Citation: Yuchen ZHANG, Jingliang LIU, Xiaobo WANG, Jingjing CAO, Jingya SUN. Degradation of tannic acid on activation of peroxymonosulfate mediated by β-MnO₂[J]. Chinese Journal of Inorganic Chemistry, ;2026, 42(7): 1505-1512. doi: 10.11862/CJIC.20260003 shu

Degradation of tannic acid on activation of peroxymonosulfate mediated by β-MnO₂

School of Environmental Science, Nanjing XiaoZhuang University, Nanjing 211171, China

Corresponding author: Jingliang LIU, jingliangliu@njxzc.edu.cn
Received Date: 5 January 2026
Revised Date: 8 May 2026

Figures(12)

β-MnO₂ nanowires were successfully prepared, and their well-defined crystalline structure and morphology were characterized using X-ray diffraction (XRD) and transmission electron microscopy (TEM). Using the typical organic pollutant tannic acid (TA) as the target degradation substance, the oxidative degradation performance of β-MnO₂ activated peroxymonosulfate (PMS) toward tannic acid (TA)was systematically investigated. Key influencing factors, including PMS dosage, catalyst amount, initial solution pH, and reaction temperature, were thoroughly examined. The experimental results demonstrated that the β-MnO₂/PMS system exhibited excellent TA removal capability. The TA removal efficiency increased with higher PMS and MnO₂ dosages, and optimal degradation performance was achieved under acidic conditions. Elevated temperatures accelerated the reaction process, with an apparent activation energy of 11.45 kJ·mol^-1. Free radical quenching experiments further confirmed that sulfate radicals (SO₄^-·) were the primary active species involved in the reaction.
- manganese dioxide,
- peroxymonosulfate,
- tannic acid
1. [1]
  DBIRA S, BENSALAH N, ZAGHO M M, ENNAHAOUI M, BEDOUI A. Oxidative degradation of tannic acid in aqueous solution by UV/S₂O₈^2- and UV/H₂O₂/Fe²⁺ processes: A comparative study[J]. Appl. Sci., 2019, 9(1): 156 doi: 10.3390/app9010156
2. [2]
  ZHOU Z B, XIAO J W, GUAN S W, GENG Z J, ZHAO R F, GAO B T. A hydrogen-bonded antibacterial curdlan-tannic acid hydrogel with an antioxidant and hemostatic function for wound healing[J]. Carbohydr. Polym., 2022, 285: 119235 doi: 10.1016/j.carbpol.2022.119235
3. [3]
  FENG J K, YU Y L, HUANG S Q, ZHU N W, MOJIRI A, GE D D. Tannic acid as a green chemical for the removal of various heavy metals: A critical review of recent developments[J]. J. Environ. Manage., 2025, 375: 124390 doi: 10.1016/j.jenvman.2025.124390
4. [4]
  SUN C C, XIONG B W, PAN Y, CUI H. Adsorption removal of tannic acid from aqueous solution by polyaniline: Analysis of operating parameters and mechanism[J]. J. Colloid Interface Sci., 2017, 487: 175-181 doi: 10.1016/j.jcis.2016.10.035
5. [5]
  DENG Y H, WANG L, HU X B, LIU B Z, WEI Z B, YANG S G, SUN C. Highly efficient removal of tannic acid from aqueous solution by chitosan-coated attapulgite[J]. Chem. Eng. J., 2012, 181/182: 300-306 doi: 10.1016/j.cej.2011.11.082
6. [6]
  LU C Y, JIANG B C, LI A M, WANG X, MA Y F, SHEN X P. Competitive adsorption of tannic acid and phenol onto a Bi-functional polymeric adsorbent[J]. Acta Chim. Sinica, 2010, 68(5): 437-442
7. [7]
  LOFRANO G, MERIÇ S. A review on occurrence, measurement, toxicity and tannin removal processes from wastewaters[J]. Environ. Eng. Manage. J., 2019, 18(1): 109-123 doi: 10.30638/eemj.2019.012
8. [8]
  GHANBARI F, MORADI M. Application of peroxymonosulfate and its activation methods for degradation of environmental organic pollutants: Review[J]. Chem. Eng. J., 2017, 310: 41-62 doi: 10.1016/j.cej.2016.10.064
9. [9]
  ZHU J L, WANG J, SHAN C, ZHANG J, LV L, PAN B C. Durable activation of peroxymonosulfate mediated by Co-doped mesoporous FePO₄ via charge redistribution for atrazine degradation[J]. Chem. Eng. J., 2019, 375: 122009 doi: 10.1016/j.cej.2019.122009
10. [10]
