纳米片状Mn2O3@α-Fe3O4活化过碳酸盐降解偶氮染料

doi:10.16085/j.issn.1000-6613.2021-0556

化工进展 ›› 2022, Vol. 41 ›› Issue (2): 1043-1053.DOI: 10.16085/j.issn.1000-6613.2021-0556

纳米片状Mn₂O₃@α-Fe₃O₄活化过碳酸盐降解偶氮染料

徐铭骏¹^,²(), 郭兆春³, 李立¹^,², 朱紫琦¹^,², 张倩¹^,², 洪俊明¹^,²()

^1.华侨大学化工学院，福建厦门 361021
^2.福建省工业废水生化处理工程技术研究中心，福建厦门 361021
^3.厦门烟草工业有限责任公司，福建厦门 361021

收稿日期:2021-03-19 修回日期:2021-04-14 出版日期:2022-02-05 发布日期:2022-02-23
通讯作者: 洪俊明
作者简介:徐铭骏（1998—），男，硕士研究生，主要研究方向为水处理高级氧化。E-mail：mingjunxu1998@163.com。
基金资助:
国家自然科学基金(51978291);华侨大学研究生科研创新基金(20014087038)

Degradation of azo dyes by sodium percarbonate activated with nanosheet Mn₂O₃@α-Fe₃O₄

XU Mingjun¹^,²(), GUO Zhaochun³, LI Li¹^,², ZHU Ziqi¹^,², ZHANG Qian¹^,², HONG Junming¹^,²()

^1.College of Chemical Engineering, Huaqiao University, Xiamen 361021, Fujian, China
^2.Fujian Province Engineering Research Center of Industrial Wastewater Biochemical Treatment, Xiamen 361021, Fujian, China
^3.Xiamen Tobacco Industrial Company Limited, Xiamen 361021, Fujian, China

Received:2021-03-19 Revised:2021-04-14 Online:2022-02-05 Published:2022-02-23
Contact: HONG Junming

摘要/Abstract

摘要：

过碳酸钠是过氧化氢与碳酸钠的加成化合物，具有在存储、运输和使用过程中安全稳定的优点。本文采用共沉淀-高温煅烧法制备纳米片状Mn₂O₃@α-Fe₃O₄，活化过碳酸钠（SPC）产生自由基氧化降解偶氮染料活性黑5（RBK5）。采用透射电子显微镜（TEM）、X射线粉末衍射仪（XRD）、扫描电子显微镜（SEM）、傅里叶变换红外光谱仪（FTIR）、X射线光电子能谱（XPS）及比表面积测试（BET）表征制备的纳米片状Mn₂O₃@α-Fe₃O₄催化剂，分别探究催化剂投加量、过碳酸钠浓度、初始pH及RBK5溶液浓度对降解效率的影响。当催化剂投加量为0.3g/L、过碳酸钠浓度为1.0mmol/L、初始pH为3、反应时间为90min时，RBK5的降解效率达88%，反应过程符合拟一级动力学（R²＞0.9）。Mn₂O₃@α-Fe₃O₄/过碳酸钠体系中起氧化降解作用的活性物种为·OH、CO $_{3}^{-}$ ·、O $_{2}^{-}$ ·和¹O₂，其中·OH占据主导地位，XPS反映了铁锰元素存在价态以及双金属间的协同作用，依据猝灭实验及XPS分析降解机理。

关键词: 纳米片状, 过碳酸钠, 活性黑5, 羟基自由基, 催化剂活化, 动力学

Abstract:

