Wang Lianlian, Shen Dalong, Zhang Heyao, Mo Bingyan, Wu Jie, Hou Hongwei
Green Catalysis Center, College of Chemistry, Zhengzhou University, Zhengzhou, 450001, P. R. China.
Chemistry. 2022 Jan 27;28(6):e202103466. doi: 10.1002/chem.202103466. Epub 2021 Dec 29.
Photocatalytic oxidation of sulfide into sulfoxide has attracted extensive attention as an environmentally friendly strategy for chemical transformations or toxic chemicals degradation. Herein, we construct a series of In S /NU-1000 heterojunction photocatalysts, which can efficiently catalyze the oxidation of sulfides to form sulfoxides as the sole product under LED lamp (full-spectrum) illumination in air at room temperature. Especially, the sulfur mustard simulant, 2-chloroethyl ethyl sulfide (CEES), can also be photocatalytically oxidized with In S /NU-1000 to afford nontoxic 2-chloroethyl ethyl sulfoxide (CEESO) selectively and effectively. In contrast, individual NU-1000 and In S show very low catalytic activity on this reaction. The significantly improved photocatalytic activity is ascribed to the constructing of an efficient Z-scheme photocatalysts In S /NU-1000, which exhibits the enhancement of light harvesting, the promotion of photogenerated electron-hole separation, and the retention of high porosity of the parent MOF. Moreover, mechanism studies in photocatalytic oxidation reveal that the superoxide radical ( O ) and singlet oxygen ( O ) are the main oxidative species in the oxidation system. This work exploits the opportunities for the construction of porous Z-scheme photocatalysts based on the photoactive MOFs materials and inorganic semiconductors for promoting catalytic organic transformations. More importantly, it provides a route to the rational design of efficient photocatalysts for the detoxification of mustard gas.
硫化物光催化氧化为亚砜作为一种用于化学转化或有毒化学品降解的环境友好策略已引起广泛关注。在此,我们构建了一系列In S /NU-1000异质结光催化剂,其能够在室温下空气中LED灯(全光谱)照射下高效催化硫化物氧化形成亚砜作为唯一产物。特别地,硫芥模拟物2-氯乙基乙基硫醚(CEES)也能被In S /NU-1000光催化氧化,选择性且有效地生成无毒的2-氯乙基乙基亚砜(CEESO)。相比之下,单独的NU-1000和In S在此反应中表现出非常低的催化活性。显著提高的光催化活性归因于构建了高效的Z型光催化剂In S /NU-1000,其表现出光捕获增强、光生电子-空穴分离促进以及母体MOF高孔隙率的保留。此外,光催化氧化的机理研究表明超氧自由基(O )和单线态氧(O )是氧化体系中的主要氧化物种。这项工作利用了基于光活性MOF材料和无机半导体构建多孔Z型光催化剂以促进催化有机转化的机会。更重要的是,它为合理设计用于芥子气解毒的高效光催化剂提供了一条途径。