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Preparation of Thiosemicarbazide-decorated Porphyrin-based Polymers and Their Adsorption of CO2 and Hg2+
增强出版- ACTA POLYMERICA SINICA Vol. 54, Issue 4, Pages: 520-528(2023)
- 作者机构：
1.长沙学院生物与化学工程学院 长沙 410003
2.中南大学化学化工学院 长沙 410083
- 作者简介：
Xiao-mei Wang, E-mail: wxm11@ccsu.edu.cn
- 基金信息：
DOI：10.11777/j.issn1000-3304.2022.22303
CLC：Published：20 April 2023，
Published Online：02 December 2022，
Received：05 September 2022，
Accepted：10 November 2022
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王小梅,郭江飞,王立志等.氨基硫脲修饰卟啉基聚合物的制备及对CO2和Hg2+的吸附[J].高分子学报,2023,54(04):520-528.
Wang Xiao-mei,Guo Jiang-fei,Wang Li-zhi,et al.Preparation of Thiosemicarbazide-decorated Porphyrin-based Polymers and Their Adsorption of CO2 and Hg2+[J].ACTA POLYMERICA SINICA,2023,54(04):520-528.
王小梅,郭江飞,王立志等.氨基硫脲修饰卟啉基聚合物的制备及对CO2和Hg2+的吸附[J].高分子学报,2023,54(04):520-528. DOI： 10.11777/j.issn1000-3304.2022.22303.
Wang Xiao-mei,Guo Jiang-fei,Wang Li-zhi,et al.Preparation of Thiosemicarbazide-decorated Porphyrin-based Polymers and Their Adsorption of CO2 and Hg2+[J].ACTA POLYMERICA SINICA,2023,54(04):520-528. DOI： 10.11777/j.issn1000-3304.2022.22303.
摘要
利用四苯基卟啉和三种酰基化交联剂(草酰氯、对苯二甲酰氯和均苯三甲酰氯)经Friedel-Crafts酰基化反应，制备了卟啉基聚合物中间体，进一步用氨基硫脲与之发生席夫碱反应，得到了氨基硫脲修饰卟啉基聚合物. 结果发现，聚合物的交联结构使其具有高比表面积和丰富的超微孔，显示出优异的CO
2
吸附(138 mg/g，273 K，10
5
Pa)及CO
2
/N
2
选择性. 同时，聚合物表面氨基和硫脲的引入使得其对Hg
2+
的吸附量可达311.0 mg/g，吸附机理也证实了N和S对Hg
2+
的配位作用.
Abstract
The hyper-cross-linked polymers (HCPs) are considered one of the most famous porous organic polymers for their great advantages of high Brunauer-Emmett-Teller (BET) surface area (
S
BET
)
abundant micropores
and tunable porosity. Furthermore
the extensive aromatic monomers
inexpensive Lewis acid catalysts
and simply construction process make the HCPs developed greatly. In this way
the Friedel-Crafts alkylation was widely used for the construction of HCPs. However
the shortage of functional groups and reaction sites make the HCPs limited in the adsorption performance. The Friedel-Crafts acylation would take ketone carbonyl to the resulting polymers
which will performed well in the adsorption performance after the post-functionalization. However
it is still difficult to construct the HCPs with high
S
BET
through Friedel-Crafts acylation. Therefore
in this work
a series of porphyrin-based polymers with high specific surface area was constructed through the Friedel-Crafts acylation reaction by using three different acylated crosslinking agents (
p
-phthaloyl chloride
trimesoyl chloride
and oxalyl chloride) and 5
10
15
20-tetraphenylporphyrin. The polymers show abundant ketone carbonyl groups. Therefore
thiosemicarbazide
which has amino and thiourea structure
was used for post-functionalization through Schiff-based reaction and a series of functionalized porphyrin-based polymers were obtained. Due to the hyper-cross-linked structure of the polymer with high
S
BET
and abundant micropores
The polymer showed remarkable CO
2
adsorption performance (138 mg/g
273 K
10
5
Pa) and excellent CO
2
/N
2
selectivity. Remarkable
the post-functionalization of thiosemicarbazide decreased the
S
BET
and the
V
micro
of the polymers
the introducing of the N and S heteroatoms greatly improved the CO
2
adsorption capacity for the strong interaction between the heteroatoms and the CO
2
moleculars. Especially for HTMb-TSC
the post-functionalization make the CO
2
capture capacity increased from 37 mg/g to 91 mg/g (273 K
10
5
Pa). At the same time
the adsorption capacity of Hg
2+
was increased from 210.2 mg/g to 311.0 mg/g due to the introduction of amino and thiourea structures
and the adsorption mechanism also confirmed the coordination between N and S with Hg
2+
. The porphyrin-based polymers also showed good reusability. This work confirmed the advantages of the porphyrin structure in the adsorption applications and expand the application of Friedel-Crafts acylation reaction in the construction of porous organic polymers.
关键词
Friedel-Crafts酰基化反应席夫碱反应卟啉CO2Hg2+
Keywords
Friedel-Crafts acylation reactionSchiff-based reactionPorphyrinCO2Hg2+
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