Customizable Three-Dimensional Printed Zerovalent Iron: An Efficient and Reusable Fenton-like Reagent for Florfenicol Degradation
Dan Li, Yibo Fu, Wentao Hong, Shunlu Li, Mulan Qiu, Hongdie Yu, Heli Wang, Junhong Wu, Qian Yang, Sen Yang, Jianhui Xu, Yunfei Zhang, Shenggui Chen, Yin Zhong, Ping’an Peng
Abstract
High Resolution Image Download MS PowerPoint Slide Zerovalent iron (Fe 0 )-based Fenton-like technology has great potential for treating recalcitrant organic pollutants (ROPs) in wastewater. However, rapidly and precisely manufacturing Fe 0 -based materials with the desired geometries is challenging. Herein, novel three-dimensional printed Fe 0 (3DP-Fe 0 ) and bimetallic 3DP-Ni/Fe 0 were customized by 3D printing for efficient Fenton-like degradation of florfenicol (FLO), a typical antibiotic in wastewater. 3DP-Ni/Fe 0 with hydrogen peroxide (H 2 O 2 ) exhibited superior reactivity toward FLO than 3DP-Fe 0, generating hydroxyl radicals (·OH) and atomic hydrogen to achieve >90% dehalogenation and >70% total organic carbon removal within 10 min. The resulting degradation intermediates possessed lower antibacterial activity than FLO and did not cause resistance gene proliferation in activated sludge. The Fenton-like activity of 3DP-Ni/Fe 0 was similar across different shapes but increased with increasing porosity and size. Compared with powdered Ni/Fe 0, 3DP-Ni/Fe 0 exhibited faster electron transfer during Fe(II)/Fe(III) cycling, which increased the utilization efficiency of dissolved Fe 2+ and H 2 O 2 for ·OH production. Moreover, 3DP-Ni/Fe 0 could be reused >150 times, 5-fold more than powdered Ni/Fe 0, owing to its lower metal ion release and Fe 0 depletion. 3DP-Ni/Fe 0 with H 2 O 2 can also efficiently remove chemical oxygen demand from real wastewater and other ROPs (e.g., acetaminophen, carbamazepine, thiamphenicol, and tetrabromobisphenol A).