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Hexnuclear, octanuclear, dodecanuclear, and hexadecnuclear polyoxomolybdenum()-based porous materials for selective adsorption of gases
Neutral hexnuclear and octanuclear polymolybdate-based porous complexes [Mo 6 O 6 (μ 2 -O) 9 (Hbtz) 6 ]·21H 2 O ( 1 , Hbtz = 1 H -benzotriazole) and [Mo 8 O 8 (μ 2 -O) 12 (Hdatrz) 8 ]·28H 2 O ( 2 , Hdatrz = 1 H -1,2,4-triazole-3,5-diamine), dodecanuclear and hexadecnuclear complexes Na 4 [Mo 12 O 12...
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| Published in: | CrystEngComm 2023-10, Vol.25 (42), p.5942-595 |
|---|---|
| Main Authors: | , , , |
| Format: | Article |
| Language: | English |
| Subjects: | |
| Citations: | Items that this one cites Items that cite this one |
| Online Access: | Get full text |
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| Summary: | Neutral hexnuclear and octanuclear polymolybdate-based porous complexes [Mo
6
O
6
(μ
2
-O)
9
(Hbtz)
6
]·21H
2
O (
1
, Hbtz = 1
H
-benzotriazole) and [Mo
8
O
8
(μ
2
-O)
12
(Hdatrz)
8
]·28H
2
O (
2
, Hdatrz = 1
H
-1,2,4-triazole-3,5-diamine), dodecanuclear and hexadecnuclear complexes Na
4
[Mo
12
O
12
(μ
2
-O)
4
(μ
3
-O)
12
(3-trz)
8
]·14H
2
O (
3
, 3-trz = 1,2,4-triazol-3-amine) and Na
8
[Mo
16
O
16
(μ
2
-O)
16
(μ
2
-OH)
16
(3-trz)
8
]·29H
2
O (
4
) have been successfully obtained and well characterized respectively. As the pH values of the solutions increase, the central metallic nuclei of
1-4
decrease gradually. Under basic conditions, isolated intrinsic microporous materials
1
and
2
can be constructed as six- and eight-membered rings with pore diameters of 3.2 and 4.8 Å, respectively, while dodecanuclear molybdenum(
v
) cluster
3
aggregates as an isopolyacidic anion. Interestingly, two {Mo
8
} units in
4
are linked by strong intramolecular hydrogen bonds [2.692(5) and 2.691(5) Å] into a dimer between bridged hydroxy groups and bridged oxygen atoms. There are diversiform pores presented in
1-4
, and the gas adsorption experiments show that
1-4
are obviously favorable for the adsorption of gases O
2
and CO
2
under different pressures, while little or no adsorption for gases N
2
, CH
4
and H
2
respectively. The CO
2
adsorption capacities of
1-4
are attributed to the pore sizes and the functions of the amines and uncoordinated triazolate N-donor groups. The influences of neutral and anion complexes have been discussed on the skeletons and porous sizes.
As the pH values decreased, triazole derivative assisted hexa-, octa-, hexadec- and dodeca-polynuclear molybdate-based porous complexes
1-4
are constructed successively.
1-4
have a good adsorption effect on O
2
and CO
2
respectively. |
|---|---|
| ISSN: | 1466-8033 1466-8033 |
| DOI: | 10.1039/d3ce00736g |