Integrating Uranyl Complexes into Porous Organic Cages for Enhanced Photocatalytic Oxidation of A Mustard‐Gas Simulant

• Published in: European journal of inorganic chemistry Vol. 28; no. 21
• Main Authors: Hu, Bo‐wen, Jin, Wei, Huang, Zhi‐wei, Zhou, Zhi‐heng, Hu, Kong‐qiu, Yuan, Li‐yong, He, Hui‐bing, Shi, Wei‐qun, Mei, Lei
• Format: Journal Article
• Language: English
• Published: Weinheim Wiley Subscription Services, Inc 29.07.2025
• Subjects: Cages; calixresorcinarene; Catalysts; Catalytic activity; Catalytic oxidation; Contaminants; Mass transfer; Mustard gas; Oxidation; Photocatalysis; Photocatalysts; porous organic cages; post‐synthetic modification; uranyl
• DOI: 10.1002/ejic.202500153
• ISSN: 1434-1948

In this work, a new kind of uranyl‐based photocatalysts, i.e., uranyl‐modified porous organic cages, U@HPOCs, are prepared for the first time via a post‐synthetic modification (PSM) of preassembled porous organic cages (POCs) by uranyl sources. The successful integration of uranyl into U@HPOCs, as well as coordination environments of uranyl centers, are well characterized by a combination of analysis techniques, and the catalytic performance of these uranyl compounds as photocatalysts is further evaluated. The results show that all U@HPOCs working as stable heterogeneous catalysts exhibit enhanced photocatalytic activity compared with the corresponding molecular uranyl complex for the oxidation of a mustard gas mimetic 2‐chloroethyl ethyl sulfide (CEES), among which U20@HPOC with the highest amount of uranyl loading exhibits the highest catalytic oxidation efficiency. The enhanced catalytic effect of U@HPOCs demonstrates the important role of POCs with restrained nanotraps, which can expedite mass transfer of catalytic substrates effectively and help to improve the chemical stability. This work not only provides a promising uranyl photocatalyst for effective detoxification of toxic contaminants, but also paves the way to acquiring new catalysts by integrating molecular complexes with POCs, which is expected to inspire more systems with improved catalytic activities in the future. Utilizing the post‐synthetic modification strategy, uranyl ions are successfully incorporated into the [6+12]‐type octahedral porous organic cage, leading to the creation of uranyl‐functionalized porous organic cages U@HPOCs, which serve as effective heterogeneous catalysts for selective oxidation of a sulfide CEES.