Highly efficient removal of tetracyclines from water by a superelastic MOF-based aerogel: Mechanism quantitative analysis and dynamic adsorption.

Metal-organic frameworks (MOFs) were promising adsorbents for removing antibiotics, but the inherent poor recyclability of MOF powders limits further application. Moreover, the dominant adsorption mechanisms and their quantitative assessment are less studied. Here, ultrahigh adsorption capacities of 821.51 and 931.87 mg g for tetracycline (TC) and oxytetracycline (OTC), respectively, were realised by a novel adsorbents (biochar loaded with MIL-88B(Fe), denoted as BC@MIL-88B(Fe)), which were further immobilised in a 3D porous gelatin (GA) substrate. The obtained BCM/GA showed superior adsorption performance under wide pH ranges and under the interference of humic acid. Moreover, it can survive >8 cycles and even maintain high adsorption efficiency in different actual water samples. Notably, BCM/GA can selectively remove tetracyclines in a multivariate system containing other kinds of antibiotics and from a dynamic adsorption system. Most importantly, the results of X-ray photoelectron spectroscopy, 2D Fourier transform infrared correlation spectroscopy (2D-FTIR-COS) and density functional theory techniques revealed that (1) for TC adsorption, at pH < 4.0, the contribution of complexation was 25 %-45 %, whereas pore filling and hydrogen bonding accounted for 39 %-72 % of the total uptake. At 4.0 < pH < 10.0, the contribution of complexation increased to 60 %-82 %, whereas electrostatic attraction and π-π interaction were 4 %-13 % and 2 %-10 %, respectively. (2) For OTC adsorption, complexation was dominant at 3.0 < pH < 10.0, accounting for 55 %-86 % of the total uptake, and electrostatic attraction and π-π interactions caused 3 %-10 % and 3 %-15 %, respectively. (3) At pH > 10.0, pore filling dominated TC and OTC adsorption. Finally, the reaction sequences of the main adsorption mechanisms were also probed by 2D-FTIR-COS. This work solves the poor recyclability of MOF powders and provides a mechanistic insight into antibiotic removal by MOFs.