Macro-manufacturing robust and stable metal-organic framework beads for antibiotics removal from wastewater

Metal-organic frameworks (MOFs) have shown great prospects in wastewater remediation. However, the easy aggregation, difficult separation and inferior reusability greatly limit their large-scale application. Herein, we proposed a facile, green and low-cost strategy to construct robust and stable MOF-based hydrogel beads (Fe-BTC-HBs) in a gram scale, and employed them to remove antibiotics from wastewater. As a result, the Fe-BTC-HBs demonstrated outstanding adsorption capacity for both ofloxacin (OFL) and tetracycline (TC) (281.17 mg/g for OFL and 223.60 mg/g for TC) under a near-neutral environment. The main adsorption mechanisms of OFL and TC were hydrogen bonding and π-π stacking interaction. Owing to its macroscopic granule and stable structure, Fe-BTC-HBs can be separated rapidly from wastewater after capturing antibiotics, and more than 85% adsorption capacity still remained after six cycles, while the powdered Fe-BTC only showed less than 6% recovery efficiency with massive weight loss (around 92%). In real industrial effluent, the adsorption performance of Fe-BTC-HBs toward two antibiotics exhibited negligible decreases (2.9% for OFL and 2.2% for TC) compared with that in corresponding solutions. Furthermore, Fe-BTC-HBs also had appealing economic and environmental benefit. Overall, the macro-manufactured MOF beads have the promising potential for the large-scale wastewater treatment.