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.
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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
Bish DL, Post JE (1989) Thermal behavior of complex, tunnel-structure manganese oxides. Am Miner 74:177–186
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
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
Burgot J-L (2012) Ionic equilibria in analytical chemistry. Springer, New York, NY doi:https://doi.org/10.1007/978-1-4419-8382-4
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
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
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
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
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
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
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
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
Golden DC, Chen CC, Dixon JB (1986) Synthesis of todorokite. Science 231:717–719. https://doi.org/10.1126/science.231.4739.717
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
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
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
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
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
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
Mathur N, Bhatnagar P, Sharma P (2012) Review of the mutagenicity of textile dye products. Univers J Environ Res Technol 2:1–18
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
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
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
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
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
Post JE, Bish DL (1988) Rietveld refinement of the todorokite structure. Am Miner 73:861–869
Potter RM, Rossman GR (1979) The tetravalent manganese oxides: identification, hydration, and structural relationships by infrared spectroscopy. Am Miner 64:1199–1218
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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.
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Bletsa, E., Zaccone, C., Miano, T. et al. Natural Mn-todorokite as an efficient and green azo dye–degradation catalyst. Environ Sci Pollut Res 27, 9835–9842 (2020). https://doi.org/10.1007/s11356-019-07524-6
- Electron paramagnetic resonance
- Redox evolution
- Mn centers
- Oxidation potential
- Methyl orange