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Licensed Unlicensed Requires Authentication Published by De Gruyter December 16, 2015

Manganese Oxides in Heterogeneous (Photo)Catalysis: Possibilities and Challenges

Simon Ristig

Dr. Simon Ristig studied at the University of Duisburg-Essen, where he completed his Ph.D. in 2014 in inorganic chemistry, conducting research on alloyed noble metal nanoparticles. Since 2015 he is a postdoctoral researcher at the Max-Planck-Institute for Chemical Energy Conversion in the area of Nanobased Heterogeneous Catalysts with specialization on manganese oxide based photocatalysis materials.

, Niklas Cibura

Niklas Cibura obtained his M.Sc. degree of chemistry at the Ruhr-University-Bochum with the specialization on industrial chemistry and photocatalysis. At the beginning of September 2015, he has started his Ph.D. studies at the Max-Planck-Institute for Chemical Energy Conversion in the field of Nanobased Heterogeneous Catalysts with a focus on photocatalysis.

and Jennifer Strunk

Dr. Jennifer Strunk received her diploma and her PhD in industrial chemistry from the Ruhr-University Bochum in Germany. From 2008 to 2010 she stayed as postdoctoral fellow at the University of California, Berkeley, in the group of Prof. Alexis T. Bell. From 2010 to 2014 she was Junior Research Group Leader at the Ruhr-University Bochum, where she and her research group conducted fundamental studies of the reduction of carbon dioxide and of hydrogen evolution under highly controlled conditions. Since October 2014 she is Research Group Leader of the “Nanobased Heterogeneous Catalysts” (NanoCat) group at the Max-Planck-Institute for Chemical Energy Conversion. She is also a member of the “Center for Nanointergration Duisburg-Essen” (CENIDE) at the University Duisburg-Essen. Her current research focuses on structure-function relationships of photocatalysts in energy conversion reactions.

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The aim to develop active photocatalysts based on abundant elements for solar energy conversion reactions has sparked wide interest in manganese oxides as visible light-absorbing alternative to TiO2. Today, a multitude of different routes are available for the synthesis of MnOx species with specific stoichiometry, crystal structure, morphology, size or surface properties. Still, even for the bulk manganese oxides, some controversy remains, for example, with respect to the band gap, which hinders the targeted development of specific manganese oxide catalysts for photocatalysis. In classical heterogeneous catalysis and electrocatalysis, manganese oxides have been successfully used for a wide range of reactions, in particular in the field of (selective) oxidations. Photocatalytic applications have also been reported, but a true photocatalyst for the famous water-splitting reaction, deep insight into the prevailing mechanisms and an understanding of the involved processes has yet to be found. With this review, we aim to give a comprehensive overview over the structural, physical and catalytic properties of manganese oxides, together with an overview over suitable synthesis procedures. This will then serve as a basis for the discussion of the state of the art in the application of manganese oxides in catalysis and photocatalysis.

Funding statement: Funding: Part of this work was generously funded by the Mercator Research Center Ruhr (MERCUR) within the scope of the project “Photoactive Oxide Materials for the Visible Spectral Range,” project-ID Pr-2013-0047

About the authors

Simon Ristig

Dr. Simon Ristig studied at the University of Duisburg-Essen, where he completed his Ph.D. in 2014 in inorganic chemistry, conducting research on alloyed noble metal nanoparticles. Since 2015 he is a postdoctoral researcher at the Max-Planck-Institute for Chemical Energy Conversion in the area of Nanobased Heterogeneous Catalysts with specialization on manganese oxide based photocatalysis materials.

Niklas Cibura

Niklas Cibura obtained his M.Sc. degree of chemistry at the Ruhr-University-Bochum with the specialization on industrial chemistry and photocatalysis. At the beginning of September 2015, he has started his Ph.D. studies at the Max-Planck-Institute for Chemical Energy Conversion in the field of Nanobased Heterogeneous Catalysts with a focus on photocatalysis.

Jennifer Strunk

Dr. Jennifer Strunk received her diploma and her PhD in industrial chemistry from the Ruhr-University Bochum in Germany. From 2008 to 2010 she stayed as postdoctoral fellow at the University of California, Berkeley, in the group of Prof. Alexis T. Bell. From 2010 to 2014 she was Junior Research Group Leader at the Ruhr-University Bochum, where she and her research group conducted fundamental studies of the reduction of carbon dioxide and of hydrogen evolution under highly controlled conditions. Since October 2014 she is Research Group Leader of the “Nanobased Heterogeneous Catalysts” (NanoCat) group at the Max-Planck-Institute for Chemical Energy Conversion. She is also a member of the “Center for Nanointergration Duisburg-Essen” (CENIDE) at the University Duisburg-Essen. Her current research focuses on structure-function relationships of photocatalysts in energy conversion reactions.


We thank Pascal Düngen (MPI-CEC) for the Raman microscope measurements and Dr. Thomas Reinecke (Department of Mineralogy, Ruhr-University Bochum) for the PXRD measurements.


