Fe-MOF-74前体制备铁-碳/氮复合材料及其活化过硫酸盐性能

doi:10.11949/0438-1157.20231263

摘要/Abstract

摘要：

利用Fe-MOF-74和g-C₃N₄前体制备了复合材料铁-碳/氮(记为Fe-MOF-C/N)，并研究了其活化过硫酸氢钾（PMS)的性能。XRD、SEM和XPS分析表明，Fe-MOF-C/N呈多孔状结构，主要由物相Fe₃N、C_0.08Fe_1.92和石墨组成。利用Fe-MOF-C/N活化PMS降解双酚A (BPA)结果表明，与前期的Fe-C/N-0.5∶1(由FeC₂O₄和g-C₃N₄制备)相比，Fe-MOF-C/N具有更优异的催化性能，相同条件下Fe-MOF-C/N/PMS对BPA的降解率达95.21% (6 min)，比Fe-C/N-0.5∶1/PMS高30.4%。优化相应的实验条件后，6 min内BPA的化学需氧量(COD)去除率达59.72%。自由基猝灭实验表明，Fe-MOF-C/N/PMS的活性物种主要是¹O₂。稳定性实验表明Fe-MOF-C/N稳定性较好，使用5次后，BPA的降解率仅下降9.0%，应用前景良好。

关键词: 高级氧化, 活化, 过硫酸氢钾, 降解, 复合材料, 金属有机框架

Abstract:

The composite Fe-carbon/nitrogen (Fe-MOF-C/N) was prepared from the precusors of Fe-MOF-74 and g-C₃N₄ and its performance in activating peroxymonosulfate (PMS) was studied. The results of XRD, SEM and XPS analysis showed that Fe-MOF-C/N had a porous structure and was mainly composed of Fe₃N, C_0.08Fe_1.92 and graphite. The results of using Fe-MOF-C/N to activate PMS to degrade bisphenol A (BPA) show that compared with the previous Fe-C/N-0.5∶1 (prepared from FeC₂O₄ and g- C₃N₄), Fe-MOF-C/ N has better catalytic performance. The degradation rate of BPA by Fe-MOF-C/N/PMS under the same conditions reaches 95.21% (6 min), which is 30.4% higher than Fe-C/N-0.5∶1/PMS. The chemical oxygen demand (COD) removal rate of BPA reached 59.72% within 6 min under the optimized experimental conditions. Free radical quenching experiments showed that ¹O₂ was the main active species in Fe-MOF-C/N/PMS. The recycle tests indicated Fe-MOF-C/N had a good stability, the degradation rate of BPA only decreased by 9.0% in 5 runs, implying it has a good application prospect.

Key words: advanced oxidation, activation, peroxymonosulfate, degradation, composites, metal-organic framework

中图分类号:

X 703

张林, 张子怡, 李勇, 童少平. Fe-MOF-74前体制备铁-碳/氮复合材料及其活化过硫酸盐性能[J]. 化工学报, 2024, 75(5): 1882-1889.

Lin ZHANG, Ziyi ZHANG, Yong LI, Shaoping TONG. Preparation of Fe-carbon/nitrogen composites from Fe-MOF-74 precusor and its performance in activating peroxymonosulfate[J]. CIESC Journal, 2024, 75(5): 1882-1889.

图/表 12

图1 Fe-MOF-C/N-1∶0.5的XRD谱图

Fig.1 XRD patterns of Fe-MOF-C/N-1∶0.5

图2 Fe-MOF-C/N-1∶0.5煅烧前后的SEM图像

Fig. 2 SEM images of Fe-MOF-C/N-1∶0.5 before and after calcination

图3 煅烧后Fe-MOF-C/N-1∶0.5的mapping图和各元素分布

Fig.3 Mapping of Fe-MOF-C/N-1∶0.5 after calcination and distribution of each element

图4 Fe-MOF-C/N-1∶0.5的XPS全谱图及元素高分辨率谱图

Fig.4 XPS full spectra and high-resolution spectra of elements of Fe-MOF-C/N-1∶0.5

图5 前体不同质量比对BPA降解效率的影响

Fig.5 Effect of mass ratio of precursors on degradation efficiency of BPA

图6 Fe-MOF-C/N-1∶0.5与Fe-C/N-0.5∶1活化PMS降解BPA的效率

Fig.6 Efficiencies of Fe-MOF-C/N-1∶0.5/PMS and Fe-C/N-0.5∶1/PMS in degradation of BPA

图7 不同初始pH对BPA降解效率的影响

Fig.7 Effect of different initial pH on degradation efficiency of BPA

图8 不同Fe-MOF-C/N-1∶0.5投加量对BPA降解效率的影响

Fig.8 Effect of different dosage of Fe-MOF-C/N-1∶0.5 on degradation efficiency of BPA

图9 不同PMS投加量对BPA降解效率的影响

Fig.9 Effect of different dosage of PMS on degradation efficiency of BPA

图10 Fe-MOF-C/N-1∶0.5的稳定性实验

Fig.10 Stability test of Fe-MOF-C/N-1∶0.5

图11 Fe-MOF-C/N-1∶0.5使用前后的XRD谱图

Fig.11 XRD patterns of fresh and used Fe-MOF-C/N-1∶0.5

图12 猝灭剂（乙醇、糠醇、叔丁醇）对BPA降解率的影响

Fig.12 Effect of ethanol, TBA, and FA on the degradation of BPA

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