Qingshan Zhu, Haiyan An, Yuting Wei, Hao Sun, Jie Fu, Tie-Qi Xu
{"title":"在卟啉基多孔阳离子聚合物中限制聚氧化金属,促进可见光驱动的硫氧化物合成和芥子气模拟物的解毒","authors":"Qingshan Zhu, Haiyan An, Yuting Wei, Hao Sun, Jie Fu, Tie-Qi Xu","doi":"10.1016/j.jcat.2024.115627","DOIUrl":null,"url":null,"abstract":"<div><p>Visible-light-driven oxidation of sulfides has attracted the profound attention to synthesize sulfoxides and purify mustard gas simulant. In this work, a series of visible-light-responsive polyoxometalate-based porous cationic polymers, i.e. SiW<sub>12</sub>-PCP <strong>1</strong>, PW<sub>12</sub>-PCP <strong>2</strong>, SiW<sub>11</sub>-PCP <strong>3</strong>, SiW<sub>10</sub>-PCP <strong>4</strong>, SiW<sub>9</sub>-PCP <strong>5</strong> (PCP = porphyrin-based porous cationic polymer), were synthesized by ion exchange process. These POM-PCPs exhibit excellent ability of trapping visible light due to their built-in porphyrin units, which can rapidly oxidize sulfides and degrade 2-chloroethyl ethyl sulfide (CEES) in the presence of a 10 W white LED light and O<sub>2</sub>. Benefiting from the synergistic effect between [SiW<sub>12</sub>] and PCP, hybrid <strong>1</strong> has the highest photocatalytic efficiency, attaining 99 % conversion of sulfides within 16 min and 99 % CEES purification in 8 min, much higher than PCP precursor. The reaction mechanism reveals that both O<sub>2</sub><sup>•−</sup> and <sup>1</sup>O<sub>2</sub> are involved in the photocatalytic process. What's more, hybrid <strong>1</strong> has remarkable applicability to numerous sulfides and robust six-round recycling with no reduction in catalytic efficiency.</p></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":null,"pages":null},"PeriodicalIF":6.5000,"publicationDate":"2024-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Confining polyoxometalates in porphyrin-based porous cationic polymer toward boosting visible-light-driven synthesis of sulfoxides and detoxification of mustard gas simulants\",\"authors\":\"Qingshan Zhu, Haiyan An, Yuting Wei, Hao Sun, Jie Fu, Tie-Qi Xu\",\"doi\":\"10.1016/j.jcat.2024.115627\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>Visible-light-driven oxidation of sulfides has attracted the profound attention to synthesize sulfoxides and purify mustard gas simulant. In this work, a series of visible-light-responsive polyoxometalate-based porous cationic polymers, i.e. SiW<sub>12</sub>-PCP <strong>1</strong>, PW<sub>12</sub>-PCP <strong>2</strong>, SiW<sub>11</sub>-PCP <strong>3</strong>, SiW<sub>10</sub>-PCP <strong>4</strong>, SiW<sub>9</sub>-PCP <strong>5</strong> (PCP = porphyrin-based porous cationic polymer), were synthesized by ion exchange process. These POM-PCPs exhibit excellent ability of trapping visible light due to their built-in porphyrin units, which can rapidly oxidize sulfides and degrade 2-chloroethyl ethyl sulfide (CEES) in the presence of a 10 W white LED light and O<sub>2</sub>. Benefiting from the synergistic effect between [SiW<sub>12</sub>] and PCP, hybrid <strong>1</strong> has the highest photocatalytic efficiency, attaining 99 % conversion of sulfides within 16 min and 99 % CEES purification in 8 min, much higher than PCP precursor. The reaction mechanism reveals that both O<sub>2</sub><sup>•−</sup> and <sup>1</sup>O<sub>2</sub> are involved in the photocatalytic process. What's more, hybrid <strong>1</strong> has remarkable applicability to numerous sulfides and robust six-round recycling with no reduction in catalytic efficiency.</p></div>\",\"PeriodicalId\":346,\"journal\":{\"name\":\"Journal of Catalysis\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":6.5000,\"publicationDate\":\"2024-07-01\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of Catalysis\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S0021951724003403\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Catalysis","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0021951724003403","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
Confining polyoxometalates in porphyrin-based porous cationic polymer toward boosting visible-light-driven synthesis of sulfoxides and detoxification of mustard gas simulants
Visible-light-driven oxidation of sulfides has attracted the profound attention to synthesize sulfoxides and purify mustard gas simulant. In this work, a series of visible-light-responsive polyoxometalate-based porous cationic polymers, i.e. SiW12-PCP 1, PW12-PCP 2, SiW11-PCP 3, SiW10-PCP 4, SiW9-PCP 5 (PCP = porphyrin-based porous cationic polymer), were synthesized by ion exchange process. These POM-PCPs exhibit excellent ability of trapping visible light due to their built-in porphyrin units, which can rapidly oxidize sulfides and degrade 2-chloroethyl ethyl sulfide (CEES) in the presence of a 10 W white LED light and O2. Benefiting from the synergistic effect between [SiW12] and PCP, hybrid 1 has the highest photocatalytic efficiency, attaining 99 % conversion of sulfides within 16 min and 99 % CEES purification in 8 min, much higher than PCP precursor. The reaction mechanism reveals that both O2•− and 1O2 are involved in the photocatalytic process. What's more, hybrid 1 has remarkable applicability to numerous sulfides and robust six-round recycling with no reduction in catalytic efficiency.
期刊介绍:
The Journal of Catalysis publishes scholarly articles on both heterogeneous and homogeneous catalysis, covering a wide range of chemical transformations. These include various types of catalysis, such as those mediated by photons, plasmons, and electrons. The focus of the studies is to understand the relationship between catalytic function and the underlying chemical properties of surfaces and metal complexes.
The articles in the journal offer innovative concepts and explore the synthesis and kinetics of inorganic solids and homogeneous complexes. Furthermore, they discuss spectroscopic techniques for characterizing catalysts, investigate the interaction of probes and reacting species with catalysts, and employ theoretical methods.
The research presented in the journal should have direct relevance to the field of catalytic processes, addressing either fundamental aspects or applications of catalysis.