Assembly of polyoxometalates and Ni-bpy cationic units into the molecular core-shell structures as bifunctional electrocatalystsElectronic supplementary information (ESI) available: Structural figures, TGA, IR and CIF file. CCDC 1495993 for 1, 1495994 for 2 and 1495995 for 3. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c6ra19257b
Four polyoxometalate-based supramolecular assemblies were designed and synthesized under hydrothermal conditions: [Ni(2,2-bpy) 3 ] 5 [PW 11 NiO 39 (H 2 O)] 2 ·1.08H 2 O ( 1 ), [Ni(2,2-bpy) 3 ] 1.5 [Ni(2,2-bpy) 2 (H 2 O)BW 12 O 40 ] ( 2 ), {[Ni(2,2-bpy) 3 ] 1.5 [Ni(2,2-bpy) 2 (H 2 O)GeW 12 O 40 ]} −...
Saved in:
| Main Authors | , , , , |
|---|---|
| Format | Journal Article |
| Language | English |
| Published |
17.10.2016
|
| Online Access | Get full text |
Cover
Loading…
| Summary: | Four polyoxometalate-based supramolecular assemblies were designed and synthesized under hydrothermal conditions: [Ni(2,2-bpy)
3
]
5
[PW
11
NiO
39
(H
2
O)]
2
·1.08H
2
O (
1
), [Ni(2,2-bpy)
3
]
1.5
[Ni(2,2-bpy)
2
(H
2
O)BW
12
O
40
] (
2
), {[Ni(2,2-bpy)
3
]
1.5
[Ni(2,2-bpy)
2
(H
2
O)GeW
12
O
40
]}
−
(
3
), and {[Ni(2,2-bpy)
3
]
1.5
[Ni(2,2-bpy)
2
(H
2
O)PW
12
O
40
]}
2−
(
4
). These structures were characterized by IR, TG analysis, elemental analysis, X-ray powder diffraction and single-crystal X-ray diffraction. In compound
1
, two mono-substituted [PW
11
NiO
39
(H
2
O)]
5−
anions were fused together
via
the H-bonding interactions forming a dimeric polyoxoanion [PW
11
NiO
39
(H
2
O)]
2
10−
, which was surrounded by Ni-bpy cationic units into the molecular core-shell structures. Compounds
2-4
were composed of saturated polyoxoanions [BW
12
O
40
]
5−
, [GeW
12
O
40
]
4−
and [PW
12
O
40
]
3−
, respectively. These saturated anions were surrounded by [Ni(2,2-bpy)
3
]
2+
and [Ni(2,2-bpy)
2
(H
2
O)]
2+
cationic units forming isostructural core-shell organic-inorganic hybrid materials. These isostructural polyoxometalates with different heteroatoms and charges all formed the isostructural materials, indicating that their charges do not have a significant influence on the structure of supramolecular assemblies. A detail study showed that substituted polyoxometalate with the terminal H
2
O molecule is essential for constructing the larger core-shell structure. An electrocatalytic study indicated that these four compounds are bifunctional electrocatalysts towards water oxidation and reduction of nitrite.
Four core-shell organic-inorganic hybrid materials composed of polyoxometalates and Ni-bpy units were designed and synthesized, which exhibited bifunctional electrocatalytic activity for the reduction of NO
2
−
and water oxidation. |
|---|---|
| Bibliography: | 1 For ESI and crystallographic data in CIF or other electronic format see DOI Electronic supplementary information (ESI) available: Structural figures, TGA, IR and CIF file. CCDC 2 3 10.1039/c6ra19257b and for , 1495994 1495993 1495995 |
| ISSN: | 2046-2069 |
| DOI: | 10.1039/c6ra19257b |