Modulator-assisted solvent-free synthesis of amorphous zirconium terephthalate catalyst for efffcient oxidative desulfurization

Journal:Journal of Hazardous Materials

Key Words:Defect engineering Amorphous Oxidative desulfurization Metal-organic framework Catalytic mechanism

Abstract:Oxidative desulfurization (ODS) emerges as a critical player in enhancing efffcient fuel desulfurization and promoting sustainable clean energy. Metal-organic frameworks (MOFs) show great potential as ODS catalysts because of their exceptional porosity and versatility. This study explores the use of amorphous metal-organic frameworks (aMOFs), which combine MOFs’ structural advantages with unique properties of amorphous materials, to enhance catalytic efffciency in ODS. Traditional methods for synthesizing MOFs rely on solventthermal or solvent-free methods, each with limitations in environmental impact or scalability. To address this, we introduce a novel strategy utilizing a small quantity of benzoic acid (BA) modiffer to facilitate the solventfree, one-pot, mechanical synthesis of amorphous zirconium terephthalate (GU-2BA-3h). The resulting GU2BA-3h demonstrates exceptional ODS performance, efffciently removing 1000 ppm of dibenzothiophene (DBT) in just 6 min at 60 ◦C. Amorphous GU-2BA-3h features an expanded external surface area, increased acidic sites, and exceptional stability, resulting in a high turnover frequency (19.6 h− 1 ) and outstanding catalyticactivity (53.2 mmol g− 1 h− 1 ), establishing it as a highly efffcient ODS catalyst. This remarkable performance arises from the formation of dangling carboxyl groups and active metal sites due to the competitive coordination of benzoic acid with the linker. Experimental evidence conffrms that these carboxyl groups and exposed Zr-OH sites interact with oxidants, generating hydroxyl radicals that effectively eliminate sulfur-containing compounds. Furthermore, the methodology exhibits universality in constructing amorphous Zr-based MOFs, and provides an eco-friendly, cost-effective route for efffcient ODS catalyst production.

Co-author:Junzhen Guo,Zhaokun Wang,Haibin Yang,Zhaohui Liu,Zhi Huang,Liyan Wang

First Author:Liang Chu

Indexed by:Journal paper

Correspondence Author:Mu Yang,Ge Wang

Volume:469,

Page Number:133886.

Translation or Not:no

Date of Publication:2024-02-22

Included Journals:SCI