Skip to main content
SpringerLink
Log in

Insights into the electron transfer mechanisms of permanganate activation by carbon nanotube membrane for enhanced micropollutants degradation

  • Research Article
  • Published:
Frontiers of Environmental Science & Engineering Aims and scope Submit manuscript

Abstract

Numerous reagents have been proposed as electron sacrificers to induce the decomposition of permanganate (KMnO4) by producing highly reactive Mn species for micropollutants degradation. However, this strategy can lead to low KMnO4 utilization efficiency due to limitations associated with poor mass transport and high energy consumption. In the present study, we rationally designed a catalytic carbon nanotube (CNT) membrane for KMnO4 activation toward enhanced degradation of micropollutants. The proposed flow-through system outperformed conventional batch reactor owing to the improved mass transfer via convection. Under optimal conditionals, a > 70% removal (equivalent to an oxidation flux of 2.43 mmol/(h·m2)) of 80 µmol/L sulfamethoxazole (SMX) solution can be achieved at single-pass mode. The experimental analysis and DFT studies verified that CNT could mediate direct electron transfer from organic molecules to KMnO4, resulting in a high utilization efficiency of KMnO4. Furthermore, the KMnO4/CNT system had outstanding reusability and CNT could maintain a long-lasting reactivity, which served as a green strategy for the remediation of micropollutants in a sustainable manner. This study provides new insights into the electron transfer mechanisms and unveils the advantages of effective KMnO4 utilization in the KMnO4/CNT system for environmental remediation.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  • Bavasso I, Montanaro D, Di Palma L, Petrucci E (2020). Electrochemically assisted decomposition of ozone for degradation and mineralization of Diuron. Electrochimica Acta, 331: 135423

    Article  CAS  Google Scholar 

  • Casida M E, Jamorski C, Casida K C, Salahub D R (1998). Molecular excitation energies to high-lying bound states from time-dependent density-functional response theory: characterization and correction of the time-dependent local density approximation ionization threshold. Journal of Chemical Physics, 108(11): 4439–4449

    Article  CAS  Google Scholar 

  • Chen J, Qu R, Pan X, Wang Z (2016). Oxidative degradation of triclosan by potassium permanganate: kinetics, degradation products, reaction mechanism, and toxicity evaluation. Water Research, 103: 215–223

    Article  CAS  Google Scholar 

  • Chen J, Rao D, Dong H, Sun B, Shao B, Cao G, Guan X (2020). The role of active manganese species and free radicals in permanganate/bisulfite process. Journal of Hazardous Materials, 388: 121735

    Article  CAS  Google Scholar 

  • Cheng H, Ma J, Jiang J, Pang S Y, Yang T, Wang P (2019). Aggregation kinetics of manganese oxides formed from permanganate activated by (Bi)sulfite: dual role of Ca2+ and MnII/III. Water Research, 159: 454–463

    Article  CAS  Google Scholar 

  • Derakhshani E, Naghizadeh A (2013). Ultrasound regeneration of multi wall carbon nanotubes saturated by humic acid. Desalination and Water Treatment, 52(40–42): 7468–7472

    Google Scholar 

  • Du J K, Xiao G F, Xi Y X, Zhu X W, Su F, Kim S H (2020). Periodate activation with manganese oxides for sulfanilamide degradation. Water Research, 169: 115278

    Article  CAS  Google Scholar 

  • Gao J, Hedman C, Liu C, Guo T, Pedersen J A (2012). Transformation of sulfamethazine by manganese oxide in aqueous solution. Environmental Science & Technology, 46(5): 2642–2651

    Article  CAS  Google Scholar 

  • Gao Y, Jiang J, Zhou Y, Pang S Y, Ma J, Jiang C, Yang Y, Huang Z S, Gu J, Guo Q, Duan J B, Li J (2018). Chlorination of bisphenol S: kinetics, products, and effect of humic acid. Water Research, 131: 208–217

    Article  CAS  Google Scholar 

  • Gao Y, Zhou Y, Pang S Y, Jiang J, Yang Z, Shen Y, Wang Z, Wang P X, Wang L H (2019). New insights into the combination of permanganate and bisulfite as a novel advanced oxidation process: importance of high valent manganese-oxo species and sulfate radical. Environmental Science & Technology, 53(7): 3689–3696

    Article  CAS  Google Scholar 

  • Guan X H, He D, Ma J, Chen G H (2010). Application of permanganate in the oxidation of micropollutants: a mini review. Frontiers of Environmental Science & Engineering in China, 4(4): 405–413

    Article  CAS  Google Scholar 

  • Guo D L, You S J, Li F, Liu Y B (2022). Engineering carbon nanocatalysts towards efficient degradation of emerging organic contaminants via persulfate activation: a review. Chinese Chemical Letters, 33(1): 1–10

