Hydrolytically Stable Nanotubular Cationic Metal-Organic Framework for Rapid and Efficient Removal of Toxic Oxo-Anions and Dyes from Water.

Abstract

Cationic framework materials capable of removing anionic pollutants from wastewater are highly desirable but relatively rarely reported. Herein, a cationic MOF (SCNU-Z1-Cl) possessing tubular channels with diameter of 1.5 nm based on Ni(II) and a nitrogen-containing ligand has been synthesized and applied to capture hazardous anionic contaminants from water. The SCNU-Z1-Cl exhibits high BET surface area of 1636 m2/g, and shows high hydrolytically stability in pH range from 4 to 10. Owing to the large tubular channels and the uncoordinated anions in the framework, the aqueous-phase anion-exchange applications of SCNU-Z1-Cl were explored with environmentally toxic oxo-anions including CrO42-, Cr2O72-, MnO4-, and ReO4-, and organic dyes. The adsorption of oxoanions exhibits high uptake kinetics and the adsorption capacities of CrO42-, Cr2O72-, MnO4-, and ReO4- are 126, 241, 292, and 318 mg/g, respectively, which were some of the highest values in the field of MOF/COF. In additional, the selectively is high when other concurrent anions are exist. The anionic dyes with different sizes including methyl orange, acid orange A, congo red, as well as methyl blue can be adsorbed by SCNU-Z1-Cl in few minutes to about 1 h. The adsorption capacities for them are 285, 180, 585, and 262 mg/g, respectively. In contrast, the adsorption kinetics for catinionic dyes with different sizes is obviously lower and exhibit a size-selectively adsorption that only cationic dye with suitable size (rhodamine B) can be adsorbed by SCNU-Z1-Cl. Consequently, SCNU-Z1-Cl can sepearate organic dyes in three different modes: size-dependent, charge-dependent, and kinetics-dependent selective adsorption. The excellent adsorption and separation properties of SCNU-Z1-Cl is attribute to the cationic framework, large tubular channel, as well as the high positive Zeta potential.