Wang Haiqing, Liang Zhenda, Liu Chao, Zhu Lishan, Xu Yongtao, Zhou Li, Yan Bing
Institute of Environmental Research at Greater Bay Area, Key Laboratory for Water Quality and Conservation of the Pearl River Delta, Ministry of Education, Guangzhou University, Guangzhou, 510006, PR China; School of Environmental Science and Engineering, Shandong University, Qingdao, 266237, PR China.
Institute of Environmental Research at Greater Bay Area, Key Laboratory for Water Quality and Conservation of the Pearl River Delta, Ministry of Education, Guangzhou University, Guangzhou, 510006, PR China.
Chemosphere. 2022 Jun;297:134104. doi: 10.1016/j.chemosphere.2022.134104. Epub 2022 Feb 23.
Developing low-cost and efficient materials for dye pollutant removal under mild condition remains a great challenge. Here K and Tb co-doped porous MnO (K-Tb-MnO) nanoparticles with tailored properties including crystal structure, surface area and catalytic activity have been synthesized. Experimental results reveal that K-Tb-MnO nanoparticle has higher specific surface area, Mn content and surface oxygen vacancies than pristine MnO nanoparticle and single-doped MnO materials, showing the uniqueness of dual-doped metal ions. Using methyl blue (MB) as a model pollutant, its removal efficiency by K-Tb-MnO nanoparticles within 5 min is 93.6%, which is 18, 8.3, and 2.9 times higher than that of MnO, K-MnO, and Tb-MnO nanomaterials, respectively. Oxalic acid triggered MnO material dissolving assay and FT-IR spectrum suggested that remarkable performance of K-Tb-MnO nanoparticle toward MB removal can be attributed to a combined effect of adsorption (16% MB removal) and catalytic degradation (84% MB removal). Moreover, K-Tb-MnO nanoparticle mediated MB degradation is demonstrated to be a combination of non-radical oxidation by Mn and radical-participated degradation, with O as the main species. And the intermediates and pathways of MB degradation were studied by liquid chromatography-mass spectrometry. Importantly, cell viability experiment suggests that the toxicity of MB dye could be efficiently alleviated after the treatment with K-Tb-MnO nanoparticle. These results demonstrate the great potential of the novel K-Tb-MnO particles to be used as a highly effective nanomaterials to reduce the risk of dye wastes toward the environment and human health.
开发在温和条件下去除染料污染物的低成本高效材料仍然是一个巨大的挑战。在此，合成了具有定制特性（包括晶体结构、表面积和催化活性）的K和Tb共掺杂多孔MnO（K-Tb-MnO）纳米颗粒。实验结果表明，K-Tb-MnO纳米颗粒比原始MnO纳米颗粒和单掺杂MnO材料具有更高的比表面积、Mn含量和表面氧空位，显示出双掺杂金属离子的独特性。以亚甲基蓝（MB）为模型污染物，K-Tb-MnO纳米颗粒在5分钟内对其去除效率为93.6%，分别比MnO、K-MnO和Tb-MnO纳米材料高18倍、8.3倍和2.9倍。草酸引发的MnO材料溶解试验和傅里叶变换红外光谱表明，K-Tb-MnO纳米颗粒对MB去除的显著性能可归因于吸附（去除16%的MB）和催化降解（去除84%的MB）的综合作用。此外，K-Tb-MnO纳米颗粒介导的MB降解被证明是Mn的非自由基氧化和自由基参与降解的组合，其中O为主要物种。通过液相色谱-质谱联用研究了MB降解的中间体和途径。重要的是，细胞活力实验表明，用K-Tb-MnO纳米颗粒处理后，MB染料的毒性可以有效减轻。这些结果证明了新型K-Tb-MnO颗粒作为高效纳米材料用于降低染料废物对环境和人类健康风险的巨大潜力。
