High-Efficiency Separation of Aromatic Sulfide from Liquid Hydrocarbon Fuel in Conjugated Porous Organic Framework with Polycarbazole Unit.

We synthesized three conjugated polycarbazole porous organic frameworks named o-Cz-POF, m-Cz-POF, and p-Cz-POF for hydrocarbon fuels' adsorptive desulfurization. The carbazole building blocks possessed ortho, meta, and para steric configuration, which resulted in POFs exhibiting adjustable specific surface area and pore structure. Adsorption kinetics experiments and DFT calculations were carried out to understand the competitive adsorption of 3-methylthiophene and octane in the Cz-POF. The instantaneous adsorption rate and adsorption energy calculation analyses gave a convincing demonstration on preferential selective adsorption of 3-methylthiophene in Cz-POFs. Furthermore, the fixed bed breakthrough experiment demonstrated that the Cz-POFs can selectively adsorb 3-methylthiophene efficiently, and hydrocarbon fuel with sulfide content close to 0 ppm was obtained. The features of high stability and high desulfurization efficiency of Cz-POFs make them hold the promise as a new type of porous adsorbent for ultradeep adsorption desulfurization.