Li Zhangli, Huang Di, Wang Yazhou, Yan Jiaying, Liu Yue, Zhao Haiyu, Lan Xianyong, Huang Yingping, Astruc Didier, Liu Xiang
Engineering Research Center of Eco-Environment in Three Gorges Reservoir Region of Ministry of Education, College of Hydraulic & Environmental Engineering, College of Materials and Chemical Engineering, China Three Gorges University, Yichang, 443002, China.
College of Animal Science and Technology, Northwest A&F University, Yangling, 712100, China.
Angew Chem Int Ed Engl. 2025 May;64(19):e202502408. doi: 10.1002/anie.202502408. Epub 2025 Apr 2.
With the increasing requirement for phosphorus resources and their shortage in nature, cyclic utilization of organophosphorus pollutants into phosphatic fertilizer might offer a sustainable approach to achieve the recycling of phosphorus. Herein, we first report the selective degradation of organophosphorus pollutants, via the synergistic effect of peroxymonosulfate (PMS) and sodium percarbonate (SPC), into phosphates (o-PO ), which are continually converted into phosphatic fertilizer by struvite precipitation on the continuous-flow reactor. Quenching experiments, electron paramagnetic resonance (EPR) results, electrochemical analysis, and density functional theory (DFT) calculation suggest that the transfer of electrons from SPC to PMS results in the synthesis of catalytically active species (i.e., ·OH, ·O , O, and CO·) for hydroxyethylidene-1,1-diphosphonicacid (HEDP) degradation. For the real glyphosate wastewater, the PMS/SPC system exhibits excellent catalytic activity with 69.20% decrease in chemical oxygen demand (COD) and 37.80% decrease in the total organic carbon (TOC) after 90 min. Indeed, high performance liquid chromatography (HPLC) confirms that glyphosate is completely degraded in 90 min with the formation of 271.93 µmol/L of o-PO , which is further converted into phosphatic fertilizer by the precipitation of struvite with 87.20% yield on continuous-flow reactor. Finally, biotoxicity of glyphosate to zebrafish and wheat seeds are significantly deceased after treatment of PMS/SPC system by zebrafish toxicology assays and germination tests of wheat seeds.
随着对磷资源需求的增加以及自然界中磷资源的短缺,将有机磷污染物循环利用制成磷肥可能提供一种实现磷循环利用的可持续方法。在此,我们首次报道通过过一硫酸盐(PMS)和过碳酸钠(SPC)的协同作用将有机磷污染物选择性降解为磷酸盐(o-PO),这些磷酸盐在连续流反应器上通过鸟粪石沉淀不断转化为磷肥。淬灭实验、电子顺磁共振(EPR)结果、电化学分析和密度泛函理论(DFT)计算表明,电子从SPC转移到PMS导致合成用于降解羟基亚乙基二膦酸(HEDP)的催化活性物种(即·OH、·O、O和CO·)。对于实际的草甘膦废水,PMS/SPC系统表现出优异的催化活性,90分钟后化学需氧量(COD)降低69.20%,总有机碳(TOC)降低37.80%。事实上,高效液相色谱(HPLC)证实草甘膦在90分钟内完全降解,生成271.93µmol/L的o-PO,在连续流反应器上通过鸟粪石沉淀进一步转化为磷肥,产率为87.20%。最后,通过斑马鱼毒理学试验和小麦种子发芽试验,在PMS/SPC系统处理后,草甘膦对斑马鱼和小麦种子的生物毒性显著降低。