    Article  Google Scholar 

  • Han C, Duan X G, Zhang M J, Fu W Z, Duan X Z, Ma W J, Liu S M, Wang S B, Zhou X G (2019). Role of electronic properties in partition of radical and nonradical processes of carbocatalysis toward peroxymonosulfate activation. Carbon, 153: 73–80

    Article  CAS  Google Scholar 

  • Hao X M, Wang G L, Chen S, Yu H T, Quan X (2019). Enhanced activation of peroxymonosulfate by CNT-TiO2 under UV-light assistance for efficient degradation of organic pollutants. Frontiers of Environmental Science & Engineering, 13(5): 77

    Article  Google Scholar 

  • Hu Y B, Lo S L, Li Y F, Lee Y C, Chen M J, Lin J C (2018). Autocatalytic degradation of perfluorooctanoic acid in a permanganate-ultrasonic system. Water Research, 140: 148–157

    Article  CAS  Google Scholar 

  • Jiang J, Pang S Y, Ma J (2010). Role of ligands in permanganate oxidation of organics. Environmental Science & Technology, 44(11): 4270–4275

    Article  CAS  Google Scholar 

  • Jin L, You S, Duan X, Yao Y, Yang J, Liu Y (2022). Peroxymonosulfate activation by Fe3O4-MnO2/CNT nanohybrid electroactive filter towards ultrafast micropollutants decontamination: performance and mechanism. Journal of Hazardous Materials, 423: 127111

    Article  CAS  Google Scholar 

  • Kostka J E, Lutheriii G W, Nealson K H (1995). Chemical and biological reduction of Mn(III)-pyrophosphate complexes: potential importance of dissolved Mn(III) as an environmental oxidant. Geochimica et Cosmochimica Acta, 59: 885–894

    CAS  Google Scholar 

  • Lee H, Kim H I, Weon S, Choi W, Hwang Y S, Seo J, Lee C, Kim J H (2016). Activation of persulfates by graphitized nanodiamonds for removal of organic compounds. Environmental Science & Technology, 50(18): 10134–10142

    Article  CAS  Google Scholar 

  • Liu Q Q, Li M, Liu X, Zhang Q, Liu R, Wang Z L, Shi X T, Quan J, Shen X H, Zhang F W (2018). Removal of sulfamethoxazole and trimethoprim from reclaimed water and the biodegradation mechanism. Frontiers of Environmental Science & Engineering, 12(6): 6

    Article  CAS  Google Scholar 

  • Liu Y B, Gao G D, Vecitis C D (2020). Prospects of an electroactive carbon nanotube membrane toward environmental applications. Accounts of Chemical Research, 53(12): 2892–2902

    Article  CAS  Google Scholar 

  • Liu Y B, Li J H, Zhou B X, Bai J, Zheng Q, Zhang J L, Cai W M (2009). Comparison of photoelectrochemical properties of TiO2-nanotube-array photoanode prepared by anodization in different electrolyte. Environmental Chemistry Letters, 7(4): 363–368

    Article  CAS  Google Scholar 

  • Ma X Y, Hu S F, Wang H Y, Li J, Huang J, Zhang Y, Lu W G, Li Q S (2012). Kinetics of oxidation of dimethyl trisulfide by potassium permanganate in drinking water. Frontiers of Environmental Science & Engineering, 6(2): 171–176

    Article  CAS  Google Scholar 

  • Mustafa M, Wang H J, Lindberg R H, Fick J, Wang Y Y, Tysklind M (2021). Identification of resistant pharmaceuticals in ozonation using QSAR modeling and their fate in electro-peroxone process. Frontiers of Environmental Science & Engineering, 15(5): 106

    Article  CAS  Google Scholar 

  • Pan F, Ji H, Du P, Huang T, Wang C, Liu W (2021). Insights into catalytic activation of peroxymonosulfate for carbamazepine degradation by MnO2 nanoparticles in-situ anchored titanate nanotubes: mechanism, ecotoxicity and DFT study. Journal of Hazardous Materials, 402: 123779

    Article  CAS  Google Scholar 

  • Pearson R G (1986). Absolute electronegativity and hardness correlated with molecular orbital theory. Proceedings of the National Academy of Sciences of the United States of America, 83(22): 8440–8441

    Article  CAS  Google Scholar 

  • Peng J, Zhou P, Zhou H, Liu W, Zhang H, Zhou C, Lai L, Ao Z, Su S, Lai B (2021). Insights into the electron-transfer mechanism of permanganate activation by graphite for enhanced oxidation of sulfamethoxazole. Environmental Science & Technology, 55(13): 9189–9198

