Construction of Pillared-Layer Metal–Organic Frameworks as an All-Visible-Light Switchable Photocatalyst for Aqueous Cr(VI) Reduction

Abstract

Recently, two-dimensional metal–organic frameworks that are photoactive have shown great potential for efficiently converting solar energy into chemical energy. In this work, we successfully synthesized and designed two M2-MOFs ([Cu(L1)((CH3)2NH)]n (Cu-MOF) and [Zn(L1)(CH3)2NH)]n (Zn-MOF), H2 L1 = 4,4′-(benzo[c][1,2,5]thiadiazole-4,7-diyl)dibenzoic acid). Structural analysis suggests that the five-coordinated M(II) ion is surrounded by four oxygen ions from two ligands and one nitrogen atom from one dimethylamine molecule. The ligand spacer acts as a bridge between two SBUs and forms a 2D layer with rhomboid windows. These moieties are arranged in a staggered ABAB pattern, which likely aids in exfoliation. The UV–vis diffuse reflectance spectra (DRS) test shows that when the metal center in the MOF framework is replaced with Cu(II) ions, the light absorption range covers 200–1100 nm, which is much larger than the light absorption range of Zn-MOF. Moreover, the photoelectric current, electrochemical impedance spectra (EIS), and Mott–Schottky tests all indicate that Cu-MOF has better photoelectric properties. When applied to the photocatalytic reduction of Cr(VI), Cu-MOF and Zn-MOF can completely reduce Cr(VI) within 100 min under 450 nm LED light irradiation. Under sunlight irradiation, Cu-MOF can completely reduce Cr(VI) within 40 min, achieving the removal of Cr(VI) ions, which is much faster than the rate of Cr(VI) removal by Zn-MOF.