  XIAO P F, AN L, WU D D. The use of carbon materials in persulfate-based advanced oxidation processes: A review[J]. New Carbon Mater., 2020, 35(6): 667-683 doi: 10.1016/S1872-5805(20)60521-2
11. [11]
  LI J X, SHI Q X, ZHAO R, LIU Y, CHEN J J, WANG X F, LIU J M, LIU P P, JIA J P. Research progress on manganese based catalysts for activating persulfate degradation of organic wastewater[J]. Environmental Chemistry, 2023, 42(11): 3861-3877
12. [12]
  WANG Y F, LI X D, HOU M R, WANG Z H. Activation of persulfate with Mn-based oxides for degradation of organic pollutants in water: A Review[J]. Research of Environmental Sciences, 2021, 34(8): 1899-1908
13. [13]
  WANG Y H, SUN Y L, GAO M C, XIN Y J, ZHANG G S, XU P, MA D. Degradation of dimethyl phthalate by morphology controlled β-MnO₂ activated peroxymonosulfate: The overlooked roles of high- valent manganese species[J]. J. Hazard. Mater., 2023, 459: 132199 doi: 10.1016/j.jhazmat.2023.132199
14. [14]
  ZHU S S, LI X J, KANG J, DUAN X G, WANG S B. Persulfate activation on crystallographic manganese oxides: Mechanism of singlet oxygen evolution for nonradical selective degradation of aqueous contaminants[J]. Environ. Sci. Technol., 2019, 53(1): 307-315 doi: 10.1021/acs.est.8b04669
15. [15]
  ZHANG H, HE J H, MA C, ZHANG Y, HE Y, YU Y Y, MENG T, ZHANG M. α-MnO₂ reactive lattice oxygen promotes peroxymonosulfate-activated sulfamethoxazole degradation[J]. Catalysts, 2025, 5(9): 824
16. [16]
  SALVESTRINI S, FENTI A, QIAN L, KOPINKE F D. Oxidation of organic pollutants over MnO₂ in cold water assisted by peroxydisulfate[J]. Chem. Eng. J., 2024, 479: 147170 doi: 10.1016/j.cej.2023.147170
17. [17]
  OUYANG H, WU C, QIU X H, TANAKA K, OHNUKI T, YU Q Q. New insight of Mn(Ⅲ) in δ-MnO₂ for peroxymonosulfate activation reaction: Via direct electron transfer or via free radical reactions[J]. Environ. Res., 2023, 217: 114874 doi: 10.1016/j.envres.2022.114874
18. [18]
  ZENG G S, YANG Y L, LI D X, KUANG C Z, WANG R Y, ZHONG J P, TIAN F H, GUO W, LI C H. Enhanced peroxymonosulfate activation by δ-MnO₂ nanocatalyst enriched with oxygen vacancies for phenolic pollutants polymerization[J]. Appl. Catal. B‒Environ. Energy., 2024, 357: 124327 doi: 10.1016/j.apcatb.2024.124327
19. [19]
  ZHANG L Z, MA J, LI X, WANG S T. Enhanced removal of organics by permanganate preoxidation using tannic acid as a model compound-Role of in situ formed manganese dioxide[J]. J. Environ. Sci., 2009, 21(7): 872-876 doi: 10.1016/S1001-0742(08)62355-4
20. [20]
  WANG X, LI Y D. Synthesis and formation mechanism of manganese dioxide nanowires/nanorods[J]. Chemistry, 2003, 9(1): 300-306 doi: 10.1002/chem.200390024
21. [21]
  ANIPSITAKIS G P, DIONYSIOU D D. Radical generation by the interaction of transition metals with common oxidants[J]. Environ. Sci. Technol., 2004, 38: 3705-3712 doi: 10.1021/es035121o
22. [22]
  HAAG W R, HOIGNÉ J, GASSMAN E, BRAUN A M. Singlet oxygen in surface waters—Part Ⅰ: Furfuryl alcohol as a trapping agent[J]. Chemosphere, 1984, 13(5): 631-640
23. [23]
  SALVADO A P A, CAMPANHOLI L B, FONSECA J M, TARLEY C R T, CAETANO J, DRAGUNSKI D C. Lead􀃭 adsorption by peach palm waste[J]. Desalin. Water Treat., 2012, 48(1/2/3): 335-343
24. [24]
  HUANG J Z, DAI Y F, SINGEWALD K, LIU C C, SAXENA S, ZHANG H C. Effects of MnO₂ of different structures on activation of peroxymonosulfate for bisphenol A degradation under acidic conditions[J]. Chem. Eng. J., 2019, 370: 906-915 doi: 10.1016/j.cej.2019.03.238
25. [25]
  KANG L P, ZHANG M M, LIU Z H, OOI K. IR spectra of manganese oxides with either layered or tunnel structures[J]. Spectroc. Acta Pt. A‒Molec. Biomolec. Spectr., 2007, 67(3): 864-869
26. [26]
  KIM H S, STAIR P C. Bacterially produced manganese oxide and todorokite: UV raman spectroscopic comparison[J]. J. Phys. Chem. B, 2004, 108(44): 17019-17026 doi: 10.1021/jp048810a
27. [27]
