Elucidating charge-transfer mechanisms and their effect on the light-induced reactivity of metastable MIL-125(Ti)

IF 20.2 1区化学 Q1 CHEMISTRY, PHYSICAL

Applied Catalysis B: Environmental Pub Date : 2024-01-04 DOI:10.1016/j.apcatb.2024.123692

Rassu Pietro , Cappai Luca , Stagi Luigi , Liu Ruirui , Enzo Stefano , Mulas Gabriele , Garroni Sebastiano , Malfatti Luca , Innocenzi Plinio , Ma Xiaojie , Wang Bo

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Abstract

Alcohol and water photooxidation reactions are employed in concert with optical spectroscopy analyses to demonstrate the occurrence of multiple and distinctive charge-transfer (CT) mechanisms in the environmental photocatalyst MIL-125(Ti). The contribution of ligand-to-metal CT (LMCT) mechanisms increases at wavelengths lower than 320 nm while that of node oxygen-to-metal CT (OMCT) mechanisms increases at longer wavelengths. The localization of photogenerated holes on different atoms leads to a selective reactivity of the framework depending on the mechanism and, during hydroxylation processes, to its spontaneous transition to the isostructural MIL-125-OH(Ti) and the development of an additional LMCT mechanism with a long-lived emission. Furthermore, a previously unidentified and extrinsic CT mechanism is spectroscopically related to the formation of terephthalate-based oligomers. The coexistence of distinctive CT mechanisms in MIL-125(Ti) implies their critical role in catalyst efficiency, and mastering them proves to be a powerful and simple strategy to produce the valuable MIL-125-OH(Ti).

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阐明电荷转移机制及其对可蜕变 MIL-125(Ti)光诱导反应性的影响

酒精和水的光氧化反应与光学光谱分析相结合，证明了环境光催化剂 MIL-125(Ti)中存在多种独特的电荷转移（CT）机制。当波长低于 320 纳米时，配体-金属 CT（LMCT）机制的贡献增加，而当波长较长时，节点氧-金属 CT（OMCT）机制的贡献增加。光生空穴在不同原子上的定位导致了框架的选择性反应（取决于机制），以及在羟基化过程中，框架自发转变为等结构的 MIL-125-OH(Ti)，并发展出具有长寿命发射的附加 LMCT 机制。此外，一种以前未被发现的外在 CT 机制在光谱学上与对苯二甲酸酯基低聚物的形成有关。在 MIL-125(Ti)中同时存在不同的 CT 机制意味着它们在催化剂效率中起着至关重要的作用，掌握这些机制被证明是生产有价值的 MIL-125-OH(Ti) 的一种强大而简单的策略。

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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.