Post-synthetic acid treatment of aqueous synthesized bimetallic Ce/Zr MOF-801 enables efficient oxidative desulfurization of model fuels

Journal:Fuel

Key Words:Bimetallic metal–organic framework Defect engineering Oxidative desulfurization Catalytic mechanism

Abstract:Host-guest catalysts are promising for tailored applications but require innovative synthesis strategies. Herein, we report the first ambient aqueous-phase synthesis of bimetallic Ce/Zr MOF-801, followed by acid posttreatment. Utilizing defect engineering, Ce species are preferentially exposed within the robust Zr-MOF-801 substrate. This structural modification substantially enhances the host–guest catalyst’s oxidative desulfurization (ODS) performance. We systematically investigate synthesis parameters, spatiotemporal yield, and defect characterization, and refines catalytic conditions. Post-acid-treated Ce/Zr-MOF-801-H displays augmented external surface area (189 m2 g�� 1), and exposed acidic sites while upholding the outstanding intrinsic stability of the Zr-MOF-801 substrate. Under optimal conditions (60 ◦C, 6 min), Ce/Zr-MOF-801-H completely eliminates dibenzothiophene (1000 ppm S), with a turnover frequency of 39.3 h�� 1 and catalytic activity of 53.2 mmol g�� 1 h�� 1, far surpassing Zr-UiO-66-H. It maintains a desulfurization rate of 96.6% after five cycles. FTIR spectroscopy, quenching experiments, and ESR spectroscopy reveal that the exposed Ce sites serve dual roles: (1) activating the substrate by reducing the electron density of sulfur atoms and (2) facilitating H2O2 into hydroxyl and superoxide radicals, driving ODS. This strategy not only advances industrial ODS applications but also sheds light on the synthesis of MOF-based host–guest catalysts.

Co-author:Zhaokun Wang,Zhaohui Liu,Teng Zhao,Liyan Wang

First Author:Liang Chu

Indexed by:Journal paper

Correspondence Author:Mu Yang,Ge Wang

Volume:401,

Page Number:135846

Translation or Not:no

Date of Publication:2025-05-28

Included Journals:SCI