Yufei Shu, Xun Liu, Meng Zhang, Bei Liu, Zhongying Wang
{"title":"高级氧化过程中卟啉金属有机框架的失活：光漂白与基本机制","authors":"Yufei Shu, Xun Liu, Meng Zhang, Bei Liu, Zhongying Wang","doi":"10.1016/j.apcatb.2024.123746","DOIUrl":null,"url":null,"abstract":"<p>Porphyrin metal-organic frameworks (MOFs) are widely used in photocatalytic advanced oxidation processes (AOP). However, the stability and deactivation of MOFs, crucial for reusability, have been understudied compared to their catalytic activity. We investigated photobleaching in porphyrin MOFs PCN-224-M (M= H<sub>2</sub>, Fe, Co, Cu, Zn) under visible light and H<sub>2</sub>O<sub>2</sub>. The MOFs exhibited crystallinity loss, ring-opening cleavage, and linker degradation. Photobleaching resulted from direct redox reactions between porphyrin sites and H<sub>2</sub>O<sub>2</sub>. Metal-oxo-porphyrin intermediates played a key role in the \"group effect,\" with different functional groups affecting the photobleaching rate: PCN-224-Fe ≈ PCN-224-Co > PCN-224-H<sub>2</sub> > PCN-224-Cu ≈ PCN-224-Zn. This trend related to chelated metal ions' electronic structures and their propensity for metal-oxo intermediate formation, establishing a structure-stability relationship. Our study enhances understanding of deactivation mechanisms in porphyrin MOFs during AOP, aiding the design of resilient and efficient MOF catalysts for environmental applications.</p>","PeriodicalId":244,"journal":{"name":"Applied Catalysis B: Environmental","volume":"7 1","pages":""},"PeriodicalIF":20.2000,"publicationDate":"2024-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Deactivation of Porphyrin Metal-Organic Framework in Advanced Oxidation Process: Photobleaching and Underlying Mechanism\",\"authors\":\"Yufei Shu, Xun Liu, Meng Zhang, Bei Liu, Zhongying Wang\",\"doi\":\"10.1016/j.apcatb.2024.123746\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>Porphyrin metal-organic frameworks (MOFs) are widely used in photocatalytic advanced oxidation processes (AOP). However, the stability and deactivation of MOFs, crucial for reusability, have been understudied compared to their catalytic activity. We investigated photobleaching in porphyrin MOFs PCN-224-M (M= H<sub>2</sub>, Fe, Co, Cu, Zn) under visible light and H<sub>2</sub>O<sub>2</sub>. The MOFs exhibited crystallinity loss, ring-opening cleavage, and linker degradation. Photobleaching resulted from direct redox reactions between porphyrin sites and H<sub>2</sub>O<sub>2</sub>. Metal-oxo-porphyrin intermediates played a key role in the \\\"group effect,\\\" with different functional groups affecting the photobleaching rate: PCN-224-Fe ≈ PCN-224-Co > PCN-224-H<sub>2</sub> > PCN-224-Cu ≈ PCN-224-Zn. This trend related to chelated metal ions' electronic structures and their propensity for metal-oxo intermediate formation, establishing a structure-stability relationship. Our study enhances understanding of deactivation mechanisms in porphyrin MOFs during AOP, aiding the design of resilient and efficient MOF catalysts for environmental applications.</p>\",\"PeriodicalId\":244,\"journal\":{\"name\":\"Applied Catalysis B: Environmental\",\"volume\":\"7 1\",\"pages\":\"\"},\"PeriodicalIF\":20.2000,\"publicationDate\":\"2024-01-16\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Applied Catalysis B: Environmental\",\"FirstCategoryId\":\"1\",\"ListUrlMain\":\"https://doi.org/10.1016/j.apcatb.2024.123746\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Applied Catalysis B: Environmental","FirstCategoryId":"1","ListUrlMain":"https://doi.org/10.1016/j.apcatb.2024.123746","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
Deactivation of Porphyrin Metal-Organic Framework in Advanced Oxidation Process: Photobleaching and Underlying Mechanism
Porphyrin metal-organic frameworks (MOFs) are widely used in photocatalytic advanced oxidation processes (AOP). However, the stability and deactivation of MOFs, crucial for reusability, have been understudied compared to their catalytic activity. We investigated photobleaching in porphyrin MOFs PCN-224-M (M= H2, Fe, Co, Cu, Zn) under visible light and H2O2. The MOFs exhibited crystallinity loss, ring-opening cleavage, and linker degradation. Photobleaching resulted from direct redox reactions between porphyrin sites and H2O2. Metal-oxo-porphyrin intermediates played a key role in the "group effect," with different functional groups affecting the photobleaching rate: PCN-224-Fe ≈ PCN-224-Co > PCN-224-H2 > PCN-224-Cu ≈ PCN-224-Zn. This trend related to chelated metal ions' electronic structures and their propensity for metal-oxo intermediate formation, establishing a structure-stability relationship. Our study enhances understanding of deactivation mechanisms in porphyrin MOFs during AOP, aiding the design of resilient and efficient MOF catalysts for environmental applications.
期刊介绍：
Applied Catalysis B: Environment and Energy (formerly Applied Catalysis B: Environmental) is a journal that focuses on the transition towards cleaner and more sustainable energy sources. The journal's publications cover a wide range of topics, including:
1.Catalytic elimination of environmental pollutants such as nitrogen oxides, carbon monoxide, sulfur compounds, chlorinated and other organic compounds, and soot emitted from stationary or mobile sources.
2.Basic understanding of catalysts used in environmental pollution abatement, particularly in industrial processes.
3.All aspects of preparation, characterization, activation, deactivation, and regeneration of novel and commercially applicable environmental catalysts.
4.New catalytic routes and processes for the production of clean energy, such as hydrogen generation via catalytic fuel processing, and new catalysts and electrocatalysts for fuel cells.
5.Catalytic reactions that convert wastes into useful products.
6.Clean manufacturing techniques that replace toxic chemicals with environmentally friendly catalysts.
7.Scientific aspects of photocatalytic processes and a basic understanding of photocatalysts as applied to environmental problems.
8.New catalytic combustion technologies and catalysts.
9.New catalytic non-enzymatic transformations of biomass components.
The journal is abstracted and indexed in API Abstracts, Research Alert, Chemical Abstracts, Web of Science, Theoretical Chemical Engineering Abstracts, Engineering, Technology & Applied Sciences, and others.
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