1. Fox MA, Dulay MT. Heterogeneous photocatalysis.Chem Rev 1993;93:341–57.10.1021/cr00017a016Search in Google Scholar

2. Pelaez M, Nolan NT, Pillai SC, Seery MK, Falaras P, Kontos AG, et al. A review on the visible light active titanium dioxide photocatalysts for environmental applications.Appl Catal B 2012;125:331–49.10.1016/j.apcatb.2012.05.036Search in Google Scholar

3. Mills A, Le Hunte S. An overview of semiconductor photocatalysis.J Photochem Photobiol A Chem 1997;108:1–35.10.1016/S1010-6030(97)00118-4Search in Google Scholar

4. Lüken A, Muhler M, Strunk J. On the role of gold nanoparticles in the selective photooxidation of 2-propanol over Au/TiO2. Phys Chem Chem Phys 2015;17:10391–7.10.1039/C4CP05423GSearch in Google Scholar PubMed

5. Panayotov DA, Burrows SP, Morris JR. Photooxidation mechanism of methanol on rutile TiO2 nanoparticles. J Phys Chem C 2012;116:6623–35.10.1021/jp209215cSearch in Google Scholar

6. Xu C, Xu C, Yang W, Ren Z, Dai D, Guo Q, et al. Strong photon energy dependence of the photocatalytic dissociation rate of methanol on TiO2(110). J Am Chem Soc 2013;135:19039–45.10.1021/ja4114598Search in Google Scholar PubMed

7. Habisreutinger SN, Schmidt-Mende L, Stolarczyk JK. Photocatalytic reduction of CO2 on TiO2 and other semiconductors. Angew Chem Int Ed 2013;52:7372–408.10.1002/anie.201207199Search in Google Scholar PubMed

8. Lubitz W, Reijerse EJ, Messinger J. Solar water-splitting into H2 and O2: design principles of photosystem II and hydrogenases. Energy Environ Sci 2008;1:15.10.1039/b808792jSearch in Google Scholar

9. Peter LM, Upul Wijayantha, KG. Photoelectrochemical water splitting at semiconductor electrodes: fundamental problems and new perspectives. Chem Phys Chem 2014;15:1983–95.10.1002/cphc.201402024Search in Google Scholar PubMed

10. Lyons ME, Doyle RL, Fernandez D, Godwin IJ, Browne MP, Rovetta A. The mechanism and kinetics of electrochemical water oxidation at oxidized metal and metal oxide electrodes. Part 2. The surfaquo group mechanism: a mini review. Electrochem Commun 2014;45:56–9.10.1016/j.elecom.2014.04.019Search in Google Scholar

11. Dau H, Limberg C, Reier T, Risch M, Roggan S, Strasser P. The mechanism of water oxidation: from electrolysis via homogeneous to biological catalysis. Chem Cat Chem 2010;2:724–61.10.1002/cctc.201000126Search in Google Scholar

12. Al-Oweini R, Sartorel A, Bassil BS, Natali M, Berardi S, Scandola F, et al. Photocatalytic water oxidation by a mixed-valent Mn(III)₃Mn(IV)O₃ manganese oxo core that mimics the natural oxygen-evolving center. Angew Chem Int Ed Engl 2014;53:11182–5.10.1002/anie.201404664Search in Google Scholar PubMed

13. Brimblecombe R, Chen J, Wagner P, Buchhorn T, Dismukes GC, Spiccia L, et al. Photocatalytic oxygen evolution from non-potable water by a bioinspired molecular water oxidation catalyst. J Mol Catal A Chem 2011;338:1–6.10.1016/j.molcata.2011.02.006Search in Google Scholar

14. Brimblecombe R, Swiegers GF, Dismukes GC, Spiccia L. Sustained water oxidation photocatalysis by a bioinspired manganese cluster. Angew Chem Int Ed Engl 2008;47:7335–8.10.1002/anie.200801132Search in Google Scholar PubMed

15. Jiao F, Frei H. Nanostructured manganese oxide clusters supported on mesoporous silica as efficient oxygen-evolving catalysts. Chem Commun 2010;46:2920–2.10.1039/b921820cSearch in Google Scholar PubMed

16. El-Deab MS, Awad MI, Mohammad AM, Ohsaka T. Enhanced water electrolysis: Electrocatalytic generation of oxygen gas at manganese oxide nanorods modified electrodes. Electrochem Commun 2007;9:2082–7.10.1016/j.elecom.2007.06.011Search in Google Scholar

17. Najafpour MM, Ehrenberg T, Wiechen M, Kurz P. Calcium manganese(III) oxides (CaMn2O4.xH2O) as biomimetic oxygen-evolving catalysts. Angew Chem Int Ed Engl 2010;49:2233–7.10.1002/anie.200906745Search in Google Scholar PubMed

18. Mukhopadhyay S, Mandal SK, Bhaduri S, Armstrong WH. Manganese clusters with relevance to photosystem II. Chem Rev 2004;104:3981–4026.10.1021/cr0206014Search in Google Scholar PubMed

