铁氮掺杂碳微球的制备及其活化PS降解罗丹明B

doi:10.16085/j.issn.1000-6613.2024-1060

化工进展 ›› 2025, Vol. 44 ›› Issue (9): 5406-5415.DOI: 10.16085/j.issn.1000-6613.2024-1060

• 资源与环境化工 • 上一篇

铁氮掺杂碳微球的制备及其活化PS降解罗丹明B

操江飞¹^,²(), 雷晓彤¹, 黄芷怡¹, 黄建凯³, 陈凡¹, 杨翩翩¹, 谢春生¹^,²()

^1.肇庆学院环境与化学工程学院，广东肇庆 526061
^2.广东省环境健康与资源利用重点实验室，广东肇庆 526061
^3.广东天泽环保科技有限公司，广东东莞 523073

收稿日期:2024-07-01 修回日期:2024-08-30 出版日期:2025-09-25 发布日期:2025-09-30
通讯作者: 谢春生
作者简介:操江飞（1989—），男，实验师，硕士，研究方向为新材料和高级氧化技术。E-mail：594247917@qq.com。
基金资助:
肇庆市创新指导项目(2023040301007);广东省教育厅重点领域专项创新项目(2023ZDZX4062);肇庆学院创新科研团队(TD202411);创新训练项目(X202410580132)

Preparation of iron-nitrogen doped carbon microspheres and their activation for PS degradation of rhodamine B

CAO Jiangfei¹^,²(), LEI Xiaotong¹, HUANG Zhiyi¹, HUANG Jiankai³, CHEN Fan¹, YANG Pianpian¹, XIE Chunsheng¹^,²()

^1.School of Environmental and Chemical engineering, Zhaoqing University, Zhaoqing 526061, Guangdong, China
^2.Provincial Key Laboratory of Environmental Health and Land Resource, Zhaoqing University, Zhaoqing 526061, Guangdong, China
^3.Guangdong Tianze Environmental Protection Technology Co. , Dongguan 523073, Guangdong, China

Received:2024-07-01 Revised:2024-08-30 Online:2025-09-25 Published:2025-09-30
Contact: XIE Chunsheng

摘要/Abstract

摘要：

以廉价无毒、可持续获得的可溶性淀粉为碳源，通过使用简单的水热法合成了碳微球，再以六水合氯化铁为铁源，尿素为氮源，使用共热解法制备了铁-氮掺杂碳微球（Fe-N@CMSs）。表征结果显示，Fe-N@CMSs为粒径较为均匀的球体，Fe/N改性后，碳微球孔径增大，为介孔结构；Fe-N@CMSs中存在Fe⁰、Fe₃O₄和吡啶氮、吡咯氮、石墨氮等结构。优化了Fe-N@CMSs/K₂S₂O₈（PS）体系降解罗丹明B（RhB）的条件，当Fe-N@CMSs用量为0.4g/L、PS浓度为1mmol/L、RhB浓度为50mg/L、pH为3~7时，室温下30min内RhB的降解率可达到99.7%。Fe-N@CMSs具有出色的去除RhB的能力，3个循环后RhB的降解率仍超过75%。RhB降解机理包括自由基途径（·SO₄^-）和非由基途径（¹O₂）。Fe-N@CMSs具有降解、分离和再利用能力，在处理染料废水方面具有广阔的前景。

关键词: 铁-氮掺杂碳微球, 过硫酸钾, 降解, 罗丹明B, 降解机理

Abstract:

Carbon microspheres were synthesized by using a simple hydrothermal method with cheap, non-toxic and sustainably available soluble starch as the carbon source, and then iron-nitrogen doped carbon microspheres (Fe-N@CMSs) were prepared by using a co-pyrolysis method with ferric chloride hexahydrate as the iron source and urea as the nitrogen source. Characterization results showed that Fe-N@CMSs were spheres with a relatively uniform particle size. After Fe/N modification, the pore size of carbon microspheres increased to a mesoporous structure. Fe⁰, Fe₃O₄ and pyridine nitrogen, pyrrole nitrogen and graphite nitrogen structures were present in Fe-N@CMSs. The conditions for the degradation of rhodamine B (RhB) in the Fe-N@CMSs/K₂S₂O₈(PS) system were optimized, and the degradation rate of RhB could reach 99.7% within 30min at room temperature at Fe-N@CMSs dosage of 0.4g/L, PS concentration of 1 mmol/L, RhB concentration of 50mg/L and pH of 3—7. Fe-N@CMSs had an excellent ability to remove RhB and the degradation rate of RhB was still more than 75% after 3 cycles. The RhB degradation mechanism included both the radical pathway (·SO₄^-) and the non-radical pathway (¹O₂). Fe-N@CMSs was promising for the treatment of dye wastewater due to their degradation, separation and reuse capabilities.

Key words: iron-nitrogen doped carbon microspheres, potassium persulfate (K₂S₂O₈), degradation, rhodamine B, degradation mechanism

中图分类号:

TQ630

操江飞, 雷晓彤, 黄芷怡, 黄建凯, 陈凡, 杨翩翩, 谢春生. 铁氮掺杂碳微球的制备及其活化PS降解罗丹明B[J]. 化工进展, 2025, 44(9): 5406-5415.

CAO Jiangfei, LEI Xiaotong, HUANG Zhiyi, HUANG Jiankai, CHEN Fan, YANG Pianpian, XIE Chunsheng. Preparation of iron-nitrogen doped carbon microspheres and their activation for PS degradation of rhodamine B[J]. Chemical Industry and Engineering Progress, 2025, 44(9): 5406-5415.

图/表 16

图1 RhB标准曲线

图2 不同材料的晶体结构和官能团分析

表1 C、H、N元素的含量 (mg/g)

材料	C	H	N	Fe
CMSs	877.2	28.7	1.4	0
N@CMSs	867.3	27.1	44.4	0
Fe@CMSs	739.1	22.1	1.7	58.53
Fe-N@CMSs	735.4	22.1	41.3	57.17

图3 不同材料的SEM形貌分析

图4 不同材料的吸附等温线和Density-Functional-Theory（DFT）孔径分布

表2 Fe-N@CMSs、N@CMSs、Fe@CMSs、CMSs的比表面积和孔结构参数

样品	比表面积（BET）/m²‧g^-1	总孔体积/cm³‧g^-1	微孔体积/cm³‧g^-1	平均孔径/nm
CMSs	536.257	0.4186	0.108	0.666
N@CMSs	495.045	0.3007	0.144	0.640
Fe@CMSs	483.223	0.3273	0.129	0.640
Fe-N@CMSs	234.978	0.4718	0	4.220

图5 CMSs、N@CMSs、Fe@CMSs、Fe-N@CMSs的XPS谱图

图6 不同材料的XPS拟合图

图7 不同体系对RhB降解影响分析

图8 Fe-N@CMSs的用量对降解RhB的影响

图9 PS浓度对降解RhB的影响

图10 pH对降解RhB的影响

图11 不同阴离子对降解RhB的影响

图12 Fe-N@CMSs/PS体系稳定性分析

图13 不同清除剂对RhB降解的影响[RhB 50mg/L（pH=6.5）；体积100mL；Fe-N@CMSs 40mg；K2S2O8 1mmol/L；TBA、FFA、MeOH均为3mL；BQ 40mg]

图14 RhB降解机理

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铁氮掺杂碳微球的制备及其活化PS降解罗丹明B

Preparation of iron-nitrogen doped carbon microspheres and their activation for PS degradation of rhodamine B

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