Decoding Desulfurization Pathways in Metal-Organic Frameworks (MOFs) via Experimental and Computational Approaches: A...

Area of Science:

• Materials Science
• Chemistry
• Nanotechnology

Background:

• Metal-organic frameworks (MOFs) offer tunable porous structures for various applications.
• Developing efficient adsorbents for removing sulfur compounds from fuels is crucial for environmental protection.

Purpose of the Study:

• To synthesize and characterize two new MOFs, MM-1 and MM-2, using mixed linkers.
• To evaluate the desulfurization performance of the synthesized MOFs, particularly for dibenzothiophene (DBT) and benzothiophene (BT).

Main Methods:

• Solvothermal synthesis of MOFs using biphenyl-4,4'-dicarboxylic acid (BPDC) and 4,4'-bipyridine (Bipy).
• Structural characterization via single-crystal X-ray diffraction (SCXRD), FTIR, TGA, PXRD, and XPS.
• Porosity analysis using N2 sorption (BET) and adsorption studies for DBT and BT.
• Density Functional Theory (DFT) calculations to understand adsorption mechanisms.

Main Results:

• Two new MOFs, MM-1 ({[Cu2(BPDC)2(Bipy)2]·2DMF}n) and MM-2 ({[Zn3(BPDC)3(Bipy)]4H2O·2DMF}n), with sra topology were successfully synthesized.
• MM-1 exhibited high surface area (597.29 m2 g-1) and excellent adsorption capacities for DBT (91.82 mg g-1) and BT (78.80 mg g-1), achieving ~87% DBT removal.
• DFT calculations indicated strong thermodynamic binding in MM-1, driven by π-π stacking and O···S interactions, confirming its potential for desulfurization.

Conclusions:

• The synthesized MOFs, particularly MM-1, demonstrate significant potential as efficient adsorbents for desulfurization.
• The robust structure, high surface area, and specific host-guest interactions of MM-1 contribute to its superior performance.
• This study highlights the design of MOFs with tailored properties for environmental remediation applications.