Enhancing Adsorption Desulfurization Performance Using Enriched Cu(I) Sites over Microenvironment‐Modulated HKUST‐1

Abstract High‐efficiency adsorption of aromatic sulfur‐containing compounds from liquid hydrocarbon fuels over metal‐organic frameworks (MOFs) is challenging because of inert metal sites. A new method, the Ce‐enhanced modulation of MOFs’ microenvironment, is proposed to modulate the –COO···Cu(II)– coordination microenvironment of Hong Kong University of Science and Technology (HKUST‐1) using Ce(III) as a molecular scalpel for fabricating abundant high‐efficiency Cu(I) and Cu‐coordination‐unsaturated sites and improving the pore structures around adsorptive sites. The optimal CH‐250 thus exhibits adsorptive capacities for 20.2, 28.0, and 58.3 mg S g –1 of thiophene, benzo‐thiophene, and dibenzothiophene, respectively, which are superior to most reported MOFs, zeolites, and nanoporous carbons. The constructed Cu(I) sites show stronger affinity for dibenzothiophene (−0.86 eV) than the initial Cu(II) (−0.74 eV) for out‐of‐plane adsorption. Further, they are far stronger in‐plane adsorption interactions in DBT/CH‐250 (−0.90 eV) than those in DBT/HKUST‐1 (−0.37 eV). Thus, molecular engineering for modulating the coordination microenvironment of MOFs shows great potential for adsorption desulfurization.