A recyclable porphyrin photocatalyst for highly efficient visible-light-driven aerobic oxidation of sulfides

IF 10.6 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Green Chemistry Pub Date : 2026-06-22 Epub Date: 2026-05-26 DOI:10.1039/d6gc01903j

Congjia Xie , Heng Tang , Maolin Yang , Tianzhen Xie , Long Shi , Xiao Peng , Zhongxia Zhao , Wenyun Tan

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Abstract

Herein, we report a highly efficient, environmentally benign, and sustainable photocatalytic system for aerobic sulfide oxidation, employing a porphyrin-based catalyst in green solvents under visible light irradiation at room temperature. Synergistically modulating the photostability, solubility, and photoactivity of porphyrins by tailoring their peripheral substituents enabled both high catalytic efficiency and facile recovery. Notably, porphyrins bearing carboxyl groups (tetrakis(4-carboxyphenyl) porphyrin, TCPP) exhibited superior catalytic activity and recyclability, and could be easily reused for at least eight cycles with consistent performance. This method delivers sulfoxides with excellent selectivity (>99%) and high isolated yields (86–99%) within exceptionally short reaction times (15–40 min) and a low catalyst loading (0.1–1.0 mol%). In addition, the protocol exhibits a broad substrate scope across various sulfide skeletons (30 examples), encompassing alkyl aryl sulfides bearing strong electron-withdrawing groups (–CN, –NO₂) as well as notoriously oxidation-resistant diaryl sulfides, and can be successfully scaled up to the gram scale within 40 min. Mechanistic studies reveal that the oxidation proceeds mainly via an energy transfer pathway, with singlet oxygen identified as the reactive oxygen species. This work opens a new avenue for developing practical visible-light-initiated oxidations and serves as an inspiration for the design of recyclable organic photocatalysts.

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一种可回收的卟啉光催化剂，用于高效可见光驱动的硫化物好氧氧化

在此，我们报道了一种高效、环保、可持续的有氧硫化物氧化光催化系统，该系统采用基于卟啉的催化剂，在室温可见光照射下在绿色溶剂中进行。通过调整卟啉的外围取代基，协同调节卟啉的光稳定性、溶解度和光活性，从而实现高催化效率和易于回收。值得注意的是，含羧基的卟啉（四（4-羧基苯基）卟啉，TCPP）表现出优异的催化活性和可回收性，并且可以很容易地重复使用至少8个循环，并且性能一致。该方法在极短的反应时间（15-40 min）和较低的催化剂负载（0.1-1.0 mol%）内提供了极好的亚砜选择性（>99%）和高分离率（86-99%）。此外，该方案在各种硫化物骨架（30个例子）中展示了广泛的底物范围，包括具有强吸电子基团（-CN, -NO2）的烷基芳基硫化物以及众所周知的抗氧化二芳基硫化物，并且可以在40分钟内成功缩放到克尺度。机理研究表明，氧化主要通过能量传递途径进行，单线态氧被确定为活性氧。这项工作为开发实用的可见光引发氧化开辟了新的途径，并为设计可回收的有机光催化剂提供了灵感。

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来源期刊

Green Chemistry 化学-化学综合

CiteScore

16.10

自引率

7.10%

发文量

677

审稿时长

1.4 months

期刊介绍： Green Chemistry is a journal that provides a unique forum for the publication of innovative research on the development of alternative green and sustainable technologies. The scope of Green Chemistry is based on the definition proposed by Anastas and Warner (Green Chemistry: Theory and Practice, P T Anastas and J C Warner, Oxford University Press, Oxford, 1998), which defines green chemistry as the utilisation of a set of principles that reduces or eliminates the use or generation of hazardous substances in the design, manufacture and application of chemical products. Green Chemistry aims to reduce the environmental impact of the chemical enterprise by developing a technology base that is inherently non-toxic to living things and the environment. The journal welcomes submissions on all aspects of research relating to this endeavor and publishes original and significant cutting-edge research that is likely to be of wide general appeal. For a work to be published, it must present a significant advance in green chemistry, including a comparison with existing methods and a demonstration of advantages over those methods.