    Article  CAS  Google Scholar 

  • Rasool K, Pandey R P, Rasheed P A, Buczek S, Gogotsi Y, Mahmoud K A (2019). Water treatment and environmental remediation applications of two-dimensional metal carbides (MXenes). Materials Today, 30: 80–102

    Article  CAS  Google Scholar 

  • Ren W, Xiong L L, Nie G, Zhang H, Duan X G, Wang S B (2020). Insights into the electron-transfer regime of peroxydisulfate activation on carbon nanotubes: the role of oxygen functional groups. Environmental Science & Technology, 54(2): 1267–1275

    Article  CAS  Google Scholar 

  • Shao P, Yu S, Duan X, Yang L, Shi H, Ding L, Tian J, Yang L, Luo X, Wang S (2020). Potential difference driving electron transfer via defective carbon nanotubes toward selective oxidation of organic micropollutants. Environmental Science & Technology, 54(13): 8464–8472

    Article  CAS  Google Scholar 

  • Shen Z C, Zhan L, Xu Z M (2022). Thermal defluorination behaviors of PFOS, PFOA and PFBS during regeneration of activated carbon by molten salt. Frontiers of Environmental Science & Engineering, 16(8): 103

    Article  CAS  Google Scholar 

  • Shi Z, Jin C, Bai R, Gao Z, Zhang J, Zhu L, Zhao Z, Strathmann T J (2020). Enhanced transformation of emerging contaminants by permanganate in the presence of redox mediators. Environmental Science & Technology, 54(3): 1909–1919

    Article  CAS  Google Scholar 

  • Simandi L I, Jaky M, Schelly Z A (1984). Short-lived manganate(VI) and manganate(V) intermediates in the permanganate oxidation of sulfite ion. Journal of the American Chemical Society, 106(22): 6866–6867

    Article  CAS  Google Scholar 

  • Sun B, Guan X H, Fang J Y, Tratnyek P G (2015). Activation of manganese oxidants with bisulfite for enhanced oxidation of organic contaminants: the Involvement of Mn(III). Environmental Science & Technology, 49(20): 12414–12421

    Article  CAS  Google Scholar 

  • Sun B, Xiao Z, Dong H, Ma S, Wei G, Cao T, Guan X (2019). Bisulfite triggers fast oxidation of organic pollutants by colloidal MnO2. Journal of Hazardous Materials, 363: 412–420

    Article  CAS  Google Scholar 

  • Sun B, Zhang J, Du J S, Qiao J L, Guan X H (2013). Reinvestigation of the role of humic acid in the oxidation of phenols by permanganate. Environmental Science & Technology, 47(24): 14332–14340

    Article  CAS  Google Scholar 

  • Tang L, Liu Y, Wang J, Zeng G, Deng Y, Dong H, Feng H, Wang J, Peng B (2018). Enhanced activation process of persulfate by mesoporous carbon for degradation of aqueous organic pollutants: electron transfer mechanism. Applied Catalysis B: Environmental, 231: 1–10

    Article  CAS  Google Scholar 

  • Tian S Q, Wang L, Liu Y L, Yang T, Huang Z S, Wang X S, He H Y, Jiang J, Ma J (2019). Enhanced permanganate oxidation of sulfamethoxazole and removal of dissolved organics with biochar: formation of highly oxidative manganese intermediate species and in situ activation of biochar. Environmental Science & Technology, 53(9): 5282–5291

    Article  CAS  Google Scholar 

  • Wang X, Wang Y, Zhao C, Zhu Y, Sun Z, Fan H S, Hu X, Zheng H (2021). Ciprofloxacin removal by ultrasound-enhanced carbon nanotubes/permanganate process: in situ generation of free reactive manganese species via electron transfer. Water Research, 202: 117393

    Article  CAS  Google Scholar 

  • Wu L, Wu T, Liu Z, Tang W, Xiao S, Shao B, Liang Q, He Q, Pan Y, Zhao C, Liu Y, Tong S (2022). Carbon nanotube-based materials for persulfate activation to degrade organic contaminants: properties, mechanisms and modification insights. Journal of Hazardous Materials, 431: 128536

    Article  CAS  Google Scholar 

  • Xu K, Ben W, Ling W, Zhang Y, Qu J, Qiang Z (2017). Impact of humic acid on the degradation of levofloxacin by aqueous permanganate: kinetics and mechanism. Water Research, 123: 67–74

    Article  CAS  Google Scholar 

  • Yang S, Wang S, Liu X, Li L (2019). Biomass derived interconnected hierarchical micro-meso-macro-porous carbon with ultrahigh capacitance for supercapacitors. Carbon, 147: 540–549

