NiCo2O4@纤蛇纹石活化过硫酸钾降解甲基橙

doi:10.16085/j.issn.1000-6613.2024-0544

化工进展 ›› 2025, Vol. 44 ›› Issue (4): 2352-2364.DOI: 10.16085/j.issn.1000-6613.2024-0544

NiCo₂O₄@纤蛇纹石活化过硫酸钾降解甲基橙

苏晓洁¹^,²(), 严群¹^,²(), 李欣城¹^,²^,³, 薛文慧¹^,², 陈奕浩¹^,²

^1.河流源头水生态保护江西省重点实验室，江西赣州 341000
^2.赣州市赣江流域水质安全保障技术创新中心，江西赣州 341000
^3.江西理工大学资源与环境工程学院，江西赣州 341000

收稿日期:2024-04-02 修回日期:2024-06-20 出版日期:2025-04-25 发布日期:2025-05-07
通讯作者: 严群
作者简介:苏晓洁（2000—），女，硕士研究生，研究方向为水污染控制高级氧化技术。E-mail：1042660813@qq.com。
基金资助:
江西省教育厅科学技术研究项目(GJJ2200823)

Activation of potassium persulfate by NiCo₂O₄@chrysotile to degrade methyl orange

SU Xiaojie¹^,²(), YAN Qun¹^,²(), LI Xincheng¹^,²^,³, XUE Wenhui¹^,², CHEN Yihao¹^,²

^1.Jiangxi Provincial Key Laboratory of Water Ecological Conservation at Headwater Regions, Ganzhou 341000, Jiangxi, China
^2.Innovation Center for Water Quality Security Technology at Ganjiang River Basin, Ganzhou 341000, Jiangxi, China
^3.School of Resource and Environmental Engineering, Jiangxi University of Science and Technology, Ganzhou 341000, Jiangxi, China

Received:2024-04-02 Revised:2024-06-20 Online:2025-04-25 Published:2025-05-07
Contact: YAN Qun

摘要/Abstract

摘要：

为了更好地处理水环境中的偶氮染料污染问题，充分利用我国储量丰富的天然矿物资源，实验中直接使用纤蛇纹石矿物纤维作为非均相催化剂载体处理难降解废水问题。在保证矿物资源应用经济性的同时，充分利用纤蛇纹石中的多种活性组分，以探索纤蛇纹石矿产资源利用新路径。本文通过水热-煅烧法制备具有核壳结构的复合材料NiCo₂O₄@纤蛇纹石纤维（NC@CF），将其用于活化过二硫酸盐（PDS）降解甲基橙（MO），并结合扫描电子显微镜、傅里叶变换红外光谱等材料表征手段对NC@CF/PDS体系降解MO的机理展开探究。结果表明：NiCo₂O₄和纤蛇纹石的结合在MO的降解过程中具有协同作用，负载比为2∶1的NC@CF-2/PDS体系在最优条件下降解MO，去除率可达94.50%，降解过程符合准一级动力学模型。此外，结合自由基淬灭实验、电子顺磁共振、X射线光电子能谱分析以及电化学实验表明，NC@CF-2/PDS体系中MO的降解是在·OH和SO $4 -$ ·的自由基途径和电子转移的非自由基途径的协同作用下完成的。

关键词: 过硫酸钾, 非均相催化, 纤蛇纹石, 钴酸镍, 甲基橙

Abstract:

In order to preferably deal with the problem of azo dye pollution in the aquatic environment and make full use of China's abundant natural mineral resources, chrysotile mineral fibers were directly used as heterogeneous catalyst carriers in the experiment. While ensuring the economic application of mineral resources, it should make full use of various active components in chrysotile to explore a new path for the utilization of chrysotile mineral resources. NiCo₂O₄@chrysotile fiber (NC@CF) with core-shell structure was prepared by hydrothermal-calcination method, which was used to activate peroxydisulfate (PDS) to degrade methyl orange (MO). The mechanism of MO degradation in NC@CF/PDS system was investigated by scanning electron microscopy, Fourier transform infrared spectroscopy and other material characterization methods. The results showed that the combination of NiCo₂O₄ and chrysotile had a synergistic effect in the degradation process of MO. The removal rate of MO by NC@CF-2/PDS system with a load ratio of 2∶1 could reach 94.50% under the optimal conditions, and the degradation process conformed to the pseudo-first-order kinetic model. In addition, combined with free radical quenching experiments, electron paramagnetic resonance, X-ray photoelectron spectroscopy and electrochemical experiments, it was shown that the degradation of MO in the NC@CF-2/PDS system was completed by the synergistic effect of the free radical pathway of ·OH and SO₄^-· and the non-free radical pathway of electron transfer.

