Iron-nickel bimetallic metal-organic frameworks as bifunctional Fenton-like catalysts for enhanced adsorption and degradation of organic contaminants under visible light: Kinetics and mechanistic studies.

Iron-nickel bimetallic organic frameworks (FeNiX-BDC, H2BDC: terephthalic acid) were developed as bifunctional materials for adsorption and photo-Fenton degradation of organic dyes with different charge properties. Significantly enhanced adsorption capacity of FeNi1/15-BDC towards methylene blue (MB) and methyl orange (MO) was achieved, 5.3 and 2.6 times higher than that of pristine Fe-BDC, which was attributed to enlarged specific surface area and pore volume and the decreased surface charges induced by Ni doping. The adsorption kinetics demonstrated that chemisorption was dominant and intra-particle diffusion was the rate-controlling step. Two-stage degradation including slow induction stage and rapid oxidation stage fitted with pseudo-zero-order kinetics well. The increased rate constants (2.472 vs. 1.188 min-1 for MB; 0.616 vs. 0.421 min-1 for MO) in the induction stage as well as the superior removal capability by asynchronism relative to synchronism jointly corroborating the improved adsorption performance was favor for subsequent degradation. Notably, this heterogeneous system not only exhibited obvious advantages like wider pH working range (3-9), better stability and reusability of catalysts, but also achieved the dual objectives of in-situ decontamination and adsorbent regeneration. The coupling of adsorption and degradation along with synergism between photocatalysis and Fenton-like process are responsible for the reinforced removal of organic contaminants.