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. Bisphenol A (BPA) was selected to degrade, and the results showed that Fe-MOF-C/N had better catalytic performance than Fe-C/N-0.5:1 (prepared by FeC₂O₄ and g-C₃N₄). Under the same conditions, the degradation rate of BPA by Fe-MOF-C/N/PMS reached 95.21% in 6 min, 30.4% higher than that by 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^th run, 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, DOI: 10.11949/0438-1157.20231263.

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, DOI: 10.11949/0438-1157.20231263.

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 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 values 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

参考文献 36

1	Peng Y T, Tang H M, Yao B, et al. Activation of peroxymonosulfate (PMS) by spinel ferrite and their composites in degradation of organic pollutants: a Review[J]. Chemical Engineering Journal, 2021, 414: 128800.
2	Do S H, Jo J H, Jo Y H, et al. Application of a peroxymonosulfate/cobalt (PMS/Co(II)) system to treat diesel-contaminated soil[J]. Chemosphere, 2009, 77(8): 1127-1131.
3	Zhou M Z, Li Q H, Wang X, et al. Electrokinetic combined peroxymonosulfate (PMS) remediation of PAH contaminated soil under different enhance methods[J]. Chemosphere, 2022, 286: 131595.
4	刘祺, 陈蕾. 基于硫酸根自由基的高级氧化技术在污水处理中的应用[J]. 应用化工, 2022, 51(5): 1383-1388.
	Liu Q, Chen L. Application of advanced oxidation technology based on sulfate radical in wastewater treatment[J]. Applied Chemical Industry, 2022, 51(5): 1383-1388.
5	Gao Y, Wu T W, Yang C D, et al. Activity trends and mechanisms in peroxymonosulfate-assisted catalytic production of singlet oxygen over atomic metal-N-C catalysts[J]. Angewandte Chemie (International Ed. In English), 2021, 60(41): 22513-22521.
6	Ma C Y, Guo Y J, Zhang D F, et al. Metal-nitrogen-carbon catalysts for peroxymonosulfate activation to degrade aquatic organic contaminants: rational design, size-effect description, applications and mechanisms[J]. Chemical Engineering Journal, 2023, 454: 140216.
7	Zhou X Q, Zhao Q D, Wang J, et al. Nonradical oxidation processes in PMS-based heterogeneous catalytic system: generation, identification, oxidation characteristics, challenges response and application prospects[J]. Chemical Engineering Journal, 2021, 410: 128312.
8	Tan L, Xia Y, Wang S Y, et al. Hierarchical porous-enhanced peroxymonosulfate activation via 3D ordered macro-microporous Fe-NC: Role of high-valent iron-oxo species and electron-transfer mechanism[J]. Journal of Cleaner Production, 2023, 383: 135500.
9	Liu J W, Peng C S, Shi X L. Preparation, characterization, and applications of Fe-based catalysts in advanced oxidation processes for organics removal: a review[J]. Environmental Pollution, 2022, 293: 118565.
10	Ren M, Hou J Q, Ma J, et al. Superior electron utilization of the intermetallic L10-FePt-dispersed g-C₃N₄ for high-efficiency activating peroxymonosulfate[J]. Separation and Purification Technology, 2022, 302: 122105.
11	Wang S Z, Wang J L. Synergistic effect of PMS activation by Fe⁰@Fe₃O₄ anchored on N, S, O co-doped carbon composite for degradation of sulfamethoxazole[J]. Chemical Engineering Journal, 2022, 427: 131960.
12	Wang J J, Wang C, Tong S P. A novel composite Fe-N/O catalyst for the effective enhancement of oxidative capacity of persulfate at ambient temperature[J]. Catalysis Communications, 2018, 103: 105-109.
13	Wang C, Yang Q Q, Li Z H, et al. A novel carbon-coated Fe-C/N composite as a highly active heterogeneous catalyst for the degradation of Acid Red 73 by persulfate[J]. Separation and Purification Technology, 2019, 213: 447-455.
14	赵晨. Fe-MOFs衍生的碳包覆铁纳米粒子催化剂的制备及傅克酰基化反应性能[D]. 长春: 吉林大学, 2022.
	Zhao C. Carbon-wrapped iron nanoparticle catalysts derived from Fe-MOFs for friedel-crafts acylation reaction[D]. Changchun: Jilin University, 2022.
15	Wang Z, Laddha G, Kanitkar S, et al. Metal organic framework-mediated synthesis of potassium-promoted cobalt-based catalysts for higher oxygenates synthesis[J]. Catalysis Today, 2017, 298: 209-215.
16	Li Y J, Zhang Z Y, Zhang L, et al. Preparation of metal organic frame derived MgO-porous carbon composite and its high catalytic activity in ozonation with excellent stability[J]. Journal of the Taiwan Institute of Chemical Engineers, 2024, 156: 105339.
