半焦活性炭负载CuCo-MOF-74的制备及其活化过硫酸盐降解水中双酚A的研究

芦天姣; 王家宏

PDF(3188 KB)

中国环境科学 ›› 2025, Vol. 45 ›› Issue (11) : 6079-6090.

水污染与控制

半焦活性炭负载CuCo-MOF-74的制备及其活化过硫酸盐降解水中双酚A的研究

芦天姣, 王家宏

作者信息 +

The preparation of semi-coke activated carbon supported CuCo-MOF-74 and degradation of BPA in water via peroxymonosulfate activation

LU Tian-jiao, WANG Jia-hong

Author information +

文章历史 +

摘要

采用一锅水热合成法,成功制备了半焦活性炭(SC)负载CuCo-MOF-74的双金属催化剂(CuCo-MOF-74_x/SC),研究了其活化过一硫酸盐(PMS)氧化降解水中双酚A(BPA)的行为和机制.表征结果表明,CuCo-MOF-74成功均匀负载到半焦活性炭表面,比表面积为582.04m²/g.BPA降解实验表明,在最佳条件下(0.2g/L PMS、0.1g/L催化剂),CuCo-MOF-74₂/SC/PMS在30min内对20mg/L BPA的降解效率达到95.01%,矿化率为54.7%,显著优于CuCo-MOF-74/PMS体系,且CuCo-MOF-74₂/SC(0.1113min^-1)的反应速率常数是CuCo-MOF-74(0.0324min^-1)的3.4倍.5次循环后,CuCo-MOF-74₂/SC的降解效率由94.83%降至72.56%,显著高于CuCo-MOF-74(由76.95%降至21.49%).在CuCo-MOF-74₂/SC/PMS系统中,自由基(•OH、SO•－4和O•－2)和非自由基(¹O₂和电子转移)都参与了BPA的降解,其中自由基起主要作用.将CuCo-MOF-74负载到半焦活性碳上,有效提高了CuCo-MOF-74的稳定性和比表面积,强化了其对水中BPA的降解效果,该研究对MOF基催化剂的开发具有重要指导意义.

Abstract

In this study, a catalyst with bimetallic CuCo-MOF-74 dispersed on semi-coke (SC) (CuCo-MOF-74_x/SC) was successfully prepared by one-pot hydrothermal synthesis, and the degradation behavior and mechanism for aqueous bisphenol A (BPA) via persulfate (PMS) activation was systemically studied. The characterization results showed that CuCo-MOF-74 was uniformly dispersed onto the surface of semi-coke activated carbon, and the specific surface area of CuCo-MOF-74₂/SC was 582.04m²/g. For BPA degradation, under the optimum conditions (0.2g/L PMS, 0.1g/L catalyst), the CuCo-MOF-74₂/SC/PMS system achieved a degradation efficiency of 95.01% for 20mg/L BPA in 30min and the mineralization rate of 54.7%, which was significantly higher than that of the CuCo-MOF-74/PMS system, and the reaction rate constant of CuCo-MOF-74₂/SC (0.1113min^-1) was 3.4 times of CuCo-MOF-74 (0.0324min^-1). After 5 cycles, the degradation efficiency of CuCo-MOF-74₂/SC decreased from 94.83% to 72.56%, which was remarkably higher than that of CuCo-MOF-74 (from 76.95% to 21.49%). In the CuCo-MOF-74₂/SC/PMS system, both free radicals (•OH, SO•－4and O•－2) and non-radicals (¹O₂ and electron transfer) were involved in the degradation of BPA, and free radicals oxidation played a major role. The loading of CuCo-MOF-74 on SC significantly enhances the stability and improves specific surface area of CuCo-MOF-74, thereby elevating the degradation efficiency for BPA in water. This study provides the important guiding significance for the development of MOF-based catalysts.

导出引用

芦天姣, 王家宏. 半焦活性炭负载CuCo-MOF-74的制备及其活化过硫酸盐降解水中双酚A的研究[J]. 中国环境科学. 2025, 45(11): 6079-6090

LU Tian-jiao, WANG Jia-hong. The preparation of semi-coke activated carbon supported CuCo-MOF-74 and degradation of BPA in water via peroxymonosulfate activation[J]. China Environmental Science. 2025, 45(11): 6079-6090

