Enhancing the quantum yield of singlet oxygen: photocatalytic degradation of mustard gas simulant 2-chloroethyl ethyl sulfide catalyzed by a hybrid of polyhydroxyl aluminum cations and porphyrin anions.
Enhancing the quantum yield of singlet oxygen: photocatalytic degradation of mustard gas simulant 2-chloroethyl ethyl sulfide catalyzed by a hybrid of polyhydroxyl aluminum cations and porphyrin anions.
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通过将阴离子盐meso-tetra（4-羧基苯基）卟啉（TCPP 4-）和Keggin聚氧乙烯酸盐阳离子簇[Al 13 O 4（OH）24（H2O）12]7+通过简单的离子交换方法，混合（C48H26N4O8）[Al13O4（OH）24（H2O）12]2（OH）10·18H2O制备并表征了聚氧乙烯-卟啉杂化材料（Al 13-TCPP）的光催化降解芥子气模拟物2-氯乙基乙基硫醚（CEES）。实验结果表明，在甲醇和甲醇-水（v/v = 1：1）混合溶剂中，Al 13-TCPP对CEES的催化降解率分别在180和90 min内达到96.16%和99.01%。反应遵循一级反应动力学，在甲醇和溶剂混合物中的半衰期和动力学常数分别为39.8 min，−0.017 min−1和14.7 min，−0.047 min−1。机理分析表明，在可见光照射下，CEES在甲醇和甲醇-水混合溶剂中通过氧化和醇解/水解相结合的方式降解。由Al 13-TCPP产生的超氧自由基（O2 stec −）和单线态分子氧（1 O2）选择性地将CEES氧化成无毒的亚砜。单重态氧捕获实验表明，在可见光照射下，Al 13-TCPP（Φ = 0.236）比H4 TCPP（Φ = 0.135）具有更高的单重态氧生成量子产率。材料Al 13-TCPP具有良好的可重复使用性，循环使用5次后，CEES的降解率仍能达到98.37%。以Al 13-TCPP作为聚氧乙烯-卟啉杂化材料的原型，对芥子气模拟物2-氯乙基乙基硫醚（CEES）进行了光催化降解研究。
By combining the anionic salt meso-tetra(4-carboxyphenyl)porphyrin (TCPP4−) and the Keggin polyoxometalate cation cluster [Al13O4(OH)24(H2O)12]7+via a simple ion-exchange method, a hybrid (C48H26N4O8)[Al13O4(OH)24(H2O)12]2(OH)10·18H2O (Al13–TCPP) was prepared and thoroughly characterized as a prototype of polyoxometalate–porphyrin hybrids for the photocatalytic degradation of the mustard gas simulant 2-chloroethyl ethyl sulfide (CEES). The experimental results showed that the catalytic degradation rate of CEES in the presence of Al13–TCPP reached 96.16 and 99.01% in 180 and 90 min in methanol and methanol–water solvent mixture (v/v = 1 : 1), respectively. The reaction followed first-order reaction kinetics, and the half-life and kinetic constant in methanol and solvent mixture were 39.8 min, −0.017 min−1 and 14.7 min, −0.047 min−1. Mechanism analysis indicated that under visible light irradiation in air, CEES was degraded through a combination of oxidation and alcoholysis/hydrolysis in methanol and the methanol–water solvent mixture. The superoxide radical (O2˙−) and singlet molecular oxygen (1O2) generated by Al13–TCPP selectively oxidized CEES into a non-toxic sulfoxide. The singlet oxygen capture experiments showed that Al13–TCPP (Φ = 0.236) had a higher quantum yield of singlet oxygen generation than H4TCPP (Φ = 0.135) under visible light irradiation in air. The material Al13–TCPP has good reusability, and the degradation rate of CEES can still reach 98.37% after being recycled five times. A hybrid Al13–TCPP was thoroughly characterized as a prototype of polyoxometalate–porphyrin hybrids for the photocatalytic degradation of the mustard gas simulant 2-chloroethyl ethyl sulfide (CEES).
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影响因子：
5.2
作者：
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