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

Oxidative desulfurization (ODS) emerges as a critical player in enhancing efficient 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 efficiency in ODS. Traditional methods for synthesizing MOFs rely on solvent-thermal 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) modifier to facilitate the solvent-free, one-pot, mechanical synthesis of amorphous zirconium terephthalate (GU-2BA-3h). The resulting GU-2BA-3h demonstrates exceptional ODS performance, efficiently 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) and outstanding catalytic activity (53.2 mmol g h), establishing it as a highly efficient 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 confirms 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 efficient ODS catalyst production.