Synthesis, Structure and Proton Conductivity of a Complex Based on Decorated Keggin-Type Cluster: {[Cu(dmbipy)(H2O)2Cl0.5]2[PW12O40]}·7H2O (dmbipy = 4,4′-dimethyl-2,2′-bipyridine)

Wang, Xi; Kong, Cai-Yi; Lai, Juin Yih; Wei, Mei-Lin

doi:10.1007/s10876-015-0965-8

Cited by 14 publications

(12 citation statements)

References 39 publications

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“…Although to comment exactly on the mechanistic pathway of this catalytic water oxidation by POM@ZIF‐8 is beyond the scope of our project, we presume the water molecule to become associated with Keggin cluster somewhere on its surface (this may be through hydrogen bonding), which is quite common for all POMs . A direct comparison with the earlier reports of Keggin‐catalyzed oxidation of organic substrates also encouraged us for such a logical consideration .…”

Section: Methodsmentioning

confidence: 86%

“…Although to comment exactly on the mechanistic pathway of this catalytic water oxidation by POM@ZIF-8 is beyond the scope of our project, we presume the water molecule to become associated with Keggin cluster somewhere on its surface (this may be through hydrogen bonding), which is quite common for all POMs. [54][55][56][57] Ad irect comparison with the earlier reports of Keggin-catalyzed oxidation of organic substrates also encouraged us for such al ogical consideration. [58][59][60][61][62][63][64] As the organic molecules cannot come close to the central Xof[XM 12 O 40 ] nÀ (owing to large size), they should be attached with the surface for facile catalytic reaction.…”

Section: Communicationsmentioning

confidence: 85%

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A Keggin Polyoxometalate Shows Water Oxidation Activity at Neutral pH: POM@ZIF‐8, an Efficient and Robust Electrocatalyst

et al. 2018

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Keggin-type polyoxometalate anions [XM O ] are versatile, as their applications in interdisciplinary areas show. The Keggin anion [CoW O ] turns into an efficient and robust electrocatalyst upon its confinement in the well-defined void space of ZIF-8, a metal-organic framework (MOF). [H CoW O ]@ZIF-8 is so stable to water oxidation that it retains its initial activity even after 1000 catalytic cycles. The catalyst has a turnover frequency (TOF) of 10.8 mol O (mol Co) s , one of the highest TOFs for electrocatalytic oxygen evolution at neutral pH. Controlled experiments rule out the chances of formation and participation of CoO in this electrocatalyic water oxidation.

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Section: Methodsmentioning

confidence: 86%

Section: Communicationsmentioning

confidence: 85%

A Keggin Polyoxometalate Shows Water Oxidation Activity at Neutral pH: POM@ZIF‐8, an Efficient and Robust Electrocatalyst

et al. 2018

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“…[54][55][56][57] Ad irect comparison with the earlier reports of Keggin-catalyzed oxidation of organic substrates also encouraged us for such al ogical consideration. [54][55][56][57] Ad irect comparison with the earlier reports of Keggin-catalyzed oxidation of organic substrates also encouraged us for such al ogical consideration.…”

Section: Zuschriftenmentioning

confidence: 85%

A Keggin Polyoxometalate Shows Water Oxidation Activity at Neutral pH: POM@ZIF‐8, an Efficient and Robust Electrocatalyst

et al. 2018

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Keggin-type polyoxometalate anions [XM 12 O 40 ] nÀ are versatile,a st heir applications in interdisciplinary areas show.T he Keggin anion [CoW 12 O 40 ] 6À turns into an efficient and robust electrocatalyst upon its confinement in the welldefined void space of ZIF-8, am etal-organic framework (MOF). [H 6 CoW 12 O 40 ]@ZIF-8 is so stable to water oxidation that it retains its initial activity even after 1000 catalytic cycles. The catalyst has at urnover frequency (TOF) of 10.8 mol O 2 (mol Co) À1 s À1 ,o ne of the highest TOFs for electrocatalytic oxygen evolution at neutral pH. Controlled experiments rule out the chances of formation and participation of CoO x in this electrocatalyic water oxidation.Photosynthesis,one of the most fundamental and essential processes to sustain life on earth, works on the principle of trapping solar energy via electron-hole pair formation. [1,2] This energy is ultimately utilized in splitting of water molecules into H 2 and O 2 .W ater splitting (WS) has emerged as apromising source of clean and sustainable energy. [3] Water oxidation (WO; 2H 2 O!4H + + O 2 + 4e À ; E 0 = 1.23 V), being the bottleneck process of WS owing to its high thermodynamic potential and high overpotential h,requires an efficient and stable WO catalyst (WOC). [4,5] In last few decades, various research groups have contributed towards understanding of the process of WO and designing of robust and efficient WOCs. [1][2][3][4][5][6][7] Recently enormous efforts have been devoted to prepare first-row transition-metal-ion (particularly,c obalt)-based inexpensive WOCs. [8][9][10][11][12][13][14][15][16][17][18] Development of polyoxometalates (POMs) as WOCs came as am ajor breakthrough in this regard. [19][20][21][22][23][24][25][26][27] Thek ey structural features of POMs for POM-WOCs are their complete inorganic skeleton and the scope of fast, reversible electron transfer (resulting into fast WO kinetics). [14,28] In last few years,a long with remarkable progress in this field, questions also arose about the true catalyst species (formation and participation of CoO x as true catalyst). [28][29][30][31][32] Meanwhile,H ill, Geletii, and their coworkers [23] confirmed that their starting Co-POM compound [Co 4 (H 2 O) 2 (a-PW 9 O 34 ) 2 ] 10À was atrue molecular WO catalyst (not CoO x ). Keggin-type POMs have the general formula of [XM 12 O 40 ] nÀ (X = Co 2+ ,P 5+ ,S i 4+ ,e tc.;M= W 6+ ,M o 6+ ,e tc.) and are the most stable structural variant among all POMs. [33][34][35][36] Despite ac onsiderable development in the field of POM-WOC,n ot much attention has been paid to Keggin (as such)-WOC systems as most of them do not possess suitable WOC-active site (unless it has one or more substitution of Mb yaWO-active transition-metal ion). [28,[37][38][39] Recently,S ong et al. [37] showed K 6 [CoW 12 O 40 ]t ob ei nactive to photocatalytic WO,w hile K 7 [Co III Co II (H 2 O)W 11 O 39 ], was found to be active owing to ap eripheral Co III -aqua coordination complex. We thus made an attempt to prepare WOC from [CoW 12 ...