中图分类号： X703.5

参考文献

[1] Wei Y X, Fang B, Guo J M, et al. Co₃O₄ coated carbon fiber activates PMS to degrade phenolic pollutants via ¹O₂ dominated non-radical pathway: Role of dual reaction center [J]. Journal of Environmental Chemical Engineering, 2024,12(5):113921.
[2] Sun Y P, Zhao Y, Zhan X H, et al. A ZIF-8-derived copper-nitrogen co-hybrid carbon catalyst for peroxymonosulfate activation to degrade BPA [J]. Chemosphere, 2022,308:136489.
[3] 王诗生,杨玉,盛广宏,等.改性生物炭活化过硫酸盐降解盐酸四环素 [J]. 中国环境科学, 2024,44(11):6122-6131. Wang S S, Yang Y, Sheng G H, et al. Activation of modified biochar by peracetic acid for the degradation of tetracycline in hydrochloric acid solution [J]. China Environmental Science, 2024,44(11):6122-6131.
[4] 蒋函灵,吴晨曦,周艾娟,等.活性碳催化膜活化过硫酸盐氧化水中氨氮 [J]. 中国环境科学, 2025,45(6):3063-3072. Jiang H L, Wu C X, Zhou A J, et al. Activated carbon catalytic membrane activation of persulfate for the oxidation of ammonia nitrogen in water [J]. China Environmental Science, 2025,45(6):3063-3072.
[5] Chang X, Xu X Y, Gao Z F, et al. Activation of persulfate by heterogeneous catalyst ZnCo₂O₄rGO for efficient degradation of bisphenol A [J]. Canadian Journal of Chemistry, 2020,98(12):771-778.
[6] Wu L Y, Zhang Q, Hong J M, et al. Degradation of bisphenol A by persulfate activation via oxygen vacancy-rich CoFe₂O₄-x [J]. Chemosphere, 2019,221:412-422.
[7] He Y L, He C S, Lai L D, et al. Activating peroxymonosulfate by N and O co-doped porous carbon for efficient BPA degradation: A re-visit to the removal mechanism and the effects of surface unpaired electrons [J]. Applied Catalysis B-Environment and Energy, 2022, 314:121390.
[8] Hu L M, Zhang G S, Liu M, et al. Enhanced degradation of bisphenol A (BPA) by peroxymonosulfate with Co₃O₄-Bi₂O₃ catalyst activation: Effects of pH, inorganic anions, and water matrix [J]. Chemical Engineering Journal, 2018,338:300-310.
[9] Peng X Z, Yu S H, Chen J J, et al. Enhanced degradation of bisphenol A over CFO/CMK-3involved PMS activation: Insights into the synergistic effect between the spinel and mesoporous carbon [J]. Separation and Purification Technology, 2023,307:122861.
[10] Hu X N, Zhu M S. Were persulfate-based advanced oxidation processes really understood? Basic concepts, cognitive biases, and experimental details [J]. Environmental Science & Technology, 2024, 58(24):10415-10444.
[11] Dong Z Y, Zhang Q, Chen B Y, et al. Oxidation of bisphenol A by persulfate via Fe₃O₄-α-MnO₂ nanoflower-like catalyst: Mechanism and efficiency [J]. Chemical Engineering Journal, 2019,357:337-347.
[12] Zhao L, Ji Y F, Kong D Y, et al. Simultaneous removal of bisphenol A and phosphate in zero-valent iron activated persulfate oxidation process [J]. Chemical Engineering Journal, 2016,303:458-466.
[13] Du W Y, Zhang Q Z, Shang Y N, et al. Sulfate saturated biosorbent-derived Co-S@NC nanoarchitecture as an efficient catalyst for peroxymonosulfate activation [J]. Applied Catalysis B- Environmental, 2020,262:118302.
[14] Shahzad A, Ali J, Ifthikar J, et al. Non-radical PMS activation by the nanohybrid material with periodic confinement of reduced graphene oxide (rGO) and Cu hydroxides [J]. Journal of Hazardous Materials, 2020,392:122316.
[15] Ding J F, Shen L L, Yan R P, et al. Heterogeneously activation of H₂O₂ and persulfate with goethite for bisphenol A degradation: A mechanistic study [J]. Chemosphere, 2020,261:127715.
[16] Yang J A, Sun Y X, Chang X J, et al. MOF-derived N-doped porous carbons activate peroxomonosulfate to efficiently degrade organic pollutants via non-radical pathways [J]. Journal of Water Process Engineering, 2023,56:104295.
[17] Shahzadi S, Akhtar M, Arshad M, et al. A review on synthesis of MOF-derived carbon composites: innovations in electrochemical, environmental and electrocatalytic technologies [J]. Rsc Advances, 2024,14(38):27575-27607.