Key words: potassium persulfate, inhomogeneous oxidation, chrysotile, nickel cobalt oxide (NiCo₂O₄), methyl orange

中图分类号:

X703

苏晓洁, 严群, 李欣城, 薛文慧, 陈奕浩. NiCo₂O₄@纤蛇纹石活化过硫酸钾降解甲基橙[J]. 化工进展, 2025, 44(4): 2352-2364.

SU Xiaojie, YAN Qun, LI Xincheng, XUE Wenhui, CHEN Yihao. Activation of potassium persulfate by NiCo₂O₄@chrysotile to degrade methyl orange[J]. Chemical Industry and Engineering Progress, 2025, 44(4): 2352-2364.

图/表 23

图1 不同催化体系降解MO的效能对比（NiCo2O4+CF+PDS体系中NiCo2O4与CF的投加量与理论NC@CF-2中各成分含量相同）

表1 相关非均相催化剂/PDS体系与NC@CF-2/PDS体系对比

0.1g/L Co₃O₄/NiCo₂O₄双壳纳米笼

74μmol/L PDS催化氧化18min，T=45℃

8mg/L双酚A，97.3%

酸性pH条件下显著抑制体系催化效果，但体系具有较低的反应活化能

在pH为3~9时保持良好催化效果

[15]

0.8g/L

乙炔黑掺杂氧化锌（AB-ZnO）

2mmol/L PDS光催化60min，T=30℃

10mg/L甲基橙，95.05%

催化剂用量大，催化氧化条件复杂，但AB-ZnO循环利用性优异

在20g/L MO浓度下，催化剂投加量仅为该体系的1/8，无须添加光源，能耗较小

[16]

0.5g/L CuFe₂O₄/硅藻土

0.3g/L PMS催化氧化60min，T=25℃

50mg/L酸性橙7，96.88%

循环使用3次后降解率为63.95%，催化剂投加量大，重复利用性低，经济性较差

使用3次、4次的降解率分别为74.98%、63.18%，且反应时间较短

[17]

图2 纤蛇纹石纤维平均直径及纤蛇纹石、NiCo2O4和NC@CF-2的SEM图

图3 NC@CF-2的EDS图

表2 纤蛇纹石纤维各组分质量分数（%）

SiO₂	MgO	Fe₂O₃	CaO	NiO	Cr₂O₃	ZnO	SO₃	SrO	MnO	其他
56.200	23.400	10.600	4.690	0.874	0.806	0.773	0.525	0.459	0.425	1.248

图4 CF及NC@CF-n的XRD图

图5 NC@CF-2及CF的FTIR图

图6 PDS浓度对NC@CF-2/PDS体系去除MO的影响

图7 NC@CF-2投加量对NC@CF-2/PDS体系去除MO的影响

图8 初始pH对NC@CF-2/PDS体系去除MO的影响

图9 共存阴离子对NC@CF-2/PDS体系去除MO的影响

图10 腐殖酸浓度对NC@CF-2/PDS体系去除MO的影响

图11 反应温度对NC@CF-2/PDS体系去除MO的影响

图12 Arrhenius公式拟合结果及反应活化能的计算

图13 改变水体背景对NC@CF-2/PDS体系去除MO的影响

表3 不同水体的水质指标

水质指标	贡水	某污水厂生化池出水
pH	6.75	7.05
浊度/NTU	5.05	3.63
UV₂₅₄/cm^-1	0.031	0.064
DOC/mg·L^-1	4.548	3.485

图14 NC@CF-2稳定性探究

图15 添加淬灭剂对NC@CF-2/PDS体系去除MO的影响

图16 NC@CF-2/PDS体系在DMPO作用下的EPR 光谱

图17 NC@CF-2/PDS体系在DMPO和TEMP作用下的EPR光谱

图18 NC@CF-2-ITO电极和NiCo2O4-ITO电极依次添加PDS与MO的计时电流测试

图19 反应前后NC@CF-2中Ni、Co的XPS光谱

图20 NC@CF-2、NiCo2O4浸出液+PDS体系去除MO

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NiCo₂O₄@纤蛇纹石活化过硫酸钾降解甲基橙

Activation of potassium persulfate by NiCo₂O₄@chrysotile to degrade methyl orange

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