19. Kurz P, Berggren G, Anderlund MF, Styring S. Oxygen evolving reactions catalysed by synthetic manganese complexes: a systematic screening. Dalton Trans 2007;38:4258–61.10.1039/b710761gSearch in Google Scholar PubMed

20. Cady CW, Crabtree RH, Brudvig GW. Functional models for the oxygen-evolving complex of photosystem II. Coord Chem Rev 2008;252:444–55.10.1016/j.ccr.2007.06.002Search in Google Scholar PubMed PubMed Central

21. Shimazaki Y, Nagano T, Takesue H, Ye B, Tani F, Naruta Y. Characterization of a dinuclear MnV=O complex and is efficient evolution of O2 in the presence of water. Angew Chem Int Ed Engl 2004;43:98–100.10.1002/anie.200352564Search in Google Scholar

22. Iyer A, Galindo H, Sithambaram S, King’ondu C, Chen C, Suib SL. Nanoscale manganese oxide octahedral molecular sieves (OMS-2) as efficient photocatalysts in 2-propanol oxidation. Appl Catal A 2010;375:295–302.10.1016/j.apcata.2010.01.012Search in Google Scholar

23. Cao H, Suib SL. Highly efficient heterogeneous photooxidation of 2-propanol to acetone with amorphous manganese oxide catalysts. J Am Chem Soc 1994;116:5334–42.10.1021/ja00091a044Search in Google Scholar

24. Schurz F, Bauchert JM, Merker T, Schleid T, Hasse H, Gläser R. Octahedral molecular sieves of the type K-OMS-2 with different particle sizes and morphologies: impact on the catalytic properties in the aerobic partial oxidation of benzyl alcohol. Appl Catal A 2009;355:42–9.10.1016/j.apcata.2008.11.014Search in Google Scholar

25. Ahmed, Khalid Abdelazez Mohamed, Peng H, Wu K, Huang K. Hydrothermal preparation of nanostructured manganese oxides (MnOx) and their electrochemical and photocatalytic properties.Chem Eng J 2011;172:531–9.10.1016/j.cej.2011.05.070Search in Google Scholar

26. Chen J, Lin JC, Purohit V, Cutlip MB, Suib SL. Photoassisted catalytic oxidation of alcohols and halogenated hydrocarbons with amorphous manganese oxides. Catal Today 1997;33:205–14.10.1016/S0920-5861(96)00119-8Search in Google Scholar

27. Segal SR, Suib SL, Tang X, Satyapal S. Photoassisted decomposition of dimethyl methylphosphonate over amorphous manganese oxide catalysts. Chem Mater 1999;11:1687–95.10.1021/cm980664wSearch in Google Scholar

28. Linsebigler AL, Yates Jr, John T, Lu G, Yates JT. Photocatalysis on TiO2 surfaces: principles, mechanisms, and selected results. Chem Rev 1995;95:735–58.10.1021/cr00035a013Search in Google Scholar

29. Beranek R. (Photo)electrochemical methods for the determination of the band edge positions of TiO2-based nanomaterials. Adv Phys Chem 2011;2011:1–20.10.1155/2011/786759Search in Google Scholar

30. Kisch H. Semiconductor photocatalysis: principles and applications. Weinheim: Wiley-VCH;2015.10.1002/9783527673315Search in Google Scholar

31. Anta JA. Electron transport in nanostructured metal-oxide semiconductors. Curr Opin Colloid Interface Sci 2012;17:124–31.10.1016/j.cocis.2012.02.003Search in Google Scholar

32. Levy B. Photochemistry of nanostructured materials for energy applications. J Electroceram 1997;1:239–72.10.1023/A:1009983710819Search in Google Scholar

33. Brune H. Nanotechnology: assessment and perspectives. Berlin, New York: Springer; 2006. (Wissenschaftsethik und TechnikfolgenbeurteilungBd. 27).Search in Google Scholar

34. Arena F, Gumina B, Cannilla C, Spadaro L, Patti A, Spiccia L. Nanostructured MnOx catalysts in the liquid phase selective oxidation of benzyl alcohol with oxygen. Appl Catal B: Environ 2015;170–171:233–40.10.1016/j.apcatb.2015.01.040Search in Google Scholar

35. Anpo M, Kamat PV. Environmentally benign photocatalysts: applications of titanium oxide-based materials. New York: Springer; 2010.10.1007/978-0-387-48444-0Search in Google Scholar

36. Holleman AF, Wiberg E, Wiberg N. Lehrbuch der anorganischen Chemie. 102, stark umgearb. u. verb. Aufl. Berlin: de Gruyter, 2007.10.1515/9783110177701Search in Google Scholar

37. Jarosch D. Crystal structure refinement and reflectance measurements of hausmannite, Mn3O4. Miner Petrol 1987;37:15–23.10.1007/BF01163155Search in Google Scholar

