Superior Adsorptive Removal of Anionic Azo Dyes from Aqueous Solutions Using Sulfonic Acid Group-Modified MIL-101@Graphene Oxide Composite

Abstract

It is critical to remove organic contaminants from wastewater released by the printing and dyeing industry for addressing water pollution issue. Therefore, the fabrication of new adsorbents with excellent removal efficiencies is an urgent task. A composite of MIL-101 partially functionalized with −SO 3 H (MIL-101-SO 3 H) and graphene oxide (GO) was prepared by assembling MIL-101-SO 3 H truncated octahedrons on the GO framework. The synthesized MIL-101-SO 3 H@GO has a superior adsorption efficiency for anionic azo dyes. The maximum adsorption capacities of MIL-101-SO 3 H@GO-1 for Congo red, methyl orange, acid orange 7, and acid orange G reached 2711.3, 818.8, 551.2, and 319.8 mg/g, respectively, which are considerably higher than those obtained using unmodified MIL-101. This is because additional interactions that promote azo dye adsorption, such as hydrogen bonding between the dye and the sulfonic acid groups of MIL-101-SO 3 H or the carboxyl groups of GO, were induced, and agglomerate pores that accommodated the dye were formed in the composite. The ultrahigh removal efficiency of the composite for azo dyes is mainly driven by hydrogen bonding, electrostatic interactions, π−π stacking between the MIL-101-SO 3 H@GO and dye molecules, synergistic interactions at the interface of GO and MIL-101-SO 3 H microcrystals, and the pore-filling effect. Understanding these driving forces for dye adsorption can contribute to the development of sustainable and functionally modified metal−organic framework composite adsorbents.