Springer Nature is making SARS-CoV-2 and COVID-19 research free. View research | View latest news | Sign up for updates

Natural Mn-todorokite as an efficient and green azo dye–degradation catalyst

  • 32 Accesses


A natural Mn mineral, i.e., todorokite [(Ca,Na,K)X(Mn4+,Mn3+)6O12·3.5H2O], has been collected in the Apulia region, south of Italy, and evaluated as an oxidation catalyst for the degradation of methyl orange (MO) dye. This Mn-todorokite mineral has been firstly characterized by X-ray diffraction, wavelength-dispersive X-ray fluorescence, BET, scanning electron microscopy, attenuated total reflectance Fourier transform infrared spectroscopy, and thermogravimetry. Catalytic dye-degradation data show that this Mn-todorokite can operate under strongly oxidizing potentials (Eh > + 400 mV) vs. standard hydrogen electrode performing fast MO degradation (t1/2 < 1 min). A detailed study using electron paramagnetic resonance spectroscopy revealed that, under oxidative conditions (Eh > + 450 mV), the active Mn centers of todorokite evolve rapidly through Mn3+/Mn4+ states and this is correlated with the fast catalytic degradation of MO. These results suggest Mn-todorokite mineral as an efficient, low-cost, and green catalyst which can be used for industrial and environmental purposes.

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

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6


  1. Al-Sagheer FA, Zaki MI (2004) Synthesis and surface characterization of todorokite-type microporous manganese oxides: implications for shape-selective oxidation catalysts. Microporous Mesoporous Mater 67:43–52. https://doi.org/10.1016/j.micromeso.2003.10.005

  2. Bish DL, Post JE (1989) Thermal behavior of complex, tunnel-structure manganese oxides. Am Miner 74:177–186

  3. Brock SL, Duan N, Tian ZR, Giraldo O, Zhou H, Suib SL (1998) A review of porous manganese oxide materials. Chem Mater 10:2619–2628. https://doi.org/10.1021/cm980227h

  4. Brown JP, Dietrich PS (1983) Mutagenicity of selected sulfonated azo dyes in the Salmonella/microsome assay: use of aerobic and anaerobic activation procedures. Mutat Res 116:305–315. https://doi.org/10.1016/0165-1218(83)90068-X

  5. Burgot J-L (2012) Ionic equilibria in analytical chemistry. Springer, New York, NY doi:https://doi.org/10.1007/978-1-4419-8382-4

  6. Cui H, Liu X, Tan W, Feng X, Liu F, Ruan HD (2008) Influence of Mn(III) availability on the phase transformation from layered buserite to tunnel-structured todorokite. Clay Clay Miner 56:397–403. https://doi.org/10.1346/CCMN.2008.0560401

  7. De Santis V, Caldara M, de Torres T, Ortiz JE (2010) Stratigraphic units of the Apulian Tavoliere plain (Southern Italy): chronology, correlation with marine isotope stages and implications regarding vertical movements. Sediment Geol 228:255–270

  8. Doglioni C, Mongelli F, Pieri P (1994) The Puglia uplift (SE-Italy): an anomaly in the foreland of the Apenninic subduction due to buckling of a thick continental lithosphere. Tectonics 13:1309–1321

  9. Ember E, Gazzaz HA, Rothbart S, Puchta R, van Eldik R (2010) MnII-A fascinating oxidation catalyst: mechanistic insight into the catalyzed oxidative degradation of organic dyes by H2O2. Appl Catal B Environ 95:179–191. https://doi.org/10.1016/j.apcatb.2009.12.013

  10. Fan J, Guo Y, Wang J, Fan M (2009) Rapid decolorization of azo dye methyl orange in aqueous solution by nanoscale zerovalent iron particles. J Hazard Mater 166:904–910. https://doi.org/10.1016/j.jhazmat.2008.11.091

  11. Feng X, Zhao H, Liu F, Cui H, Tan W, Li W (2015) Transformation from phyllomanganates to todorokite under various conditions: a review of implication for formation pathway of natural todorokite. In: Feng X, Li W, Zhu M, Sparks DL (eds) Advances in the environmental biogeochemistry of manganese oxides, vol 1197. ACS Symp Ser, pp 107–134. https://doi.org/10.1021/bk-2015-1197.ch006

  12. Ghosh R, Shen X, Villegas JC, Ding Y, Malinger K, Suib SL (2006) Role of manganese oxide octahedral molecular sieves in styrene epoxidation. J Phys Chem B 110:7592–7599. https://doi.org/10.1021/jp056961n