17	Miao F, Cui P, Yu S J, et al. In situ fabrication of a 3D self-supported porous Ni-Mo-Cu catalyst for an efficient hydrogen evolution reaction[J]. Dalton Transactions, 2023, 52(25): 8654-8660.
18	Ju J, Kim M, Jang S, et al. 3D in situ hollow carbon fiber/carbon nanosheet/Fe3C@Fe₃O₄ by solventless one-step synthesis and its superior supercapacitor performance[J]. Electrochimica Acta, 2017, 252: 215-225.
19	Xu H M, Ma W S, Zhang T T, et al. Efficient inhibition of Salmonella on chestnuts via Fe3C/N-C bacteriostatic suspension prepared by electrochemical method[J]. Inorganic Chemistry Communications, 2020, 118: 108034.
20	Wang T L, Xu L C, Sun C X, et al. Synthesis of hierarchically structured Fe₃C/CNTs composites in a FeNC matrix for use as efficient ORR electrocatalysts[J]. RSC Advances, 2023, 13(6): 3835-3842.
21	Wang W, Liu L, Leng W C, et al. Coordination polymer-derived Fe₃N nanoparticles for efficient electrocatalytic oxygen evolution[J]. Inorganic Chemistry, 2021, 60(16): 12136-12150.
22	Zhao J F, Weng Y C, Xu S L, et al. Protein-mediated synthesis of Fe₃N nanoparticles embedded in hierarchical porous carbon for enhanced reversible lithium storage[J]. Journal of Power Sources, 2020, 464: 228246.
23	Ji S Y, Yang Y L, Zhou Z W, et al. Photocatalysis-Fenton of Fe-doped g-C₃N₄ catalyst and its excellent degradation performance towards RhB[J]. Journal of Water Process Engineering, 2021, 40: 101804.
24	Tang F, Lei H T, Wang S J, et al. A novel Fe-N-C catalyst for efficient oxygen reduction reaction based on polydopamine nanotubes[J]. Nanoscale, 2017, 9(44): 17364-17370.
25	Li Y B, Yan Y R, Ming H, et al. One-step synthesis Fe3N surface-modified Fe₃O₄ nanoparticles with excellent lithium storage ability[J]. Applied Surface Science, 2014, 305: 683-688.
26	Li C, Zhang R, Ba X, et al. Fe Nanoparticles Encapsulated in N-Doped Porous Carbon for Efficient Oxygen Reduction in Alkaline Media[J]. Journal of Electrochemistry, 2023, 29(5): 2210241.
27	Eissa A A, Peera S G, Kim N H, et al. G-C₃N₄ templated synthesis of the Fe₃C@NSC electrocatalyst enriched with Fe-Nx active sites for efficient oxygen reduction reaction[J]. Journal of Materials Chemistry A, 2019, 7(28): 16920-16936.
28	Lai Y Q, Chen W, Zhang Z A, et al. Fe/Fe3C decorated 3-D porous nitrogen-doped graphene as a cathode material for rechargeable Li-O₂ batteries[J]. Electrochimica Acta, 2016, 191: 733-742.
29	Ding M Y, Jiang W J, Yu T Q, et al. Electronically Modulated FeNi Composite by CeO₂ Porous Nanosheets for Water Splitting at Large Current Density[J]. Journal of Electrochemistry, 2023, 29(5): 2208121.
30	Wang X H, Nan Z D. Highly efficient Fenton-like catalyst Fe-g-C₃N₄ porous nanosheets formation and catalytic mechanism[J]. Separation and Purification Technology, 2020, 233: 116023.
31	Liu C, Liu L Y, Tian X, et al. Coupling metal-organic frameworks and g-C₃N₄ to derive Fe@N-doped graphene-like carbon for peroxymonosulfate activation: Upgrading framework stability and performance[J]. Applied Catalysis B: Environmental, 2019, 255: 117763.
32	Ma J Q, Yang Q F, Wen Y Z, et al. Fe-g-C₃N₄/graphitized mesoporous carbon composite as an effective Fenton-like catalyst in a wide pH range[J]. Applied Catalysis B: Environmental, 2017, 201: 232-240.
33	黄仕元, 邓简, 袁瀚钦, 等. 钴强化铁磁体活化过一硫酸盐的实验研究[J]. 化工学报, 2022, 73(7): 3045-3056.
	Huang S Y, Deng J, Yuan H Q, et al. Experimental study on activation of peroxymonosulfate by cobalt-enhanced ferromagnet[J]. CIESC Journal, 2022, 73(7): 3045-3056.
34	岳敏, 王璟, 韩玉泽, 等. 盐助溶液燃烧法制备MnFe₂O₄催化过一硫酸盐降解双酚A[J]. 化工学报, 2020, 71(12): 5589-5598.
	Yue M, Wang J, Han Y Z, et al. Degradation of bisphenol A by peroxymonosulfate activated by MnFe₂O₄ prepared by salt-assisted solution combustion synthesis[J]. CIESC Journal, 2020, 71(12): 5589-5598.
35	Qi F, Chu W, Xu B B. Catalytic degradation of caffeine in aqueous solutions by cobalt-MCM41 activation of peroxymonosulfate[J]. Applied Catalysis B-environmental, 2013, 134: 324-332.
36	张贤胜, 孙婧雯, 刘智峰. CoFe₂O₄/MnO₂活化过一硫酸盐降解盐酸四环素的研究[J]. 能源环境保护, 2023, 37(5): 57-70.
	Zhang X S, Sun J W, Liu Z F. Degradation of tetracycline hydrochloride by CoFe₂O₄/MnO₂activated permonosulfate[J]. Energy Environmental Protection, 2023, 37(5): 57-70.

