钴、氮共掺杂生物炭活化过一硫酸盐降解双酚 A

鄢经缘; 杨阳; 王俊辉; 叶凡; 潘翠; 覃岳隆; 刘坤; 张寒冰

钴、氮共掺杂生物炭活化过一硫酸盐降解双酚 A

鄢经缘¹,
杨阳¹,
王俊辉¹,
叶凡³,
潘翠³,
覃岳隆³,
刘坤¹,
张寒冰^{1, 2, 4, ,}

1.
广西大学资源环境与材料学院, 南宁 530004
2.
广西大学化学化工学院广西石化资源加工及过程强化技术重点实验室, 南宁 530004
3.
广西壮族自治区环境保护科学研究院, 南宁 530022
4.
广西高校环境保护重点实验室, 南宁, 530004

基金项目: 国家自然科学基金 (No. 52263029); 广西重点研发计划项目 (No. 2023AB24041) 广西自然科学基金 (No. 2020GXNSFAA297036); 广西石化资源加工及过程强化技术重点实验室主任基金 (No. 2022Z005); 广西大学大学生创新创业训练项目

详细信息

通讯作者:
张寒冰，博士，副教授，硕士生导师，研究方向为: 环保材料制备及水污染修复　E-mail: 24346260@qq.com

中图分类号: X703; TB333
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- 被引次数: 0
出版历程
- 收稿日期: 2024-03-14
- 修回日期: 2024-04-16
- 录用日期: 2024-04-20
- 网络出版日期: 2024-06-14

Cobalt and nitrogen co-doped biochar enhanced peroxymonosulfate activation for Bisphenol A degradation

1.
School of Resources, Environment and Materials, Guangxi University, Nanning 530004, China
2.
Petrochemical Resources Processing and Process Reinforcement Technology Key Laboratory of Guangxi, School of Chemistry and Chemical Engineering, Guangxi University, Nanning 530004, China
3.
Scientific Research Academy of Guangxi Environmental Protection, Nanning 530022, China
4.
Key Laboratory of Environmental Protection in Guangxi Colleges and Universities, Nanning 530004, China

Funds: National Natural Science Foundation of China (No. 52263029); Guangxi Key Technologies R&D Program (No. 2023AB24041); National Natural Science Foundation of Guangxi (No. 2020GXNSFAA297036); Petrochemical Resources Processing and Process Reinforcement Technology Key Laboratory Project of Guangxi (No. 2022Z005); Guangxi University Student Innovation and Entrepreneurship Training Program

摘要

摘要: 内分泌干扰物双酚A(Bisphenol A, BPA)在环境中对生态安全构成了潜在的威胁，因此需要寻找一种合适的处理方法。基于Co、N共掺杂材料具有反应活性高、化学稳定性高、去除污染物效率高等优势，本研究以杉木屑生物炭为原料进行Co、N共掺杂制备了具有高效PMS活化能力的钴、氮共掺杂生物炭(CoNC)复合材料，用以活化过一硫酸盐(Peroxymonosulphate, PMS)去除水体中BPA。相比于C、NC以及CoC，CoNC的表面粗糙程度增加，缺陷点位增多，电荷转移阻力减小，且结构比表面积与孔隙结构得到改善，比表面积达到70.31 m² /g；对不同Co、N掺杂比、溶液初始pH、共存阴离子对BPA去除效率的影响进行了研究。结果表明，相比于原始材料，PMS/CoNC体系表现出优异的BPA去除能力。在溶液初始pH为7，CoNC投加量为0.2 g/L，PMS浓度为0.3 mmol/L，模拟水体中BPA浓度为20 mg/L的条件下，BPA去除率在30分钟达到95%。捕获实验、电化学表征表明，在PMS/CoNC体系中，BPA主要通过直接电荷转移的非自由基途径得到降解。本研究为生物炭催化性能的优化以及BPA在高级氧化技术中的降解研究提供借鉴。
- 生物炭 /
- 钴氮共掺杂 /
- 双酚 A /
- 过一硫酸盐 /
- 非自由基途径
Abstract: The endocrine disruptor Bisphenol A(BPA) poses a potential threat to environmental ecological safety, for which a suitable treatment method needs to be found. Based on the advantages of high reactivity, chemical stability and pollutant removal efficiency of CoN co-doped material, CoN co-doped biochar(CoNC) composites with high PMS activation efficiency were prepared by Co and N co-doping with fir sawdust biochar as raw material. And the activation of peroxymonosulphate(PMS) by CoNC for the removal of BPA from environmental water has been investigated. Compared to C, NC, and CoC materials, CoNC showed improved surface roughness, more defect sites, reduced charge transfer resistance, and improved structural surface area and pore structure, with a specific surface area of 70.31 m² /g. The effects of different Co and N doping ratios, initial solution pH, and co-existing anions on the removal efficiency of BPA were also investigated. The results showed that the PMS/CoNC system exhibited excellent BPA removal compared to the original material. Under the conditions of initial solution pH 7, 0.2 g/L CoNC material, 0.3 mmol/L PMS concentration, and BPA concentration of 20 mg/L in the simulated water, the BPA removal reached 95% in 30 min. The capture experiments and electrochemical characterization showed that PMS/CoNC degraded BPA mainly through the non-radical pathway of direct charge transfer. This study provides a reference for optimising the catalytic performance of biochar and its BPA degradation in advanced oxidation technology.
- Biochar /
- Co/N co-doping /
- Bisphenol A /
- Peroxymonosulfate /
- Non-radical pathway