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“…The Si−O [1.586(15)–1.670(11) Å] and W−O [1.658(8)–2.458(10) Å] distances for 1 , the Si−O [1.55(2)–1.670(11) Å] and W−O [1.660(12)–2.45(2) Å] distances for 2 , and the P−O [1.538(4)–1.545(4) Å] and Mo−O [1.673(4)–2.455(4) Å] distances for 3 are respectively comparable to those in organic‐inorganic hybrid materials with Keggin anions as guests or ligands. Thus, the [SiW 12 O 40 ] 4− and [PMo 12 O 40 ] 3− units in 1 – 3 have normal Keggin structures [17–19] …”

Section: Resultsmentioning

confidence: 99%

Three Proton‐Conductors Based on Keggin‐Type Polyoxometalates Well‐Arranged in the Networks of Dinuclear‐Cu(II)‐Mixed‐Organic‐Ligand Clusters

et al. 2022

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Three proton‐conductors, [Cu(5‐H2L)(IN)(H2O)]2H2[SiW12O40] ⋅ 2CH3CN ⋅ 2.5H2O (1), [Cu(4‐HL)(HIN)(H2O)]2H2[SiW12O40] ⋅ 7H2O (2) and [Cu(4‐HL)(HIN)(CH3CN)]2[HIN]2H4[PMo12O40]2 ⋅ 2CH3CN ⋅ 12H2O (3) (where 5‐H2L/4‐H2L is 5,5’/4,4’‐bis(hydroxymethyl)‐2,2’‐bipyridine and HIN is isonicotinic acid), were synthesized at room temperature. Interestingly, three dinuclear‐Cu(II)‐mixed‐organic‐ligand clusters, [Cu(5‐H2L)(IN)(H2O)]22+ cluster for 1, [Cu(4‐HL)(HIN)(H2O)]22+ for 2 and [Cu(4‐HL)(HIN)(CH3CN)]22+ for 3, are in situ synthesized under the coexistence of Keggin‐type polyoxometalates. More interestingly, in 1–3, the global Keggin‐type anions are well‐arranged in the hydrogen‐bonding networks of double‐Cu(II)‐mixed‐organic‐ligand clusters to give different spatial arrangement patterns. The [SiW12O40]4− anions in 1 display two dimensional layer pattern. The [SiW12O40]4− anions in 2 act as single bidentate O,O bridge ligands. The [PMo12O40]3− anions in 3 form the pair pattern. The AC impedance measurement results reveal 3 gives a high conductivity value over 10−3∼10−2 S ⋅ cm−1 in a wide temperature range from 25 to 100 °C under a wide relative humidity range from 35 to 98 %, while 1 and 2 give a middle conductivity value over 10−5∼10−4 S ⋅ cm−1 under the same conditions.

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Synthesis, Structure and Proton Conductivity of a Complex Based on Decorated Keggin-Type Cluster: {[Cu(dmbipy)(H2O)2Cl0.5]2[PW12O40]}·7H2O (dmbipy = 4,4′-dimethyl-2,2′-bipyridine)

Cited by 14 publications

References 39 publications

A Keggin Polyoxometalate Shows Water Oxidation Activity at Neutral pH: POM@ZIF‐8, an Efficient and Robust Electrocatalyst

A Keggin Polyoxometalate Shows Water Oxidation Activity at Neutral pH: POM@ZIF‐8, an Efficient and Robust Electrocatalyst

A Keggin Polyoxometalate Shows Water Oxidation Activity at Neutral pH: POM@ZIF‐8, an Efficient and Robust Electrocatalyst

Three Proton‐Conductors Based on Keggin‐Type Polyoxometalates Well‐Arranged in the Networks of Dinuclear‐Cu(II)‐Mixed‐Organic‐Ligand Clusters

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