[1]	胡超, 董玉明, 张伟, 张红玲, 周鹏, 徐红彬. 浓硫酸活化五氧化二钒制备高浓度全钒液流电池正极电解液[J]. 化工学报, 2023, 74(S1): 338-345.
[2]	杨百玉, 寇悦, 姜峻韬, 詹亚力, 王庆宏, 陈春茂. 炼化碱渣湿式氧化预处理过程DOM的化学转化特征[J]. 化工学报, 2023, 74(9): 3912-3920.
[3]	胡兴枝, 张皓焱, 庄境坤, 范雨晴, 张开银, 向军. 嵌有超小CeO₂纳米粒子的碳纳米纤维的制备及其吸波性能[J]. 化工学报, 2023, 74(8): 3584-3596.
[4]	康超, 乔金鹏, 杨胜超, 彭超, 付元鹏, 刘斌, 刘建荣, Aleksandrova Tatiana, 段晨龙. 煤矸石中有价关键金属活化提取研究进展[J]. 化工学报, 2023, 74(7): 2783-2799.
[5]	张澳, 罗英武. 低模量、高弹性、高剥离强度丙烯酸酯压敏胶[J]. 化工学报, 2023, 74(7): 3079-3092.
[6]	王杰, 丘晓琳, 赵烨, 刘鑫洋, 韩忠强, 许雍, 蒋文瀚. 聚电解质静电沉积改性PHBV抗氧化膜的制备与性能研究[J]. 化工学报, 2023, 74(7): 3068-3078.
[7]	蔡斌, 张效林, 罗倩, 党江涛, 左栗源, 刘欣梅. 导电薄膜材料的研究进展[J]. 化工学报, 2023, 74(6): 2308-2321.
[8]	卫雪岩, 钱勇. 微米级铁粉燃料中低温氧化反应特性及其动力学研究[J]. 化工学报, 2023, 74(6): 2624-2638.
[9]	崔张宁, 胡紫璇, 吴雷, 周军, 叶干, 刘田田, 张秋利, 宋永辉. 可降解纤维素基材料的耐水性能研究进展[J]. 化工学报, 2023, 74(6): 2296-2307.
[10]	李振, 张博, 王丽伟. PEG-EG固-固相变材料的制备和性能研究[J]. 化工学报, 2023, 74(6): 2680-2688.
[11]	李瑞康, 何盈盈, 卢维鹏, 王园园, 丁皓东, 骆勇名. 电化学强化钴基阴极活化过一硫酸盐的研究[J]. 化工学报, 2023, 74(5): 2207-2216.
[12]	代佳琳, 毕唯东, 雍玉梅, 陈文强, 莫晗旸, 孙兵, 杨超. 热物性对混合型CPCMs固液相变特性影响模拟研究[J]. 化工学报, 2023, 74(5): 1914-1927.
[13]	陈韶云, 徐东, 陈龙, 张禹, 张远方, 尤庆亮, 胡成龙, 陈建. 单层聚苯胺微球阵列结构的制备及其吸附性能[J]. 化工学报, 2023, 74(5): 2228-2238.
[14]	吴学红, 栾林林, 陈亚南, 赵敏, 吕财, 刘勇. 可降解柔性相变薄膜的制备及其热性能[J]. 化工学报, 2023, 74(4): 1818-1826.
[15]	杨庆云, 李青松, 陈泽铭, 邓靖, 李玉瑛, 杨帆, 陈国元, 李国新. UV/PMS、UV/PDS、UV/SPC工艺降解尼泊金甲酯[J]. 化工学报, 2023, 74(3): 1322-1331.