[18] Hou S Y, Zhang H Z, Wang P, et al. Multiwall carbon nanotube decorated hemin/Mn-MOF towards BPA degradation through PMS activation [J]. Journal of Environmental Chemical Engineering, 2022, 10:108426.
[19] Han T T, Xiao Y L, Tong M M, et al. Synthesis of CNT@MIL-68(Al) composites with improved adsorption capacity for phenol in aqueous solution [J]. Chemical Engineering Journal, 2015,275:134-141.
[20] Huo X W, Zhou P, Zhang J, et al. N, S-Doped porous carbons for persulfate activation to remove tetracycline: Nonradical mechanism [J]. Journal of Hazardous Materials, 2020,391:122055.
[21] Li B, Zhang C Q, Zuo Q, et al. Goethite-activated carbon as a persulfate activator for effective Escherichia coli inactivation [J]. Journal of Water Process Engineering, 2024,57:104652.
[22] Li H X, Yang Z X, Lu S, et al. Nano-porous bimetallic CuCo- MOF-74 with coordinatively unsaturated metal sites for peroxymonosulfate activation to eliminate organic pollutants: Performance and mechanism [J]. Chemosphere, 2021,273:129643.
[23] Zhang W D, Descorme C, Valverde J L, et al. Cu-Co mixed oxide catalysts for the total oxidation of toluene and propane [J]. Catalysis Today, 2022,384:238-245.
[24] Li H X, Su L Y, Zheng J T, et al. MOFs derived carbon supporting CuCo nanospheres as efficient catalysts of peroxymonosulfate for rapid removal of organic pollutant [J]. Chemical Engineering Journal, 2023,451:139114.
[25] Li W, Li Y X, Zhang D Y, et al. CuO-Co₃O₄@CeO₂as a heterogeneous catalyst for efficient degradation of 2,4-dichlorophenoxyacetic acid by peroxymonosulfate [J]. Journal of Hazardous Materials, 2020,381:121209.
[26] Zhao H, Chen Y, Peng Q, et al. Catalytic activity of MOF(2Fe/ Co)/carbon aerogel for improving H₂O₂ and OH generation in solar photo–electro–Fenton process [J]. Applied Catalysis B: Environmental, 2017,203:127-137.
[27] Li H, Wan J, Ma Y, et al. Degradation of refractory dibutyl phthalate by peroxymonosulfate activated with novel catalysts cobalt metal-organic frameworks: Mechanism, performance, and stability [J]. Journal of Hazardous Materials, 2016,318:154-163.
[28] Dissegna S, Epp K, Heinz W R, et al. Defective metal-organic frameworks [J]. Advanced Materials, 2018,30(37):1704501.
[29] Liu S Y, Lai C, Zhou X R, et al. Peroxydisulfate activation by sulfur-doped ordered mesoporous carbon: Insight into the intrinsic relationship between defects and ¹O₂ generation [J]. Water Research, 2022,221:118797.
[30] Liu L, Han C J, Ding G F, et al. Oxygen vacancies-enriched Cu/Co bimetallic oxides catalysts for high-efficiency peroxymonosulfate activation to degrade TC: Insight into the increase of Cu⁺ triggered by Co doping [J]. Chemical Engineering Journal, 2022,450:138302.
[31] Li X, Wang S W, Xu B K, et al. MOF etching-induced Co-doped hollow carbon nitride catalyst for efficient removal of antibiotic contaminants by enhanced perxymonosulfate activation [J]. Chemical Engineering Journal, 2022,441:136074.
[32] Hou S Y, Zhang H Z, Wang P, et al. Multiwall carbon nanotube decorated hemin/Mn-MOF towards BPA degradation through PMS activation [J]. Journal of Environmental Chemical Engineering, 2022, 10(5):108426.
[33] Wang P F, Zhang Y M, Zhu J Y, et al. Catalytic degradation of BPA by bamboo leaf-derived KOH-activated porous biocarbon loaded with CoFe₂O₄-activated peroxymonosulfate [J]. Chemical Engineering Journal, 2024,492:151886.
[34] Hu J, Qian B B, Zeng X K, et al. Oxygen vacant Co₃O₄ in situ embedded on carbon spheres: cooperatively tuning electron transfer for boosted peroxymonosulfate activation [J]. Journal of Materials Chemistry A, 2021,9(30):16489-16499.
