供体-受体混合萘二酰亚胺-卟啉 MOF 促进胺的光催化氧化偶联,ACS Catalysis

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供体-受体混合萘二酰亚胺-卟啉 MOF 促进胺的光催化氧化偶联
ACS Catalysis ( IF 11.3 ) Pub Date : 2023-04-12 , DOI: 10.1021/acscatal.3c00284
Wen-Jie Xu ₁ , Bo-Xuan Huang ₁ , Guangli Li ₂ , Fen Yang ₁ , Wei Lin ₁ , Jia-Xin Gu ₁ , Hai-Guang Deng ₁ , Zhi-Gang Gu _{3,

4} , Hong-Guang Jin ₁

Affiliation

将电子供体和受体发色团作为配体整合到一个 MOF 中以进行光捕获和光催化似乎是一项主要的合成挑战。同时，在温和条件下将胺类高效、选择性地有氧氧化偶联为亚胺类是科学和工业领域非常需要的。在此，通过简便的一锅法合成策略，电子供体卟啉配体 5,15-二（对苯甲酸）卟啉（H ₂ DPBP）成功地整合到基于萘二亚胺（电子受体）的 Zr-MOF（Zr -NDI) 构建混合配体 MOF (Zr-NDI-H ₂DPBP) 受益于具有相似几何形状和连通性的两个配体。当用作室温下苯甲胺有氧氧化偶联的多相光催化剂时，制备的混合配体 Zr-NDI-H ₂ DPBP 表现出更高的亚胺生成速率 (136 mmol g ^–1 h ^–1 )，远远超过其他贵金属-无金属MOF光催化剂，可成功应用于各种苄胺衍生物。此外，从实验和密度泛函理论计算的结果来看，Zr-NDI-H ₂ DPBP的光催化性能归因于供体H _{2的光诱导电子转移。}DPBP向受体NDI和光敏化H ₂ DPBP在照射下促进能量转移，有效提高电子-空穴分离效率，产生丰富的超氧自由基(O ₂^•– )和单线态氧( ¹ O _{2 )}活性活性种），分别。这项工作通过利用混合配体 MOF 作为促进太阳能转换的平台，为构建基于电子供体和受体发色团的光收集系统提供了一条途径。

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Donor–Acceptor Mixed-Naphthalene Diimide-Porphyrin MOF for Boosting Photocatalytic Oxidative Coupling of Amines

Integrating electron donor and acceptor chromophores as ligands within one MOF for light harvesting and photocatalysis appears to be a major synthesis challenge. Meanwhile, high-efficiency and selective aerobic oxidative coupling of amines to imines under mild conditions is highly desirable for scientific and industrial fields. Herein, via a facile one-pot synthetic strategy, an electron donor porphyrin ligand 5,15-di(p-benzoato)porphyrin (H₂DPBP) was successfully integrated into a naphthalene diimide (electron acceptor)-based Zr-MOF (Zr-NDI) to construct a mixed-ligand MOF (Zr-NDI-H₂DPBP) benefiting from the two ligands with similar geometry and connectivity. When utilized as a heterogeneous photocatalyst for aerobic oxidative coupling of benzylamine at room temperature, the prepared mixed-ligand Zr-NDI-H₂DPBP exhibited a boosted imine generation rate (136 mmol g^–1 h^–1) far exceeding those of other noble-metal-free MOF photocatalysts and can be successfully applied to various benzylamine derivatives. Furthermore, from the results of the experiments and density functional theory calculations, the photocatalytic performance of Zr-NDI-H₂DPBP is attributed to the photoinduced electron transfer from the donor H₂DPBP to the acceptor NDI and the energy transfer facilitated by the photosensitized H₂DPBP under irradiation, which effectively improve the electron–hole separation efficiency to generate abundant reactive active species of superoxide radical (O₂^•–) and singlet oxygen (¹O₂), respectively. This work provides an avenue to construct electron donor and acceptor chromophore-based light-harvesting systems by utilizing mixed-ligand MOFs as platforms to boost the solar-energy conversion.

更新日期：2023-04-12

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