38. Geller S. Structure of [alpha]-Mn2O3, (Mn0.983Fe0.017)2O3 and (Mn0.37Fe0.63)2O3 and relation to magnetic ordering. Acta Cryst 1971;B27:821–8.10.1107/S0567740871002966Search in Google Scholar

39. Menezes PW, Indra A, Littlewood P, Schwarze M, Göbel C, Schomäcker R, et al. Nanostructured manganese oxides as highly active water oxidation catalysts: A boost from manganese precursor chemistry. Chem Sus Chem 2014;7:2202–11.10.1002/cssc.201402169Search in Google Scholar PubMed

40. Bystrom A, Bystrom AM. The crystal structure of hollandite, the related manganese oxide minerals, and [alpha]-MnO2. Acta Cryst 1950;3:146–54.10.1107/S0365110X5000032XSearch in Google Scholar

41. Byström AM. The crystal structure of ramsdellite, an orthorombic modification of MnO2. Acta Chem Scand 1949;3:163–73.10.3891/acta.chem.scand.03-0163Search in Google Scholar

42. Zachau-Christiansen B, West K, Jacobsen T, Skaarup S. Insertion of lithium into the manganese dioxides: pyrolusite and ramsdellite.Solid State lonics 1994;70:401–6.10.1016/0167-2738(94)90344-1Search in Google Scholar

43. Suib SL. Structure, porosity, and redox in porous manganese oxide octahedral layer and molecular sieve materials. J Mater Chem 2008;18:1623.10.1039/b714966mSearch in Google Scholar

44. Makwana VD, Son Y, Howell AR, Suib SL. The role of lattice oxygen in selective benzyl alcohol oxidation using OMS-2 catalyst: a kinetic and isotope-labeling study. J Catal 2002;210:46–52.10.1006/jcat.2002.3680Search in Google Scholar

45. Son Y, Makwana VD, Howell AR, Suib SL. Efficient, catalytic, aerobic oxidation of alcohols with octahedral molecular sieves. Angew Chem 2001;113:4410–3.10.1002/1521-3757(20011119)113:22<4410::AID-ANGE4410>3.0.CO;2-XSearch in Google Scholar

46. Post JE. Manganese oxide minerals: crystal structures and economic and environmental significance. Proc Nat Acad Sci 1999;96:3447–54.10.1073/pnas.96.7.3447Search in Google Scholar

47. Frey CE, Kurz P. Water oxidation catalysis by synthetic manganese oxides with different structural motifs: a comparative study. Chemistry (Weinheim an der Bergstrasse, Germany) 2015;21:14958–68.10.1002/chem.201501367Search in Google Scholar

48. Kapteijn F, Vanlangeveld AD, Moulijn JA, Andreini A, Vuurman MA, Turek AM, et al. Alumina-Supported Manganese Oxide Catalysts: I. Characterization: Effect of Precursor and Loading. J Catal 1994;150:94–104.10.1006/jcat.1994.1325Search in Google Scholar

49. Azzoni CB, Mozzati MC, Galinetto P, Paleari A, Massarotti V, Capsoni D, et al. Thermal stability and structural transition of metastable Mn5O8: in situ micro-Raman study. Solid State Commun 1999;112:375–8.10.1016/S0038-1098(99)00368-3Search in Google Scholar

50. Stobbe ER, Boer BA de, Geus JW. The reduction and oxidation behaviour of manganese oxides. Catal Today 1999;47:161–7.10.1016/S0920-5861(98)00296-XSearch in Google Scholar

51. Aboukaïs A, Abi-Aad E, Taouk B. Supported manganese oxide on TiO2 for total oxidation of toluene and polycyclic aromatic hydrocarbons (PAHs): characterization and catalytic activity. Mater Chem Phys 2013;142:564–71.10.1016/j.matchemphys.2013.07.053Search in Google Scholar

52. Picasso G, Gutiérrez M, Pina MP, Herguido J. Preparation and characterization of Ce-Zr and Ce-Mn based oxides for n-hexane combustion: Application to catalytic membrane reactors. Chem Eng J 2007;126:119–30.10.1016/j.cej.2006.09.005Search in Google Scholar

53. Carnö J, Ferrandon M, Björnbom E, Järas S. Mixed manganese oxide/platinum catalysts for total oxidation of model gas from wood boilers. Appl Catal A 1997;155:265–81.10.1016/S0926-860X(97)80129-9Search in Google Scholar

54. Xu R, Wang X, Wang D, Zhou K, Li Y. Surface structure effects in nanocrystal MnO2 and Ag/MnO2 catalytic oxidation of CO. J Catal 2006;237:426–30.10.1016/j.jcat.2005.10.026Search in Google Scholar

55. Delimaris D, Ioannides T. VOC oxidation over MnOx–CeO2 catalysts prepared by a combustion method. Appl Catal B 2008;84:303–12.10.1016/j.apcatb.2008.04.006Search in Google Scholar

56. Rankin WJ, van Deventer, JS. The kinetics of the reduction of manganous oxide by graphite. J S Afr Inst Min Metall 1980;80:239–47.Search in Google Scholar

