount is low, and the increase in Cs + adding amount improves the substitution of V for Mo in the heteropolyanions. Both the initial precipitates and the evaporation residues are mixtures of cesium and ammonium salts of heteropolyacids before calcination. Thermal treatment causes the decomposition of the ammonium salts and the formation of single-phase solid solutions from mechanical mixtures. The calcined products of the initial precipitates and the evaporation residues vary greatly in textural properties. The determinants of the catalytic performance for the oxidation of methacrolein to methacrylic acid are acidity and specific surface area of the compounds. The increase in specific surface area mainly improves the conversion of methacrolein, but not the selectivity of methacrylic acid. Insufficient acidity caused by high Cs + content in the compounds is responsible for the low selectivity.

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Dimeric assemblies of lanthanide-stabilised dilacunary Keggin tungstogermanates: A new class of catalysts for the selective oxidation of aniline

Cited by 24 publications

References 45 publications

Polioxometalatoak: Elhuyar anaien ametsak bizirik dirau!

Polioxometalatoak: Elhuyar anaien ametsak bizirik dirau!

Mechanistic Investigation into Olefin Epoxidation with H₂O₂ Catalyzed by Aqua‐Coordinated Sandwich‐Type Polyoxometalates: Role of the Noble Metal and Active Oxygen Position

Composition, Structural Evolution and the Related Property Variations in Preparation of Mixed Cesium/Ammonium Acidic Salts of Heteropolyacids

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Dimeric assemblies of lanthanide-stabilised dilacunary Keggin tungstogermanates: A new class of catalysts for the selective oxidation of aniline

Cited by 24 publications

References 45 publications

Polioxometalatoak: Elhuyar anaien ametsak bizirik dirau!

Polioxometalatoak: Elhuyar anaien ametsak bizirik dirau!

Mechanistic Investigation into Olefin Epoxidation with H2O2 Catalyzed by Aqua‐Coordinated Sandwich‐Type Polyoxometalates: Role of the Noble Metal and Active Oxygen Position

Composition, Structural Evolution and the Related Property Variations in Preparation of Mixed Cesium/Ammonium Acidic Salts of Heteropolyacids

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Product

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Mechanistic Investigation into Olefin Epoxidation with H₂O₂ Catalyzed by Aqua‐Coordinated Sandwich‐Type Polyoxometalates: Role of the Noble Metal and Active Oxygen Position