Syntheses, structures and properties of three neutral bisupporting heteropolyoxometalates

Liu, Hongbo; Sun, Yu; Chen, Ya-Guang; Meng, Fan-Xia; Shi, Decheng

doi:10.1080/00958970802001780

Cited by 14 publications

(7 citation statements)

References 15 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. [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%

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: 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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“…Fourth, due to the presence of coordinated water and lattice water, molecules of 2 are joined by π-π stacking interactions involving bpy groups and extensive hydrogen bonding between the water ligand and lattice water [figure 2(b)], with O-H…O distances of 2.714-2.977 Å, the closest contact between adjacent aromatic rings is 3.07(4) Å. Literature [8,9,[18][19][20][21][22][23][24][25][26][27][28][29] suggests that the central heteroatom of different complexes is influenced by their surroundings, such as coordination bonds, hydrogen bonds, and weak interactions; when they are symmetrical, the central heteroatom would be disordered.…”

Section: X-ray Crystallographymentioning

confidence: 99%

“…Our group is interested in applications of Keggin-type heteropolyoxotungstate-supported inorganic-organic hybrids and exploiting its linking propensity with metal ions to obtain extended structures and new materials [17][18][19][20][21][22][23][24][25][26][27][28][29]. Recently, we began to use H 4 GeW 12 O 40 as a ligand to synthesize POM-supported transition metal complexes, and have succeeded in connecting this versatile building unit [GeW 12 O 40 ] 4-to complete germanium-tungsten cluster-supported transition metal complexes, [Cu 2 (phen) 4 (GeW 12 O 40 )] (1) and [Ni 2 (bpy) 4 (H 2 O) 2 (GeW 12 O 40 )]·2H 2 O (2).…”

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confidence: 99%

α-Keggin tungstogermanate-supported transition metal complexes: hydrothermal synthesis, characterization, and magnetism of Cu₂(phen)₄(GeW₁₂O₄₀) and [Ni₂(bpy)₄(H₂O)₂(GeW₁₂O₄₀)]⋅2H₂O

Zhang

Qiu

et al. 2014

Journal of Coordination Chemistry

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Two new α-Keggin polyoxometalates, [Cu 2 (phen) 4 (GeW 12 O 40 )] (1) and [Ni 2 (bpy) 4 (H 2 O) 2 (Ge-W 12 O 40 )]·2H 2 O (2) (phen = 1,10-phenanthroline, bpy = 2,2′-bipyridine), have been hydrothermally synthesized and characterized by elemental analysis, IR, TG, single-crystal X-ray diffraction, and magnetic properties. Compound 1 crystallizes in the monoclinic system, space group P2(1)/c, and 1 is assembled into two-dimensional (2-D) layers parallel to (1 0 1) based on the adjacent phen π···π stacking interactions (3.788(8) Å). Variable temperature magnetic measurements show ferromagnetic behavior from 300 to 2 K. Compound 2 crystallizes in the triclinic system, space group P-1, and 2 is assembled into 2-D layers parallel to (1 0 1) based on the adjacent bpy π···π stacking interactions (3.07 Å). Variable temperature magnetic measurements show a weak ferromagnetic behavior from 300 to 26 K followed by antiferromagnetic behavior below 26 K.

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Syntheses, structures and properties of three neutral bisupporting heteropolyoxometalates

Cited by 14 publications

References 15 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

α-Keggin tungstogermanate-supported transition metal complexes: hydrothermal synthesis, characterization, and magnetism of Cu₂(phen)₄(GeW₁₂O₄₀) and [Ni₂(bpy)₄(H₂O)₂(GeW₁₂O₄₀)]⋅2H₂O

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Syntheses, structures and properties of three neutral bisupporting heteropolyoxometalates

Cited by 14 publications

References 15 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

α-Keggin tungstogermanate-supported transition metal complexes: hydrothermal synthesis, characterization, and magnetism of Cu2(phen)4(GeW12O40) and [Ni2(bpy)4(H2O)2(GeW12O40)]⋅2H2O

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α-Keggin tungstogermanate-supported transition metal complexes: hydrothermal synthesis, characterization, and magnetism of Cu₂(phen)₄(GeW₁₂O₄₀) and [Ni₂(bpy)₄(H₂O)₂(GeW₁₂O₄₀)]⋅2H₂O