Zhang Duo, Zhang Hairan, Fu Mengmei, Liu Jie, Zheng Nan, Shao Xianzhao, Ji Xiaohui
School of Chemical and Environment Science, Shaanxi Key Laboratory of Catalysis, Shaanxi University of Technology, Hanzhong 723001, China.
Langmuir. 2025 Jun 24;41(24):15520-15530. doi: 10.1021/acs.langmuir.5c01543. Epub 2025 Jun 9.
The efficient removal of refractory sulfides from fuels to achieve clean oil is a primary research focus in the petrochemical industry. This study introduces extraction and catalytic oxidation desulfurization (ECODS) as a technique for effective desulfurization. A cross-linking strategy was employed to construct structurally stable isotropic microreactors based on ionic liquid (IL)-modified liposomes (poly[MimA, A][heteropolyanions]), where exposed imidazolium cations anchor catalytic heteropolyanions (e.g., [PWO]) to ensure active site accessibility. In this interfacial catalytic reaction, the microreactor resembles an emulsified droplet with a spherical surface, significantly enhancing the catalytic interface. Additionally, the isotropic imidazolium cations of spherical vesicles provide the equivalent driving force for the attachment of heteropolyanions (such as [PWO] and [PMoO]), ensuring full exposure of active sites and reducing mass transfer resistance. The optimized poly[MimA, A][PWO] catalyst achieved complete dibenzothiophene (DBT) removal within 1.5 h and retained 92.4% efficiency after six cycles, demonstrating exceptional activity and recyclability. The morphology, structure, and properties of the microreactors were characterized, and optimal reaction conditions were established. Building on this foundation, the removal performances across various systems and sulfur-containing targets were assessed, thereby confirming the structure-activity relationship of this type of microreactor. Furthermore, the desulfurization mechanism was inferred from the identified oxidation products. Overall, this isotropic poly[MimA, A][heteropolyanion] demonstrates excellent desulfurization performance and holds significant potential for broad applications.
从燃料中高效去除难熔硫化物以实现清洁油品是石化行业的主要研究重点。本研究引入萃取催化氧化脱硫(ECODS)作为一种有效的脱硫技术。采用交联策略构建基于离子液体(IL)修饰脂质体(聚[MimA,A][杂多阴离子])的结构稳定的各向同性微反应器,其中暴露的咪唑阳离子锚定催化杂多阴离子(如[PWO])以确保活性位点的可及性。在这种界面催化反应中,微反应器类似于具有球形表面的乳化液滴,显著增强了催化界面。此外,球形囊泡的各向同性咪唑阳离子为杂多阴离子(如[PWO]和[PMoO])的附着提供了等效驱动力,确保活性位点充分暴露并降低传质阻力。优化后的聚[MimA,A][PWO]催化剂在1.5小时内实现了二苯并噻吩(DBT)的完全去除,并且在六个循环后仍保留92.4%的效率,显示出优异的活性和可回收性。对微反应器的形态、结构和性能进行了表征,并确定了最佳反应条件。在此基础上,评估了不同体系和含硫目标物的去除性能,从而证实了这类微反应器的构效关系。此外,从鉴定出的氧化产物推断出脱硫机理。总体而言,这种各向同性的聚[MimA,A][杂多阴离子]表现出优异的脱硫性能,具有广阔的应用潜力。