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核壳结构的Z型CdS@MIL-88(A)Fe异质结用于苄胺高效可见光光催化氧化偶联制备亚胺

Core-shell-structured Z-scheme CdS@MIL-88(A)Fe heterojunctions for efficient visible light photocatalytic oxidative coupling of benzylamines to imines.

作者信息

Xu Xueqing, Lu Wenwen, Sun Xuan, Yang Xiaorong, Zhao Yezi, Lei Ziqiang, Yang Zhiwang

机构信息

Key Laboratory of Polymer Materials of Gansu Province, Key Laboratory of Eco-Functional Polymer Materials, Ministry of Education, College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou, 730070, Gansu Province, China.

出版信息

Nanoscale. 2025 Aug 7;17(31):18255-18264. doi: 10.1039/d5nr02282g.

Abstract

The photocatalytic oxidative coupling of benzylamines to imines has garnered extensive attention owing to its environmentally friendly and sustainable nature. However, it is profoundly desirable and essential to elaborate the structure of photocatalysts and to develop highly efficient visible-light-responsive photocatalysts for oxidative coupling of amines. Herein, a core-shell-structured Z-scheme CdS@MIL-88(A)Fe nanocomposite was successfully fabricated through a facile solvothermal and liquid deposition method for photocatalytic oxidative coupling of benzylamines to imines in air under visible light irradiation. The results demonstrated that the core-shell structure and Z-scheme heterojunction between CdS and MIL-88A(Fe) expedited the transport and separation of photon-generated carriers. Consequently, the CdS@MIL-88A(Fe) nanocomposite exhibited superior photocatalytic activities for oxidative coupling of benzylamines to imines compared to CdS and MIL-88A(Fe), respectively. Characterization of the microstructural properties and elucidation of the photocatalytic mechanism revealed that the photogenerated holes (h) and superoxide radicals (˙O) were the primary active species responsible for the reaction. This work highlights the potential of the Z-scheme heterostructure design based on metal-organic frameworks (MOFs) for green photocatalytic organic transformations and provides valuable insights into the development of advanced photocatalysts for sustainable chemical synthesis.

摘要

苄胺光催化氧化偶联生成亚胺因其环境友好和可持续的特性而受到广泛关注。然而,详细阐述光催化剂的结构并开发用于胺氧化偶联的高效可见光响应型光催化剂是非常必要且至关重要的。在此,通过简便的溶剂热法和液相沉积法成功制备了一种核壳结构的Z型CdS@MIL-88(A)Fe纳米复合材料,用于在可见光照射下空气中苄胺光催化氧化偶联生成亚胺。结果表明,CdS与MIL-88A(Fe)之间的核壳结构和Z型异质结加速了光生载流子的传输和分离。因此,与CdS和MIL-88A(Fe)相比,CdS@MIL-88A(Fe)纳米复合材料对苄胺氧化偶联生成亚胺表现出优异的光催化活性。微观结构性质的表征和光催化机理的阐明表明,光生空穴(h)和超氧自由基(˙O)是负责该反应的主要活性物种。这项工作突出了基于金属有机框架(MOF)的Z型异质结构设计在绿色光催化有机转化方面的潜力,并为开发用于可持续化学合成的先进光催化剂提供了有价值的见解。

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