57. Kwon KD, Refson K, Sposito G. On the role of Mn(IV) vacancies in the photoreductive dissolution of hexagonal birnessite. Geochim Cosmochim Acta 2009;73:4142–50.10.1016/j.gca.2009.04.031Search in Google Scholar

58. Zhang Q, Cheng X, Zheng C, Feng X, Qiu G, Tan W, et al. Roles of manganese oxides in degradation of phenol under UV-Vis irradiation: adsorption, oxidation, and photocatalysis. J Environ Sci 2011;23:1904–10.10.1016/S1001-0742(10)60655-9Search in Google Scholar

59. Sherman DM. Electronic structures of iron(III) and manganese(IV) (hydr)oxide minerals: Thermodynamics of photochemical reductive dissolution in aquatic environments. Geochim Cosmochim 2005;69:3249–55.10.1016/j.gca.2005.01.023Search in Google Scholar

60. Asahi R, Morikawa T, Ohwaki T, Aoki K, Taga Y. Visible-light photocatalysis in nitrogen-doped titanium oxides. Science 2001;293:269–71.10.1126/science.1061051Search in Google Scholar PubMed

61. Li S, Ma Z, Zhang J, Wu Y, Gong Y. A comparative study of photocatalytic degradation of phenol of TiO2 and ZnO in the presence of manganese dioxides. Catal Today 2008;139:109–12.10.1016/j.cattod.2008.08.012Search in Google Scholar

62. Barakat NA, Woo K, Ansari SG, Ko J, Kanjwal MA, Kim HY. Preparation of nanofibers consisting of MnO/Mn3O4 by using the electrospinning technique: The nanofibers have two band-gap energies. Appl Phys A 2009;95:769–76.10.1007/s00339-008-5067-0Search in Google Scholar

63. Jha A, Thapa R, Chattopadhyay KK. Structural transformation from Mn3O4 nanorods to nanoparticles and band gap tuning via Zn doping. Mater Res Bull 2012;47:813–9.10.1016/j.materresbull.2011.11.057Search in Google Scholar

64. Dubal DP, Dhawale DS, Salunkhe RR, Pawar SM, Lokhande CD. A novel chemical synthesis and characterization of Mn3O4 thin films for supercapacitor application. Appl Surf Sci 2010;256:4411–6.10.1016/j.apsusc.2009.12.057Search in Google Scholar

65. Dubal DP, Dhawale DS, Salunkhe RR, Pawar SM, Fulari VJ, Lokhande CD. A novel chemical synthesis of interlocked cubes of hausmannite Mn3O4 thin films for supercapacitor application. J Alloys Compd 2009;484:218–21.10.1016/j.jallcom.2009.03.135Search in Google Scholar

66. Xu HY, Le Xu S, Li XD, Wang H, Yan H. Chemical bath deposition of hausmannite Mn3O4 thin films. Appl Surf Sci 2006;252:4091–6.10.1016/j.apsusc.2005.06.011Search in Google Scholar

67. Hosny NM, Dahshan A. Facile synthesis and optical band gap calculation of Mn3O4 nanoparticles. Mater Chem Phys 2012;137:637–43.10.1016/j.matchemphys.2012.09.068Search in Google Scholar

68. Javed Q, Feng-Ping W, Rafique MY, Toufiq AM, Iqbal MZ. Canted antiferromagnetic and optical properties of nanostructures of Mn2O3 prepared by hydrothermal synthesis. Chinese Phys B 2012;21:117311.10.1088/1674-1056/21/11/117311Search in Google Scholar

69. Javed Q, Wang FP, Rafique MY, Toufiq AM, Li QS, Mahmood H, et al. Diameter-controlled synthesis of α-Mn2O3 nanorods and nanowires with enhanced surface morphology and optical properties. Nanotechnology 2012;23:415603.10.1088/0957-4484/23/41/415603Search in Google Scholar PubMed

70. Zhang H, Ji Z, Xia T, Meng H, Low-Kam C, Liu R, et al. Use of metal oxide nanoparticle band gap to develop a predictive paradigm for oxidative stress and acute pulmonary inflammation. ACS Nano 2012;6:4349–68.10.1021/nn3010087Search in Google Scholar PubMed PubMed Central

71. Tian Z, Tong W, Wang J, Duan N, Krishnan VV, Suib SL. Manganese oxide mesoporous structures: mixed-valent semiconducting catalysts. Science 1997;276:926–30.10.1126/science.276.5314.926Search in Google Scholar

72. Sakai N, Ebina Y, Takada K, Sasaki T. Photocurrent generation from semiconducting manganese oxide nanosheets in response to visible light. J Phys Chem B 2005;109:9651–5.10.1021/jp0500485Search in Google Scholar PubMed

73. Pinaud BA, Chen Z, Abram DN, Jaramillo TF. Thin films of sodium birnessite-type MnO2: optical properties, electronic band structure, and solar photoelectrochemistry. J Phys Chem C 2011;115:11830–8.10.1021/jp200015pSearch in Google Scholar