  13. Godelitsas A, Misaelides P, Katranas T, Triantafyllidis C, Klewe-Nebenius H, Pavlidou E, Anousis I (1999) Characterisation of natural microporous manganese oxides: the case of todorokite. In: Misaelides P, Macášek F, Pinnavaia TJ, Colella C (eds) Natural microporous materials in environmental technology, NATO science series (series E: applied sciences), vol 362. Springer, Dordrecht, pp 445–461. https://doi.org/10.1007/978-94-011-4499-5_34

  14. Golden DC, Chen CC, Dixon JB (1986) Synthesis of todorokite. Science 231:717–719. https://doi.org/10.1126/science.231.4739.717

  15. Golka K, Kopps S, Myslak ZW (2004) Carcinogenicity of azo colorants: influence of solubility and bioavailability. Toxicol Lett 151:203–210. https://doi.org/10.1016/j.toxlet.2003.11.016

  16. Kim JG, Dixon JB, Chusuei CC, Deng Y (2002) Oxidation of chromium(III) to (VI) by manganese oxides. Soil Sci Soc Am J 66:306–315. https://doi.org/10.2136/sssaj2002.3060

  17. Katranas TK, Godelitsas AC, Vlessidis AG, Evmiridis NP (2004) Propane reactions over natural todorokite. Micropor Mesopor Mat 69:165–172. https://doi.org/10.1016/j.micromeso.2004.02.007

  18. Kaur J, Bansal S, Singhal S (2013) Photocatalytic degradation of methyl orange using nanopowders synthesized via thermal decomposition of oxalate precursor method. Physica B 416:33–38. https://doi.org/10.1016/j.physb.2013.02.005

  19. Lee S, Xu H (2016) XRD and TEM studies on nanophase manganese oxides in freshwater ferromanganese nodules from Green Bay, Lake Michigan. Clay Clay Miner 64:523–536. https://doi.org/10.1346/CCMN.2016.064032

  20. Liu J, Cai J, Son YC, Gao Q, Suib SL, Aindow M (2002) Magnesium manganese oxide nanoribbons: synthesis, characterization, and catalytic application. J Phys Chem B 106:9761–9768. https://doi.org/10.1021/jp0208586

  21. Mathur N, Bhatnagar P, Sharma P (2012) Review of the mutagenicity of textile dye products. Univers J Environ Res Technol 2:1–18

  22. Matsuda E, Tanaka S, Koike K, Tanaka A, Sano M, Miyake T (2008) Synthesis of one-dimensional microporous todorokite and its catalytic activity in CO oxidation. Res Chem Intermediat 34:535–549. https://doi.org/10.1163/156856708784795527

  23. Mavrogiorgou A, Papastergiou M, Deligiannakis Y, Louloudi M (2014) Activated carbon functionalized with Mn(II) Schiff base complexes as efficient alkene oxidation catalysts: solid support matters. J Mol Catal Chem 393:8–17. https://doi.org/10.1016/j.molcata.2014.05.038

  24. Onda A, Hara S, Kajiyoshi K, Yanagisawa K (2007) Synthesis of manganese oxide octahedral molecular sieves containing cobalt, nickel, or magnesium, and the catalytic properties for hydration of acrylonitrile. Appl Catal A Gen 321:71–78. https://doi.org/10.1016/j.apcata.2007.01.037

  25. Ostwald J (1986) Some observations on the chemical composition of todorokite. Mineral Mag 50:336–340. https://doi.org/10.1180/minmag.1986.050.356.25

  26. Post JE (1999) Manganese oxide minerals: crystal structures and economic and environmental significance. Proc Natl Acad Sci 96:3447–3454. https://doi.org/10.1073/pnas.96.7.3447

  27. Post JE, Bish DL (1988) Rietveld refinement of the todorokite structure. Am Miner 73:861–869

  28. Potter RM, Rossman GR (1979) The tetravalent manganese oxides: identification, hydration, and structural relationships by infrared spectroscopy. Am Miner 64:1199–1218

  29. Rothbart S, van Eldik R (2013) Manganese compounds as versatile catalysts for the oxidative degradation of organic dyes. In: van Rudi E, Colin DH (Eds), Advances in inorganic chemistry, Academic Press, pp. 165–215, Chapter 5