    Article  CAS  Google Scholar 

  • Yu S, Peng Y, Shao P, Wang Y, He Y, Ren W, Yang L, Shi H, Luo X (2023). Electron-transfer-based peroxymonosulfate activation on defect-rich carbon nanotubes: understanding the substituent effect on the selective oxidation of phenols. Journal of Hazardous Materials, 442: 130108

    Article  CAS  Google Scholar 

  • Yun E T, Lee J H, Kim J, Park H D, Lee J (2018). Identifying the nonradical mechanism in the peroxymonosulfate activation process: singlet oxygenation versus mediated electron transfer. Environmental Science & Technology, 52(12): 7032–7042

    Article  CAS  Google Scholar 

  • Zhang P, Zhou P, Peng J L, Liu Y, Zhang H, He C S, Xiong Z K, Liu W, Lai B (2022). Insight into metal-free carbon catalysis in enhanced permanganate oxidation: changeover from electron donor to electron mediator. Water Research, 219: 118626

    Article  CAS  Google Scholar 

  • Zheng W T, You S J, Yao Y, Jin L M, Liu Y B (2021). Development of atomic hydrogen-mediated electrocatalytic filtration system for peroxymonosulfate activation towards ultrafast degradation of emerging organic contaminants. Applied Catalysis B: Environmental, 298: 120593

    Article  CAS  Google Scholar 

  • Zhou Y, Gao Y, Jiang J, Shen Y M, Pang S Y, Song Y, Guo Q (2021). A comparison study of levofloxacin degradation by peroxymonosulfate and permanganate: kinetics, products and effect of quinone group. Journal of Hazardous Materials, 403: 123834

    Article  CAS  Google Scholar 

  • Zhou Z, Liu X, Sun K, Lin C Y, Ma J, He M C, Ouyang W (2019). Persulfate-based advanced oxidation processes (AOPs) for organic-contaminated soil remediation: a review. Chemical Engineering Journal, 372: 836–851

    Article  CAS  Google Scholar 

  • Zhu S S, Huang X C, Ma F, Wang L, Duan X G, Wang S B (2018). Catalytic removal of aqueous contaminants on N-doped graphitic biochars: inherent roles of adsorption and nonradical mechanisms. Environmental Science & Technology, 52(15): 8649–8658

    Article  CAS  Google Scholar 

  • Zhu Y H, Wang X X, Zhang J, Ding L, Li J F, Zheng H L, Zhao C (2019a). Generation of active Mn(III)aq by a novel heterogeneous electro-permanganate process with manganese(II) as promoter and stabilizer. Environmental Science & Technology, 53(15): 9063–9072

    Article  CAS  Google Scholar 

  • Zhu Y H, Zhao C, Liang J L, Shang R, Zhu X M, Ding L, Deng H P, Zheng H L, Strathmann T J (2019b). Rapid removal of diclofenac in aqueous solution by soluble Mn(III)aq generated in a novel electro-activated carbon fiber-permanganate (E-ACF-PM) process. Water Research, 165: 114975

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This work was financially supported by the Natural Science Foundation of Shanghai (No. 23ZR1401300) and the National Natural Science Foundation of China (No. 52170068).

Author information

Authors and Affiliations

  1. College of Environmental Science and Engineering, Donghua University, Shanghai, 201620, China

    Xufang Wang, Dongli Guo & Yanbiao Liu

  2. State Key Laboratory of Urban Water Resource and Environment, School of Environment, Harbin Institute of Technology, Harbin, 150090, China

    Jinna Zhang

  3. MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin, 150080, China

    Yuan Yao

  4. Shanghai Institute of Pollution Control and Ecological Security, Shanghai, 200092, China

    Yanbiao Liu

Authors
  1. Xufang Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Dongli Guo
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Jinna Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Yuan Yao
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Yanbiao Liu
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding authors

Correspondence to Yuan Yao or Yanbiao Liu.

Additional information

Highlights

• A CNT filter enabled effective KMnO4 activation via facilitated electron transfer.

• Ultra-fast degradation of micropollutants were achieved in KMnO4/CNT system.

• CNT mediated electron transfer process from electron-rich molecules to KMnO4.

• Electron transfer dominated organic degradation.

Supporting Material

11783_2023_1706_MOESM1_ESM.pdf

Insights into the electron transfer mechanisms of permanganate activation by carbon nanotube membrane for enhanced micropollutants degradation

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Wang, X., Guo, D., Zhang, J. et al. Insights into the electron transfer mechanisms of permanganate activation by carbon nanotube membrane for enhanced micropollutants degradation. Front. Environ. Sci. Eng. 17, 106 (2023). https://doi.org/10.1007/s11783-023-1706-0

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1007/s11783-023-1706-0

Keywords

Search

Navigation