74. Faleev SV, van Schilfgaarde M, Kotani T. All-electron self-consistent GW approximation: application to Si, MnO, and NiO. Phys Rev Lett 2004;93:126406.10.1103/PhysRevLett.93.126406Search in Google Scholar

75. Tran F, Blaha P. Accurate Band Gaps of Semiconductors and Insulators with a Semilocal Exchange-Correlation Potential. Phys Rev Lett 2009;102:226401.10.1103/PhysRevLett.102.226401Search in Google Scholar

76. Marsman M, Paier J, Stroppa A, Kresse G. Hybrid functionals applied to extended systems. J Phys Condens Matter 2008;20:64201.10.1088/0953-8984/20/6/064201Search in Google Scholar

77. Franchini C, Podloucky R, Paier J, Marsman M, Kresse G. Ground-state properties of multivalent manganese oxides: density functional and hybrid density functional calculations. Phys Rev B 2007;75:195128.10.1103/PhysRevB.75.195128Search in Google Scholar

78. Shaughnessy DA, Nitsche H, Booth CH, Shuh DK, Waychunas GA,Wilson RE, et al. Molecular interfacial reactions between Pu(VI) and manganese oxide minerals manganite and hausmannite. Environ Sci Technol 2003;37:3367–74.10.1021/es025989zSearch in Google Scholar

79. Janusz W, Galgan A. Electrical double layer at manganese oxides/1:1 electrolyte solution interface. Physicochem Probl Miner Process 2001;35:31–41.Search in Google Scholar

80. O’Reilly S, Hochella MF. Lead sorption efficiencies of natural and synthetic Mn and Fe-oxides. Geochim Cosmochim Acta 2003;67:4471–87.10.1016/S0016-7037(03)00413-7Search in Google Scholar

81. Prélot B, Villiéras F, Pelletier M, Razafitianamaharavo A, Thomas F, Poinsignon C. Structural–chemical disorder of manganese dioxides. J Colloid Interface Sci 2003;264:343–53.10.1016/S0021-9797(03)00394-1Search in Google Scholar

82. Natarajan R, Fuerstenau DW. Adsorption and flotation behavior of manganese dioxide in the presence of octyl hydroxamate. Int J Miner Proc 1983;11:139–53.10.1016/0301-7516(83)90006-6Search in Google Scholar

83. Gray MJ, Malati MA, Rophael MW. The point of zero charge of manganese dioxides. J Electroanal Chem 1978;89:135–40.10.1016/S0022-0728(78)80038-2Search in Google Scholar

84. Kosmulski M. Compilation of PZC and IEP of sparingly soluble metal oxides and hydroxides from literature. Adv Colloid Interface Sci 2009;152:14–25.10.1016/j.cis.2009.08.003Search in Google Scholar

85. Kosmulski M. pH-dependent surface charging and points of zero charge II. Update. J Colloid Interface Sci 2004;275:214–24.10.1016/j.jcis.2004.02.029Search in Google Scholar

86. Weisz PB. Deep sea manganese nodules as oxidation catalysts. J Catal 1968;10:407–8.10.1016/0021-9517(68)90156-5Search in Google Scholar

87. Cabrera AL, Maple MB, Arrhenius G. Catalysis of carbon monoxide methanation by deep sea manganate minerals. Appl Catal 1990;64:309–20.10.1016/S0166-9834(00)81568-7Search in Google Scholar

88. Katranas TK, Godelitsas AC, Vlessidis AG, Evmiridis NP. Propane reactions over natural Todorokite. Microporous Mesoporous Mater 2004;69:165–72.10.1016/j.micromeso.2004.02.007Search in Google Scholar

89. Wagloehner S, Nitzer-Noski M, Kureti S. Oxidation of soot on manganese oxide catalysts. Chem Eng J 2015;259:492–504.10.1016/j.cej.2014.08.021Search in Google Scholar

90. Shen YF, Zerger RP, Deguzman RN, Suib SL, McCurdy L, Potter DI, et al. Manganese oxide octahedral molecular sieves: preparation, characterization, and applications. Science 1993;260:511–5.10.1126/science.260.5107.511Search in Google Scholar

91. Kanungo B. Physicochemical properties of MnO and MnO2-CuO and their relationship with the catalytic activity for H O decomposition and CO oxidation J Catal. 1979;435:419–35.10.1016/0021-9517(79)90280-XSearch in Google Scholar

92. Robinson DM, Go YB, Mui M, Gardner G, Zhang Z, Mastrogiovanni D, et al. Photochemical water oxidation by crystalline polymorphs of manganese oxides: structural requirements for catalysis. J Am Chem Soc 2013;135:3494–501.10.1021/ja310286hSearch in Google Scholar PubMed

93. Robinson DM, Go YB, Greenblatt M, Dismukes GC. Water oxidation by lambda-MnO2: catalysis by the cubical Mn4O4 subcluster obtained by delithiation of spinel LiMn2O4. J Am Chem Soc 2010;132:11467–9.10.1021/ja1055615Search in Google Scholar PubMed