HTML全文

图 1 C(a)、NC(b)、CoC(c)和CoNC(d,e)的SEM图谱，以及CoNC的EDS能谱和元素分布图(f)

Figure 1. SEM images of C(a)、NC(b)、CoC(c) and CoNC(d,e), EDS and element distribution diagram of CoNC(f)

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图 2 C、NC和CoNC的吸附脱附曲线(a)孔径分布图(b)

Figure 2. N₂ adsorption-desorption isotherms(a) Pore size distribution(b) of C, NC and CoNC

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图 3 C、NC、CoNC和使用后的CoNC的XRD谱图

Figure 3. XRD patterns of C、NC、CoNC and used CoNC

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图 4 C、NC、CoC、CoNC和使用后CoNC的拉曼光谱

Figure 4. Raman spectra of C、NC、CoC、CoNC and used CoNC

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图 5 C、NC和CoNC的XPS全谱(a)材料的XPS高分辨窄谱(b)C1 s、(c)N1和(d)Co2 p窄谱

Figure 5. XPS survey scan spectra of C、NC and CoNC(a); XPS high-resolution spectra of C1 s(b), N1 s(c) and (d)Co2 p(d)

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图 6 不同材料吸附(a)和活化PMS(b)降解BPA的性能

Figure 6. Adsorption(a) and degradation(b) via PMS activation by different materials for BPA removal

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图 7 不同体系中Co离子浸出量

Figure 7. Leaching of cobolt ions in different systems

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图 8 不同Co掺杂量(a)与不同N配比(b)的CoNC活化PMS对BPA降解的影响

Figure 8. Effect of different Co doping (a) and different N doping ratios (b) on BPA degradation by PMS/CoNC system

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图 9 不同溶液初始pH对CoNC降解BPA的影响

Figure 9. Effect of initial solution pH on degradation of BPA

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图 10 不同类型阴离子对CoNC降解BPA的影响

Figure 10. Effect of different types of anions on degradation of BPA

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图 11 活性物种捕获实验(a)、PMS/CoNC(b)以及加入BPA后的EPR波谱(c)

Figure 11. Active species capturing experiments(a), EPR spectra(b) in PMS/CoNC system and EPR spectrum after adding BPA(c)

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图 12 不同材料的EIS曲线图(a)、不同体系的LSV曲线图(b)i-t曲线(c)以及OCV曲线(d)

Figure 12. The EIS plots of different materials(a); LSV curves (b); i-t curves (c) and OCV curves of different systems(d)

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表 1 使用试剂名称以及试剂来源

Table 1. Name of used reagent and source of reagent

Sample	Purity	Producer
Bisphenol A	AR	Shanghai, China
Co(NO₃)₂•5H₂O	AR	Guangdong, China
Zn(NO₃)₂•6H₂O	AR	Guangdong, China
Dicyandiamide	AR	Guangdong, China
Peroxymonosulphate	AR	Guangdong, China
Methanol	AR	Shanghai, China Shanghai, China
Tert-Butanol	AR	Shanghai, China Shanghai, China
1,4-Benzoquinone	AR	Shanghai, China
Furfuryl alcohol	AR	Shanghai, China

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表 2 C、NC和CoNC的BET分析结果

Table 2. BET analysis of C、NC and CoNC

Sample	Surface area/ (m²·g⁻¹)	Pore volume/ (cm³·g⁻¹)	Average pore diameter /nm
C	29.25	0.02	6.61
NC	42.67	0.19	13.11
CoNC	73.01	0.23	9.49

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