  RAO Z, FENG K, TANG B B, WU P Y. Surface decoration of amino-functionalized metal-organic framework/graphene oxide composite onto polydopamine-coated membrane substrate for highly efficient heavy metal removal[J]. ACS Appl. Mater. Interfaces, 2017, 9(3): 2594-2605 doi: 10.1021/acsami.6b15873
28. [28]
  SAPUTRA E, MUHAMMAD S, SUN H Q, ANG H, TADE M, WANG S B. Different crystallographic one-dimensional MnO₂ nanomaterials and their superior performance in catalytic phenol degradation[J]. Environ. Sci. Technol., 2013, 47: 5882-5887 doi: 10.1021/es400878c
29. [29]
  WANG L H, JIANG J, PANG S Y, ZHOU Y, LI J, SUN S F, GAO Y, JIANG C C. Oxidation of bisphenol A by nonradical activation of peroxymonosulfate in the presence of amorphous manganese dioxide[J]. Chem. Eng. J., 2018, 352: 1004-1013 doi: 10.1016/j.cej.2018.07.103
30. [30]
  LIU J L, AN F X, ZHU C Y, ZHOU D M. Efficient transformation of DDT with peroxymonosulfate activation by different crystallographic MnO₂[J]. Sci. Total Environ., 2021, 759: 142864 doi: 10.1016/j.scitotenv.2020.142864
31. [31]
  LIU C N, PAN D Y, TANG X Y, HOU M F, ZHOU Q, ZHOU J. Degradation of rhodamine B by the α-MnO₂/peroxymonosulfate system[J]. Water Air Soil Pollut., 2016, 227(3): 92 doi: 10.1007/s11270-016-2782-6
32. [32]
  TAN C Q, GAO N Y, DENG Y, DENG J, ZHOU S Q, LI J, XIN X Y. Radical induced degradation of acetaminophen with Fe₃O₄ magnetic nanoparticles as heterogeneous activator of peroxymonosulfate[J]. J. Hazard. Mater., 2014, 276: 452-460 doi: 10.1016/j.jhazmat.2014.05.068
33. [33]
  LIU J L, AN F X, LI M, YANG L, WAN J Z, ZHANG S T. Efficient degradation of 2, 4-dichlorophenol on activation of peroxymonosulfate mediated by MnO₂[J]. Bull. Environ. Contam. Toxicol., 2021, 107(2): 255-262 doi: 10.1007/s00128-021-03109-7
34. [34]
  AHMADI M, GHANBARI F. Organic dye degradation through peroxymonosulfate catalyzed by reusable graphite felt/ferriferrous oxide: Mechanism and identification of intermediates[J]. Mater. Res. Bull., 2019, 111: 43-52 doi: 10.1016/j.materresbull.2018.10.027
35. [35]
  GHANBARI F, MARTÍNEZ-HUITLE C A. Electrochemical advanced oxidation processes coupled with peroxymonosulfate for the treatment of real washing machine effluent: A comparative study[J]. J. Electroanal. Chem., 2019, 847: 113182 doi: 10.1016/j.jelechem.2019.05.064
36. [36]
  QI C D, LIU X T, Ma J, LIN C Y, LI X W, ZHANG H J. Activation of peroxymonosulfate by base: Implications for the degradation of organic pollutants[J]. Chemosphere, 2016, 151: 280-288 doi: 10.1016/j.chemosphere.2016.02.089
37. [37]
  SAPUTRA E, MUHAMMAD S, SUN H Q, ANG H M, TADÉ M O, WANG S B. A comparative study of spinel structured Mn₃O₄, Co₃O₄ and Fe₃O₄ nanoparticles in catalytic oxidation of phenolic contaminants in aqueous solutions[J]. J. Colloid Interface Sci., 2013, 407: 467-473 doi: 10.1016/j.jcis.2013.06.061
38. [38]
  DUAN X G, AO Z M, ZHOU L, SUN H Q, WANG G X, WANG S B. Occurrence of radical and nonradical pathways from carbocatalysts for aqueous and nonaqueous catalytic oxidation[J]. Appl. Catal. B‒Environ., 2016, 188: 98-105 doi: 10.1016/j.apcatb.2016.01.059
39. [39]
  ZHANG X L, ZHAO Q, HE H H, ZHANGC Y, ZHAO L L, LI B N. Increasing Lewis acidic sites and promoting electron transfer of Mn₂O₃ by C-hybridization to improve the peroxymonosulfate activation for bisphenol A degradation[J]. Environ. Res., 2025, 264: 120409 doi: 10.1016/j.envres.2024.120409
40. [40]
  FU J, GAO P, WANG L X, ZHANG Y Q, DENG Y H, HUANG R F, ZHAO S F, YU Z B, WEI Y C, WANG G F, ZHOU S Q. Regulating crystal facets of MnO₂ for enhancing peroxymonosulfate activation to degrade pollutants: Performance and mechanism[J]. Catalysts, 2022, 12: 342 doi: 10.3390/catal12030342
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Degradation of tannic acid on activation of peroxymonosulfate mediated by β-MnO2

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Degradation of tannic acid on activation of peroxymonosulfate mediated by β-MnO₂