94. Jin K, Chu A, Park J, Jeong D, Jerng SE, Sim U, et al. Partially oxidized sub-10 nm MnO nanocrystals with high activity for water oxidation catalysis. Sci Rep 2015;5:10279.10.1038/srep10279Search in Google Scholar

95. Frey CE, Wiechen M, Kurz P. Water-oxidation catalysis by synthetic manganese oxides – systematic variations of the calcium birnessite theme. Dalton Trans 2014;43:4370–9.10.1039/C3DT52604FSearch in Google Scholar

96. Luo J, Zhang Q, Huang A, Giraldo O, Suib SL. Double-aging method for preparation of stabilized Na−Buserite and transformations to todorokites incorporated with various metals. Inorg Chem 1999;38:6106–13.10.1021/ic980675rSearch in Google Scholar

97. Luo S, Duan L, Sun B, Wei M, Li X, Xu A. Manganese oxide octahedral molecular sieve (OMS-2) as an effective catalyst for degradation of organic dyes in aqueous solutions in the presence of peroxymonosulfate. Appl Catal B: Environ 2015;164:92–9.10.1016/j.apcatb.2014.09.008Search in Google Scholar

98. Villalobos M, Toner B, Bargar J, Sposito G. Characterization of the manganese oxide produced by pseudomonas putida strain MnB1. Geochim Cosmochim 2003;67:2649–62.10.1016/S0016-7037(03)00217-5Search in Google Scholar

99. Zaharieva I, Najafpour MM, Wiechen M, Haumann M, Kurz P, Dau H. Synthetic manganese–calcium oxides mimic the water-oxidizing complex of photosynthesis functionally and structurally. Energy Environ Sci 2011;4:2400.10.1039/c0ee00815jSearch in Google Scholar

100. Wiechen M, Zaharieva I, Dau H, Kurz P. Layered manganese oxides for water-oxidation: alkaline earth cations influence catalytic activity in a photosystem II-like fashion. Chem Sci 2012;3:2330.10.1039/c2sc20226cSearch in Google Scholar

101. Son Y, Makwana VD, Howell AR, Suib SL. Efficient, catalytic, aerobic oxidation of alcohols with octahedral molecular sieves. Angew Chem Int Ed 2001;40:4280–3.10.1002/1521-3773(20011119)40:22<4280::AID-ANIE4280>3.0.CO;2-LSearch in Google Scholar

102. Tian Z, Yin Y, Suib SL, O’young CL. Effect of Mg2+ ions on the formation of todorokite type manganese oxide octahedral molecular sieves. Chem Mater 1997;9:1126–33.10.1021/cm960478vSearch in Google Scholar

103. Brock SL, Duan N, Tian ZR, Giraldo O, Zhou H, Suib SL. A review of porous manganese oxide materials. Chem Mater 1998;10:2619–28.10.1021/cm980227hSearch in Google Scholar

104. Takahashi Y, Manceau A, Geoffroy N, Marcus MA, Usui A. Chemical and structural control of the partitioning of Co, Ce, and Pb in marine ferromanganese oxides. Geochim Cosmochim Acta 2007;71:984–1008.10.1016/j.gca.2006.11.016Search in Google Scholar

105. Tusar NN, Jank S, Gläser R. Manganese-Containing Porous Silicates: Synthesis Structural Properties and Catalytic Applications. Chem Cat Chem 2011;3:254–69.10.1002/chin.201115209Search in Google Scholar

106. Morita M, Iwakura C, Tamura H. The anodic characteristics of massive manganese oxide electrode. Electrochim Acta 1979;24:357–62.10.1016/0013-4686(79)87019-XSearch in Google Scholar

107. Trasatti S. Electrocatalysis by oxides –Attempt at a unifying approach. J Electroanal Chem Interfacial Electrochem 1980;111:125–31.10.1016/S0022-0728(80)80084-2Search in Google Scholar

108. Singh A, Roy Chowdhury D, Amritphale SS, Chandra N, Singh IB. Efficient electrochemical water oxidation catalysis by nanostructured Mn2O3. RSC Adv 2015;5:24200–4.10.1039/C4RA15113ESearch in Google Scholar

109. Gorlin Y, Jaramillo TF. A bifunctional nonprecious metal catalyst for oxygen reduction and water oxidation. J Am Chem Soc 2010;132:13612–4.10.1021/ja104587vSearch in Google Scholar PubMed

110. Kuo C, Mosa IM, Poyraz AS, Biswas S, El-Sawy AM, Song W, et al. Robust mesoporous manganese oxide catalysts for water oxidation. ACS Catal. 2015;5:1693–9.10.1021/cs501739eSearch in Google Scholar

111. Ching S, Kriz DA, Luthy KM, Njagi EC, Suib SL. Self-assembly of manganese oxide nanoparticles and hollow spheres. Catalytic activity in carbon monoxide oxidation. Chem Commun 2011;47:8286–8.10.1039/c1cc11764eSearch in Google Scholar PubMed

