Designed Construction of 2D Honeycomb Cationic MOF Materials for Selective Removal of Sulfonic Anionic Dyes

Abstract

Various carcinogenic dyes in water bodies are difficult to degrade due to their stability to light and oxidants, causing extended pollution. In this study, MOF <b>1</b> ({[Co(tib)₂]·(H₂O)₂·SO₄}_<i>n</i>) and MOF <b>2</b> ({[Cu(tib)₂]·(H₂O)₂·SO₄}_<i>n</i>) (tib = 1,3,5-tirs(1-imidazolyl)benzene) were synthesized by the solvothermal method. MOFs <b>1</b> and <b>2</b> were successfully characterized by single-crystal X-ray diffraction (XRD) and powder X-ray diffraction (PXRD). Based on the structural characteristics of MOFs <b>1</b> and <b>2</b>, we designed two cationic MOF material skeletons, namely, MOFs <b>I</b> and <b>II</b> ([Co(tib)₂²⁺]_<i>n</i> and [Cu(tib)₂²⁺]_<i>n</i>), which were obtained by calcination in combination with the thermogravimetric curve to remove the free components in the lattice. As expected, MOFs <b>I</b> and <b>II</b> showed an excellent adsorption effect on sulfonic anionic dyes. Notably, the adsorption capacity of MOF <b>I</b> can reach 2922.8 mg g^-1 for Congo Red (CR) at room temperature (RT). The adsorption process fits the pseudo-second-order kinetic model and Freundlich isotherm model. Moreover, zeta potential tests and quantum chemical calculations indicate that electrostatic interactions and hydrogen bond between the hydroxyl group on the sulfonic acid group and the N atom on the imidazole ring mainly promote the adsorption of CR dyes on MOF <b>I</b>. MOFs <b>I</b> and <b>II</b> are revealed as a promising novel adsorption material to remove hazardous organic aromatic pollutants with high efficiency in future endeavors.