生物质基铁/氮共掺杂多孔炭的制备及其活化过一硫酸盐催化降解罗丹明B

doi:10.16085/j.issn.1000-6613.2022-1516

摘要/Abstract

摘要：

丝瓜络具有天然的三维多孔结构，是制备生物质基杂原子掺杂多孔炭的理想前体。本文以丝瓜络为碳源、尿素为氮源、九水硫酸铁为铁源，经简单的浸渍、高温炭化，成功制备了铁/氮共掺杂多孔炭（Fe@NC），通过SEM、XRD、BET和Raman等表征结果表明：制备的铁/氮共掺杂多孔炭保持了生物质前体的多孔结构，Fe/N共掺杂有利于提高碳材料的比表面积和缺陷程度。进一步研究发现所制备的Fe@NC作为催化剂可以活化过一硫酸盐（PMS），实现罗丹明B（RhB）的有效降解，详细考察了炭化温度、PMS浓度、多孔炭投加量、溶液初始pH、阴离子和腐殖酸对RhB去除率的影响。结果表明：在优化的条件下，Fe@NC-800/PMS体系在20min内对RhB去除率达到99.9%，其反应速率常数分别为Fe@C-800/PMS、NC-800/PMS和C-800/PMS反应体系的2.5倍、12.7倍和22.7倍。抑制实验和EPR分析结果表明，Fe@NC-800/PMS体系中的主要活性物种为SO₄^·-、·OH和¹O₂，RhB的降解是通过自由基和非自由基途径协同作用实现的。此外，循环实验表明Fe@NC-800具有良好的重复利用性，且能够有效抑制金属浸出。

关键词: 生物质, 铁/氮共掺杂, 过一硫酸盐, 催化剂, 降解, 染料

Abstract:

Loofah sponge has a natural three-dimensional porous structure, making it an ideal precursor for the preparation of biomass-derived heteroatom doped porous carbon. In this study, the loofah sponge, urea, and ferric sulfate nonahydrate were used as the carbon source, nitrogen source, and iron source, respectively. After simple impregnation and high-temperature carbonization, iron/nitrogen co-doped porous carbon (Fe@NC) was successfully prepared. The characterization results of SEM, XRD, and Raman showed that the prepared Fe@NC maintained the porous structure of biomass precursor, and the Fe/N co-doping was beneficial for improving the specific surface area and defect degree of carbon materials. Then, it was found that Fe@NC could serve as favorable catalysts for PMS activation, resulting in the efficient degradation of RhB. The effects of carbonization temperature, PMS concentration, the dosage of porous carbon, initial pH value of the solution, anions, and humic acid on the RhB removal efficiency were discussed in detail. The results showed that under the optimized conditions, the removal efficiency of RhB in the Fe@NC-800/PMS system would reach 99.9% within 20min and the rate constant was 2.5 times, 12.7 times, and 22.7 times that of Fe@C-800 /PMS, NC-800/PMS, and C-800/PMS systems respectively. Results of the inhibition experiments and EPR analysis revealed that SO₄^·-, ·OH, and ¹O₂ were the main active species in the Fe@NC-800/PMS system. The degradation of RhB could be achieved through both radical and non-radical processes. In addition, the cycling experiments demonstrated the good reusability of Fe@NC-800, and the metal leaching could be effectively inhibited.

Key words: biomass, iron/nitrogen co-doping, peroxymonosulfate, catalyst, degradation, dyestuff

中图分类号:

吴锋振, 刘志炜, 谢文杰, 游雅婷, 赖柔琼, 陈燕丹, 林冠烽, 卢贝丽. 生物质基铁/氮共掺杂多孔炭的制备及其活化过一硫酸盐催化降解罗丹明B[J]. 化工进展, 2023, 42(6): 3292-3301.

WU Fengzhen, LIU Zhiwei, XIE Wenjie, YOU Yating, LAI Rouqiong, CHEN Yandan, LIN Guanfeng, LU Beili. Preparation of biomass derived Fe/N co-doped porous carbon and its application for catalytic degradation of Rhodamine B via peroxymonosulfate activation[J]. Chemical Industry and Engineering Progress, 2023, 42(6): 3292-3301.

图/表 10

图1 碳材料的SEM图和元素分布图

图2 不同碳材料的XRD谱图

图3 不同碳材料的拉曼光谱图和氮气吸附-脱附等温线

图4 Fe@NC-800的XPS谱图

图5 不同反应体系对RhB的吸附降解影响

图6 Fe@NC-800投加量和PMS浓度对RhB的催化降解影响

图7 溶液初始pH和水体成分对RhB的催化降解影响

图8 不同抑制剂对RhB催化降解影响和EPR谱图

图9 Fe@NC-800的磁滞回线及其循环利用性能

表1 Fe@NC-800与其他催化剂的性能比较

催化剂	RhB浓度/mg·L^-1	催化剂浓度/g·L^-1	PMS浓度/mmol·L^-1	RhB去除率/%	多次重复使用后RhB去除率	参考文献
Ni/Co/Mn-NCM-650	20	0.5	1	98	22%（4次）	[32]
30%-CNTs-Fe-Mn	15	0.1	1.3	97	79%（3次）	[33]
C@Co₃O₄-Q5	30	0.2	1	92	80%（5次）	[34]
CuS _x /C	10	0.2	0.5	98	82%（3次）	[35]
Fe@NC-800	20	0.1	0.65	99.9	81%（5次）	本文

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