  30. Roy S (1997) Genetic diversity of manganese deposition in the terrestrial geological record. In: Nicholson K, Hein JR, Buhn B, Dasgupta S (eds) Manganese mineralization: geochemistry and mineralogy of terrestrial and marine deposits, vol 119. Geological Society, London, Spec Pub, pp 5–27

  31. Seristatidou E, Mavrogiorgou A, Konstantinou I, Louloudi M, Deligiannakis Y (2015) Recycled carbon (RC) materials made functional: an efficient heterogeneous Mn-RC catalyst. J Mol Catal Chem 403:84–92. https://doi.org/10.1016/j.molcata.2015.04.001

  32. Shen Y-F, Suib SL, O’Young C-L (1994) Effects of inorganic cation templates on octahedral molecular sieves of manganese oxide. J Am Chem Soc 116:11020–11029. https://doi.org/10.1021/ja00103a018

  33. Shen YF, Zerger RP, DeGuzman RN, Suib SL, McCurdy L, Potter DI, O’Young CL (1993) Manganese oxide octahedral molecular sieves: preparation, characterization, and applications. Science 260:511–515. https://doi.org/10.1126/science.260.5107.511

  34. Siegel MD, Turner S (1983) Crystalline todorokite associated with biogenic debris in manganese nodules. Science 219:172–174. https://doi.org/10.1126/science.219.4581.172

  35. Sinisi R, Mameli P, Mongelli G, Oggiano G (2012) Different Mn-ores in a continental arc setting: geochemical and mineralogical evidences from Tertiary deposits of Sardinia (Italy). Ore Geol Rev 47:110–125. https://doi.org/10.1016/j.oregeorev.2012.03.006

  36. Sithambaram S, Ding Y, Li W, Shen X, Gaenzler F, Suib SL (2008a) Manganese octahedral molecular sieves catalyzed tandem process for synthesis of quinoxalines. Green Chem 10:1029–1032. https://doi.org/10.1039/b805155k

  37. Sithambaram S, Kumar R, Son Y, Suib SL (2008b) Tandem catalysis: direct catalytic synthesis of imines from alcohols using manganese octahedral molecular sieves. J Catal 253:269–277. https://doi.org/10.1016/j.jcat.2007.11.006

  38. Toloman D, Mesaros A, Popa A, Raita O, Silipas TD, Vasile BS, Pana O, Giurgiu LM (2013) Evidence by EPR of ferromagnetic phase in Mn-doped ZnO nanoparticles annealed at different temperatures. J Alloys Comp 551:502–507. https://doi.org/10.1016/j.jallcom.2012.10.183

  39. Tsui EY, Agapie T (2013) Reduction potentials of heterometallic manganese–oxido cubane complexes modulated by redox-inactive metals. Proc Natl Acad Sci 110:10084–10088. https://doi.org/10.1073/pnas.1302677110

  40. Turner S, Buseck PR (1981) Todorokites: a new family of naturally occurring manganese oxides. Science 212:1024–1027. https://doi.org/10.1126/science.212.4498.1024

  41. Walton KS, Snurr RQ (2007) Applicability of the BET method for determining surface areas of microporous metal−organic frameworks. J Am Chem Soc 129:8552–8556. https://doi.org/10.1021/ja071174k

  42. Zhang Q, Cheng X, Zheng C, Feng X, Qiu G, Tan W, Liu F (2011) Roles of manganese oxides in degradation of phenol under UV-Vis irradiation: adsorption, oxidation, and photocatalysis. J Environ Sci 23:1904–1910. https://doi.org/10.1016/S1001-0742(10)60655-9

Download references


E.B. thanks Dr. George A. Sotiriou, Department of Microbiology, Tumor and Cell Biology, Karolinska Institutet (Solna, Sweden), for SSA measurements. C.Z. thanks Dr. Giorgio S. Senesi, CNR-Istituto per la Scienza e la Tecnologia dei Plasmi (Bari, Italy), for SEM analysis.

Author information

Correspondence to Claudio Zaccone.

Additional information

Publisher’s note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Responsible editor: Santiago V. Luis

Electronic supplementary material


(DOCX 447 kb)

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Bletsa, E., Zaccone, C., Miano, T. et al. Natural Mn-todorokite as an efficient and green azo dye–degradation catalyst. Environ Sci Pollut Res (2020). https://doi.org/10.1007/s11356-019-07524-6

Download citation


  • Electron paramagnetic resonance
  • Redox evolution
  • Mn centers
  • Oxidation potential
  • Methyl orange