Sodium percarbonate is the adduct of hydrogen peroxide and sodium carbonate, which is safe and stable during its storage, transportation and use. The method of co-precipitation followed by high-temperature calcination was used to prepare Mn₂O₃@α-Fe₃O₄ nanosheet, with which sodium percarbonate (SPC) was activated to generate free radicals to oxidize and degrade azo dye reactive black 5 (RBK5). The Mn₂O₃@α-Fe₃O₄ nanosheet was characterized by transmission electron microscope (TEM), X-ray powder diffractometer (XRD), scanning electron microscope (SEM), Fourier transform infrared spectrometer (FTIR), X-ray photoelectron spectroscopy (XPS) and Brunauer Emmett Teller (BET). The effects of catalyst dosage, SPC concentration, initial pH and RBK5 solution concentration on the degradation efficiency were explored. Under the conditions of SPC dosage 1.0mmol/L, Mn₂O₃@α-Fe₃O₄ dosage 0.3g/L, initial pH=7, the degradation rate of RBK5 in aqueous solution reached 88％ in 90min. The reaction kinetics could be well described by the pseudo first order kinetics model (R²>0.9). ·OH, CO $_{3}^{-}$ ·, O $_{2}^{-}$ · and ¹O₂ were the active species in the Mn₂O₃@α-Fe₃O₄/SPC system, and ·OH was the dominant species among them. XPS results reflected the valence states of iron and manganese elements and their synergistic effect. Quenching experiment and XPS were used to analyze the degradation mechanism.

Key words: nanosheet, sodium percarbonate (SPC), reactive black 5, hydroxyl radical, catalyst activation, dynamics

中图分类号:

徐铭骏, 郭兆春, 李立, 朱紫琦, 张倩, 洪俊明. 纳米片状Mn₂O₃@α-Fe₃O₄活化过碳酸盐降解偶氮染料[J]. 化工进展, 2022, 41(2): 1043-1053.

XU Mingjun, GUO Zhaochun, LI Li, ZHU Ziqi, ZHANG Qian, HONG Junming. Degradation of azo dyes by sodium percarbonate activated with nanosheet Mn₂O₃@α-Fe₃O₄[J]. Chemical Industry and Engineering Progress, 2022, 41(2): 1043-1053.

图/表 18

图1 纳米片状Mn2O3@α-Fe3O4的XRD图

图2 纳米片状Mn2O3@α-Fe3O4的SEM与TEM照片

图3 纳米片状Mn2O3@α-Fe3O4与外磁场分离过程的照片

图4 纳米片状Mn2O3@α-Fe3O4 N2吸附解吸等温线

图5 纳米片状Mn2O3@α-Fe3O4 FTIR图谱

图6 不同体系下RBK5的降解率

图7 催化剂投加量对RBK5降解效率和降解动力学的影响

表1 不同催化剂投加量下RBK5的降解动力学参数

催化剂投加量/g·L^-1	K/min^-1	R²
0.1	0.0078	0.926
0.2	0.0210	0.973
0.3	0.0272	0.953
0.4	0.0303	0.955

图8 过碳酸钠浓度对RBK5降解效率和降解动力学的影响

表2 不同过碳酸钠浓度下RBK5的降解动力学参数

过碳酸钠浓度/mmol·L^-1	K/min^-1	R²
1	0.0272	0.953
2	0.0254	0.953
3	0.0235	0.900
4	0.0025	0.986

图9 初始pH对RBK5降解效率和降解动力学的影响

表3 不同初始pH下RBK5的降解动力学参数

pH	K/min^-1	R²
3	0.0272	0.953
5	0.0038	0.961
7	0.0025	0.985
9	0.0006	0.936

图10 RBK5浓度对降解效率和降解动力学的影响

表4 不同RBK5浓度下的降解动力学参数

RBK5浓度/mmol·L^-1	K/min^-1	R²
5	0.0522	0.964
10	0.0272	0.953
20	0.0191	0.934
30	0.0093	0.936

图11 自由基种类的鉴定

图12 Fe、Mn反应前后XPS分析

图13 RBK5降解过程UV-vis扫描光谱变化

图14 Mn2O3@α-Fe3O4/PMS体系降解RBK5前后的3D-EEM光谱图

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纳米片状Mn₂O₃@α-Fe₃O₄活化过碳酸盐降解偶氮染料

Degradation of azo dyes by sodium percarbonate activated with nanosheet Mn₂O₃@α-Fe₃O₄

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