Synergistic Effect of Ion Doping and Type-II Heterojunction Construction and Ciprofloxacin Degradation by MIL-68(In,Bi)-NH2@BiOBr under Visible Light.

Heterojunction structure and ion doping techniques are viable tactics in facilitating the generation and separation of photogenerated electrons and holes in photocatalysis. In the current study, a novel Bi ion-doped MIL-68(In,Bi)-NH2@BiOBr (MIBN@BOB) type-II heterojunction was first synthesized in a one-step solvothermal reaction. Doping of Bi ions not only broadened the light-sensing range but also provided reliable anchor sites for the in situ growth of BiOBr. Meanwhile, the heterostructure supplied new channels for photogenerated carriers, accelerating the transfer and inhibiting the recombination of photogenerated electron-hole. The obtained MIBN@BOB exhibited enhanced photocatalytic performance (91.1%) than MIL-68(In)-NH2 (40.8%) and BiOBr (57.5%) in ciprofloxacin (CIP) degradation under visible light, with excellent reusability. Photocatalysts were characterized in detail, and a series of photoelectrochemical tests were utilized to analyze the photoelectric properties. MIBN@BOB were deduced to conform the electron conduction mechanism of conventional type-II heterojunctions. More importantly, based on the above experiments and density functional theory (DFT) calculation, BiOBr-Bi in MIBN@BOB can serve as the major active sites of CIP enrichment, and •O2- and 1O2 generated at the BiOBr interface can react with the adsorbed CIP directly. Lastly, the possible degradation products and pathways of CIP were analyzed by liquid chromatography-tandem mass spectrometry (LC/MS/MS). This study provides a reference for the construction of ion-doping-modified metal-organic framework (MOF)-based heterojunction photocatalysts and their application in antibiotic removal.

Upcycling of Fe-bearing sludge: preparation of erdite-bearing particles for treating pharmaceutical manufacture wastewater.

Groundwater treatment sludge is a type of solid waste with 9.0-28.9% wt.% Fe content and is precipitated in large quantity from backwash wastewater in groundwater treatment. The sludge is mainly composed of fine particles containing Fe, Si and Al oxides, such as ferrihydrite, quartz and boehmite. The Fe oxides mostly originate from the oxidation of ferrous Fe in groundwater, whilst the silicate/aluminium compounds mainly originate from the broken quartz sand filter in the backwash step. In general, the sludge is firstly coagulated, dewatered by filter pressing and finally undergoes harmless solidification before it is sent to landfills. However, this process is costly (approximately US$66.1/t) and complicated. In this study, groundwater treatment sludge was effectively recycled to prepare novel erdite-bearing particles via a one-step hydrothermal method by adding only Na2S·9H2O. After hydrothermal treatment, the quartz and boehmite of the sludge were dissolved and recrystallised to sodalite, whilst ferrihydrite was converted to an erdite nanorod at 160 °C and a hematite at 240 °C. SP160 was prepared as fine nanorod particles with 200 nm diameter and 2-5 µm length at a hydrothermal temperature of 160 °C. Nearly 100% OTC and its derivatives in pharmaceutical manufacture wastewater were removed by adding 0.1 g SP160. The major mechanism for the removal was the spontaneous hydrolysis of erdite in SP160 to generate Fe oxyhydroxide and use many hydroxyl groups for coordinating OTC and its derivatives. This study presents a novel method for the resource reutilisation of waste groundwater treatment sludge and reports efficient erdite-bearing particles for pharmaceutical manufacture wastewater treatment.