School of Environment and Civil Engineering, Dongguan University of Technology, Dongguan 523808, China.
State Key Laboratory of Organic Geochemistry, Guangdong Provincial Key Laboratory of Environmental Protection and Resources Utilization, Guangdong-Hong Kong-Macao Joint Laboratory for Environmental Pollution and Control, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Wushan, Guangzhou 510640, China.
Environ Sci Technol. 2024 Oct 29;58(43):19501-19513. doi: 10.1021/acs.est.4c06536. Epub 2024 Oct 10.
Zerovalent iron (Fe)-based Fenton-like technology has great potential for treating recalcitrant organic pollutants (ROPs) in wastewater. However, rapidly and precisely manufacturing Fe-based materials with the desired geometries is challenging. Herein, novel three-dimensional printed Fe (3DP-Fe) and bimetallic 3DP-Ni/Fe were customized by 3D printing for efficient Fenton-like degradation of florfenicol (FLO), a typical antibiotic in wastewater. 3DP-Ni/Fe with hydrogen peroxide (HO) exhibited superior reactivity toward FLO than 3DP-Fe, 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 was similar across different shapes but increased with increasing porosity and size. Compared with powdered Ni/Fe, 3DP-Ni/Fe exhibited faster electron transfer during Fe(II)/Fe(III) cycling, which increased the utilization efficiency of dissolved Fe and HO for ·OH production. Moreover, 3DP-Ni/Fe could be reused >150 times, 5-fold more than powdered Ni/Fe, owing to its lower metal ion release and Fe depletion. 3DP-Ni/Fe with HO can also efficiently remove chemical oxygen demand from real wastewater and other ROPs (e.g., acetaminophen, carbamazepine, thiamphenicol, and tetrabromobisphenol A).
零价铁（Fe）基类 Fenton 技术在处理废水中难降解有机污染物（ROPs）方面具有巨大潜力。然而，快速、精确地制造具有所需几何形状的 Fe 基材料具有挑战性。在此，通过 3D 打印定制了新颖的三维打印 Fe（3DP-Fe）和双金属 3DP-Ni/Fe，用于高效类 Fenton 降解废水中的典型抗生素氟苯尼考（FLO）。3DP-Ni/Fe 与过氧化氢（HO）相比，对 FLO 的反应性更高，生成羟基自由基（·OH）和原子氢，可在 10 min 内实现>90%的脱卤和>70%的总有机碳去除。所得降解中间体的抗菌活性低于 FLO，且不会在活性污泥中引起抗性基因增殖。3DP-Ni/Fe 的类 Fenton 活性在不同形状下相似，但随着孔隙率和尺寸的增加而增加。与粉末状 Ni/Fe 相比，3DP-Ni/Fe 在 Fe(II)/Fe(III)循环过程中表现出更快的电子转移，从而提高了溶解 Fe 和 HO 用于·OH 生成的利用率。此外，3DP-Ni/Fe 可重复使用>150 次，是粉末状 Ni/Fe 的 5 倍，这是由于其金属离子释放和 Fe 耗竭较少。3DP-Ni/Fe 与 HO 还可以有效地从实际废水中去除化学需氧量和其他 ROPs（例如，对乙酰氨基酚、卡马西平、噻苯隆和四溴双酚 A）。
