不同形貌氧化钴活化过一硫酸盐降解硝基酚

摘要通过控制形貌制备具有高活性晶面的金属氧化物可提高硝基酚的降解效果，以硝酸钴和乙酸钴为原料，制备了八面体、立方块和棒状Co₃O₄，通过X射线衍射（XRD）、扫描电子显微镜（SEM）和透射电子显微镜（TEM）对催化剂进行表征，表明合成的Co₃O₄粒径均匀、纯度较高。以3种不同形貌的Co₃O₄为催化剂，在pH值为8.0条件下活化过一硫酸盐（PMS）降解不同种类的硝基酚，采用高效液相色谱和总有机碳分析仪测定反应前后硝基酚和总有机碳含量（TOC）变化。3种Co₃O₄在Co₃O₄/PMS体系降解硝基酚时表现出不同的催化活性：棒状Co₃O₄ > 立方块Co₃O₄ > 八面体Co₃O₄，并且对不同硝基酚的降解效率存在显著的差异性。3种Co₃O₄在pH值为8.0下活化PMS所析出的Co²⁺含量较低，且均表现出良好的循环利用性。自由基淬灭实验和电子自旋共振（ESR）测试表明Co₃O₄/PMS体系降解硝基酚是通过自由基和非自由基机制共同协作完成的，起作用的活性氧化物种主要为羟基自由基（·OH）、硫酸根自由基（SO₄^·-）和单线态氧（¹O₂）。

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	张笑丛
	王琮
	吴松海

关键词： Co₃O₄ 过一硫酸盐(PMS) 硝基酚降解羟基自由基(· OH) 硫酸根自由基(SO₄^· -)

Abstract： The degradation effect of nitrophenol can be improved by controlling the morphology of metal oxides with highly active crystal planes. The octahedral, cubic and rod-like Co₃O₄ were prepared by using cobalt nitrate and cobalt acetate. The synthesized compounds were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscope (TEM), and results show that the prepared Co₃O₄ have uniform size and high purity. Peroxymonosulfate (PMS) was activated by Co₃O₄ with different morphologies to degrade nitrophenols at pH 8.0. High performance liquid chromatography (HPLC) and total organic carbon (TOC) analyzer were used to determine the changes of nitrophenols and total organic carbon content before and after the reaction. The reaction rate and nitrophenols degradation in the Co₃O₄/PMS system indicate that the activity of catalysts shows an order of rod-like Co₃O₄ > cubic Co₃O₄ > octahedral Co₃O₄, and the position of -NO₂ also affects the degradation of nitrophenol. The trace Co²⁺ leached from Co₃O₄ has no significant effect at pH 8.0, and all of the Co₃O₄ showed good reusability. Quenching experiments and electron spin resonance (ESR) spectra show that the degradation of nitrophenol in Co₃O₄/PMS system is a pathway where hydroxyl radical (·OH), sulfate radical (SO₄^·-) and singlet oxygen (¹O₂) play main roles.

Keywords： Co₃O₄； peroxymonosulfate； nitrophenols； degradation； hydroxyl radical (·OH)； sulfate radical (SO₄^·-)

Received 2020-02-09;

Corresponding Authors: 吴松海,E-mail:wusonghai@tju.edu.cn。 Email: wusonghai@tju.edu.cn

About author: 张笑丛(1995-),女,硕士研究生,现从事水处理方面的研究。

引用本文:

张笑丛, 王琮, 吴松海.不同形貌氧化钴活化过一硫酸盐降解硝基酚[J]. 化学工业与工程, 2020,37(6): 38-47

Zhang Xiaocong, Wang Cong, Wu Songhai.Degradation of Nitrophenols in Wastewater by Peroxymonosulfate Activated by Cobalt Oxide with Different Morphologies[J]. Chemcial Industry and Engineering, 2020,37(6): 38-47

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