Deactivation of Porphyrin Metal-Organic Framework in Advanced Oxidation Process: Photobleaching and Underlying Mechanism

IF 20.2 1区化学 Q1 CHEMISTRY, PHYSICAL Applied Catalysis B: Environmental Pub Date : 2024-01-16 DOI:10.1016/j.apcatb.2024.123746

Yufei Shu, Xun Liu, Meng Zhang, Bei Liu, Zhongying Wang

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Abstract

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.

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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

卟啉金属有机框架（MOFs）广泛应用于光催化高级氧化过程（AOP）。然而，与催化活性相比，MOFs 的稳定性和失活问题一直没有得到充分研究。我们研究了卟啉 MOFs PCN-224-M（M= H2、Fe、Co、Cu、Zn）在可见光和 H2O2 下的光漂白现象。这些 MOFs 表现出结晶度下降、开环裂解和连接体降解。卟啉位点与 H2O2 之间的直接氧化还原反应导致了光漂白。金属-氧化-卟啉中间体在 "基团效应 "中起着关键作用，不同的官能团会影响光漂白速率：PCN-224-Fe≈PCN-224-Co>；PCN-224-H2>；PCN-224-Cu≈PCN-224-Zn。这种趋势与螯合金属离子的电子结构及其形成金属-氧中间体的倾向有关，从而建立了一种结构-稳定性关系。我们的研究加深了人们对 AOP 过程中卟啉 MOF 失活机理的理解，有助于设计弹性、高效的 MOF 催化剂用于环境应用。

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来源期刊

Applied Catalysis B: Environmental 环境科学-工程：化工

CiteScore

38.60

自引率

6.30%

发文量

1117

审稿时长

24 days

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.