[35] Li Y, Bu J Q, Sun Y R, et al. Efficient degradation of norfloxacin by synergistic activation of PMS with a three-dimensional electrocatalytic system based on Cu-MOF [J]. Separation and Purification Technology, 2025,356:129945.
[36] 竺哲欣,马晓吉,尚志国,等.氯离子对模拟太阳光活化过一硫酸氢钾氧化卡马西平的影响规律 [J]. 环境科学学报, 2021,41(6):2131-2137. Zhu Z X, Ma X J, Shang Z G, et al. The influence of chloride ions on the oxidation of carbamazepine by potassium peroxymonosulfate activated by simulated sunlight [J]. Acta Scientiae Circumstantiae, 2021,41(6):2131-2137.
[37] 石清清,蒲生彦,杨犀.纳米Cu⁰@Fe₃O₄活化PMS降解对-硝基苯酚的协同反应机制 [J]. 环境科学, 2020,41(10):4615-4625. Shi Q Q, Pu S Y, Yang X. Synergistic reaction mechanism of nano-Cu0@Fe₃O₄ activated PMS for the degradation of p-nitrophenol [J]. Environmental Science, 2020,41(10):4615-4625.
[38] 丁春生,潘宇强,雷佳,等.铁钴金属氧化物活化过硫酸盐降解水中苯并噻唑 [J]. 浙江工业大学学报, 2025,53(1):93-103. Ding C S, Pan Y Q, Lei J, et al. Activation of Iron-Cobalt Metal Oxides by Peroxymonosulfate for the Degradation of Benzothiazole in Water [J]. Journal of Zhejiang University of Technology, 2025,53(1):93-103.
[39] Ma S C, Yang D, Guan Y A, et al. Maximally exploiting active sites on Yolk@shell nanoreactor: Nearly 100% PMS activation efficiency and outstanding performance over full pH range in Fenton-like reaction [J]. Applied Catalysis B-Environment and Energy, 2022,316:121594.
[40] Cao J, Yang Z H, Xiong W P, et al. Peroxymonosulfate activation of magnetic Co nanoparticles relative to an N-doped porous carbon under confinement: Boosting stability and performance [J]. Separation and Purification Technology, 2020,250:117237.
[41] Wu H Z, Yi Q, Li X, et al. Construction of core-shell magnetic metal-organic framework composites Fe₃O₄@MIL-101(Fe, Co) for degradation of RhB by efficiently activating PMS [J]. Rsc Advances, 2024,14(24):16727-16735.
[42] Mao S, Zhao P, Wu Y, et al. Promoting charge migration of Co(OH)₂/ g-C₃N₄by hydroxylation for improved PMS activation: Catalyst design, DFT calculation and mechanism analysis [J]. Chemical Engineering Journal, 2023,451:138503.
[43] Zhang J, Zeng H X, Bu L J, et al. Cu⁰incorporated cobalt/nitrogen doped carbonaceous frameworks derived from ZIF-67 (Cu@Co–N–C) as PMS activator for efficient degradation of naproxen: Direct electron transfer and ¹O₂ dominated nonradical mechanisms [J]. Chemical Engineering Journal, 2023,454(P1):139989.
[44] Kumar A, Ahamad A, Prasad B, et al. Discerning the role of a site cation in ACoO₃ perovskites for boosting Co³⁺/Co²⁺ redox cycle for pollutant degradation: DFT calculation, mechanism and toxicity evolution [J]. Environmental Research, 2024,259:119533.
[45] He B, Song L X, Zhao Z X, et al. CuFe₂O₄/CuO magnetic nano- composite activates PMS to remove ciprofloxacin: Ecotoxicity and DFT calculation [J]. Chemical Engineering Journal, 2022,446:137183.
[46] Huang J, Zheng H Y, Xu H, et al. Magnetic bimetallic Fe and Cu-loaded N-doped biochar for the activation of peroxomonosulfate for tetracycline degradation: DFT calculations and mechanism analysis [J]. Applied Surface Science, 2025,679:161158.
[47] Wu S H, Yang C P, Lin Y, et al. Efficient degradation of tetracycline by singlet oxygen-dominated peroxymonosulfate activation with magnetic nitrogen-doped porous carbon [J]. Journal of Environmental Sciences, 2022,115:330-340.
[48] Cai F H, Sun C Y, Sun Z Z, et al. Sulfur-functionalized CoMn₂O₄ as a Fenton-like catalyst for the efficient rhodamine B degradation [J]. Applied Surface Science, 2023,623:157044.
[49] Li X, Chen Y L, Xiao C, et al. Manipulating the morphology of self-assembly broccoli-like cobalt nickel spinel for enhancing the peroxydisulfate activation towards highly-effective ciprofloxacin degradation: Radical and non-radical pathways, mechanism and toxicity evaluation [J]. Applied Surface Science, 2023,617:156593.