Chen Chunguang, Zhang Junkai, Liu Jia, Li Jiani, Ma Shuo, Yu Aishui
Department of Chemistry, School of Materials and Chemistry, University of Shanghai for Science and Technology, Shanghai 200093, China.
Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Collaborative Innovation Center of Chemistry for Energy Materials, Department of Chemistry, Institute of New Energy, Fudan University, Shanghai 200438, China.
Molecules. 2023 Dec 26;29(1):152. doi: 10.3390/molecules29010152.
How to efficiently activate peroxymonosulfate (PMS) in a complex water matrix to degrade organic pollutants still needs greater efforts, and cobalt-based bimetallic nanomaterials are desirable catalysts. In this paper, sea urchin-like NiCoO nanomaterials were successfully prepared and comprehensively characterized for their structural, morphological and chemical properties via techniques, such as X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), among others. The sea urchin-like NiCoO nanomaterials exhibited remarkable catalytic performance in activating PMS to degrade phenol. Within the NiCoO/PMS system, the removal rate of phenol (50 mg L, 250 mL) reached 100% after 45 min, with a reaction rate constant k of 0.091 min, which was 1.4-times higher than that of the monometallic compound CoO/PMS system. The outstanding catalytic activity of sea urchin-like NiCoO primarily arises from the synergistic effect between Ni and Co ions. Additionally, a comprehensive analysis of key parameters influencing the catalytic activity of the sea urchin-like NiCoO/PMS system, including reaction temperature, initial pH of solution, initial concentration, catalyst and PMS dosages and coexisting anions (HCO, Cl, NO and humic acid), was conducted. Cycling experiments show that the material has good chemical stability. Electron paramagnetic resonance (EPR) and quenching experiments verified that both radical activation (SO, OH, O) and nonradical activation (O) are present in the NiCoO/PMS system. Finally, the possible degradation pathways in the NiCoO/PMS system were proposed based on gas chromatography-mass spectrometry (GC-MS). Favorably, sea urchin-like NiCoO-activated PMS is a promising technology for environmental treatment and the remediation of phenol-induced water pollution problems.
如何在复杂的水基质中高效激活过一硫酸盐（PMS）以降解有机污染物仍需付出更大努力，而钴基双金属纳米材料是理想的催化剂。本文成功制备了海胆状NiCoO纳米材料，并通过X射线衍射（XRD）、透射电子显微镜（TEM）、扫描电子显微镜（SEM）、X射线光电子能谱（XPS）等技术对其结构、形态和化学性质进行了全面表征。海胆状NiCoO纳米材料在激活PMS降解苯酚方面表现出显著的催化性能。在NiCoO/PMS体系中，45分钟后苯酚（50 mg L，250 mL）的去除率达到100%，反应速率常数k为0.091 min，比单金属化合物CoO/PMS体系高1.4倍。海胆状NiCoO出色的催化活性主要源于Ni和Co离子之间的协同效应。此外，还对影响海胆状NiCoO/PMS体系催化活性的关键参数进行了综合分析，包括反应温度、溶液初始pH值、初始浓度、催化剂和PMS用量以及共存阴离子（HCO、Cl、NO和腐殖酸）。循环实验表明该材料具有良好的化学稳定性。电子顺磁共振（EPR）和猝灭实验证实，NiCoO/PMS体系中同时存在自由基激活（SO、OH O）和非自由基激活（O）。最后，基于气相色谱-质谱联用（GC-MS）提出了NiCoO/PMS体系中可能的降解途径。有利的是，海胆状NiCoO激活PMS是一种有前途的环境处理技术，可用于修复苯酚引起的水污染问题。
