Integrating TEMPO into a Metal–Organic Framework for Cooperative Photocatalysis: Selective Aerobic Oxidation of Sulfides,ACS Catalysis

当前位置： X-MOL 学术 › ACS Catal. › 论文详情

Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)

Integrating TEMPO into a Metal–Organic Framework for Cooperative Photocatalysis: Selective Aerobic Oxidation of Sulfides
ACS Catalysis ( IF 11.3 ) Pub Date : 2022-08-26 , DOI: 10.1021/acscatal.2c02519
Wenlong Sheng ₁ , Xiaoxiao Wang ₁ , Yuexin Wang ₁ , Shengli Chen ₁ , Xianjun Lang ₁

Affiliation

Metal–organic frameworks (MOFs) are promising visible light photocatalysts due to their adaptable building blocks. In principle, further optimization of the activity could be envisaged by integrating a redox mediator into a MOF to assemble cooperative photocatalysis. Considering the abundant mesopores and the accessible hydroxyl binding sites, PCN-222, consisting of Zr₆(μ-OH)₈ clusters and carboxyl porphyrin ligands, was synthesized to integrate with 4-carboxy-2,2,6,6-tetramethylpiperidine-1-oxyl (HOOC-TEMPO). As a proof of concept, the selective aerobic oxidation of sulfides was selected as the model reaction. Significantly, PCN-222 exhibited a cooperative impact with HOOC-TEMPO on selective aerobic oxidation of sulfides powered by 660 nm red light. In contrast, PCN-226, devoid of accessible hydroxyl sites, only had an inconspicuous cooperation with HOOC-TEMPO. The density functional theory calculations reveal that HOOC-TEMPO could be spontaneously adsorbed on the Zr₆(μ-OH)₈ clusters via the bidentate model. Due to the lack of binding sites of Zr₆(μ-OH)₈, TEMPO was proven to be much less effective than HOOC-TEMPO in promoting the oxidation of sulfides over PCN-222. The covalent integration of HOOC-TEMPO into PCN-222 is essential for the effectiveness and durance of cooperative photocatalysis for the selective aerobic oxidation of a wide range of organic sulfides. This work suggests that MOFs, a versatile platform, could be integrated with a redox mediator to enable smooth photocatalytic selective transformations.

中文翻译：

将 TEMPO 集成到协同光催化的金属-有机框架中：硫化物的选择性好氧氧化

金属有机框架 (MOF) 因其适应性强的结构单元而成为有前途的可见光光催化剂。原则上，可以通过将氧化还原介质整合到 MOF 中来组装协同光催化来进一步优化活性。考虑到丰富的中孔和可接近的羟基结合位点，PCN-222，由 Zr ₆ (μ-OH) _8组成合成了簇和羧基卟啉配体以与 4-羧基-2,2,6,6-四甲基哌啶-1-氧基 (HOOC-TEMPO) 结合。作为概念验证，选择硫化物的选择性好氧氧化作为模型反应。值得注意的是，PCN-222 与 HOOC-TEMPO 对由 660 nm 红光驱动的硫化物选择性有氧氧化产生了协同影响。相比之下，没有可接近的羟基位点的 PCN-226 仅与 HOOC-TEMPO 有不显眼的合作。密度泛函理论计算表明HOOC-TEMPO可以通过二齿模型自发吸附在Zr ₆ (μ-OH) _8簇上。由于缺乏 Zr ₆ (μ-OH) _{8的结合位点}, TEMPO 被证明在促进硫化物在 PCN-222 上的氧化方面不如 HOOC-TEMPO 有效。HOOC-TEMPO 与 PCN-222 的共价整合对于协同光催化选择性好氧氧化多种有机硫化物的有效性和持久性至关重要。这项工作表明，多功能平台 MOF 可以与氧化还原介质相结合，以实现平滑的光催化选择性转化。

更新日期：2022-08-26

点击分享查看原文

点击收藏

阅读更多本刊新发论文本刊介绍/投稿指南