112. Wang Y, Kobayashi H, Yamaguchi K, Mizuno N. Manganese oxide-catalyzed transformation of primary amines to primary amides through the sequence of oxidative dehydrogenation and successive hydration. Chem Commun 2012;48:2642–4.10.1039/c2cc17499eSearch in Google Scholar PubMed

113. Durand JP, Senanayake SD, Suib SL, Mullins DR. Reaction of formic acid over amorphous manganese oxide catalytic systems: an In Situ study. J Phys Chem C 2010;114:20000–6.10.1021/jp104629jSearch in Google Scholar

114. Makwana V. The role of lattice oxygen in selective benzyl alcohol oxidation using OMS-2 Catalyst: A Kinetic and isotope-labeling study. J Catal 2002;210:46–52.10.1006/jcat.2002.3680Search in Google Scholar

115. Piumetti M, Fino D, Russo N. Mesoporous manganese oxides prepared by solution combustion synthesis as catalysts for the total oxidation of VOCs. Appl Catal B 2015;163:277–87.10.1016/j.apcatb.2014.08.012Search in Google Scholar

116. Rahaman H, Barman K, Jasimuddin S, Ghosh SK. Bifunctional gold–manganese oxide nanocomposites: benign electrocatalysts toward water oxidation and oxygen reduction. RSC Adv 2014;4:41976–81.10.1039/C4RA05240DSearch in Google Scholar

117. Tammam RH, Fekry AM, Saleh MM. Electrocatalytic oxidation of methanol on ordered binary catalyst of manganese and nickel oxide nanoparticles. Int J Hydrogen Energy 2015;40:275–83.10.1016/j.ijhydene.2014.03.109Search in Google Scholar

118. Li C, Melaet G, Ralston WT, An K, Brooks C, Ye Y, et al. High-performance hybrid oxide catalyst of manganese and cobalt for low-pressure methanol synthesis. Nat Commun 2015;6:6538.10.1038/ncomms7538Search in Google Scholar PubMed

119. Elmaci G, Frey CE, Kurz P, Zümreoğlu-Karan B. Water oxidation catalysis by birnessite@iron oxide core-shell nanocomposites. Inorg Chem 2015;54:2734–41.10.1021/ic502908wSearch in Google Scholar PubMed

120. Han Y, Chen F, Zhong Z, Ramesh K, Chen L, Widjaja E. Controlled synthesis, characterization, and catalytic properties of Mn(2)O(3) and Mn(3)O(4) nanoparticles supported on mesoporous silica SBA-15. J Phys Chem B 2006;110:24450–6.10.1021/jp064941vSearch in Google Scholar PubMed

121. Dong X, Shen W, Zhu Y, Xiong L, Shi J. Facile synthesis of manganese-loaded mesoporous silica materials by direct reaction between KMnO4 and an in-situ surfactant template. Adv Funct Mater 2005;15:955–60.10.1002/adfm.200400430Search in Google Scholar

122. Zhang J, Guo C, Zhang L, Li CM. Direct growth of flower-like manganese oxide on reduced graphene oxide towards efficient oxygen reduction reaction. Chem Commun 2013;49:6334–6.10.1039/c3cc42127aSearch in Google Scholar PubMed

123. Chandra S, Das P, Bag S, Bhar R, Pramanik P. Mn2O3 decorated graphene nanosheet: an advanced material for the photocatalytic degradation of organic dyes. Mater Sci Eng B 2012;177:855–61.10.1016/j.mseb.2012.04.006Search in Google Scholar

124. Lu X, Song C, Chang C, Teng Y, Tong Z, Tang X. Manganese Oxides supported on TiO 2 –graphene nanocomposite catalysts for selective catalytic reduction of NO X with NH3 at low temperature. Ind Eng Chem Res 2014;53:11601–10.10.1021/ie5016969Search in Google Scholar

125. Rekha M, Kathyayini H, Nagaraju N. Catalytic activity of manganese oxide supported on alumina in the synthesis of quinoxalines. Front Chem Sci Eng 2013;7:415–21.10.1007/s11705-013-1360-3Search in Google Scholar

126. Najafpour M, Hosseini S, Hołyńska M, Tomo T, Allakhverdiev S. Manganese oxides supported on gold nanoparticles: new findings and current controversies for the role of gold: Photosynthesis Research. Photosynth Res 2015;126:477–87.10.1007/s11120-015-0164-3Search in Google Scholar PubMed

127. Parida KM, Dash SS. Manganese containing MCM-41: Synthesis, characterization and catalytic activity in the oxidation of ethylbenzene. J Mol Catal A Chem 2009;306:54–61.10.1016/j.molcata.2009.02.022Search in Google Scholar

128. Vetrivel S, Pandurangan A. Aerial oxidation of p-isopropyltoluene over manganese containing mesoporous MCM-41 and Al-MCM-41 molecular sieves. J Mol Catal A Chem 2006;246:223–30.10.1016/j.molcata.2005.10.024Search in Google Scholar

129. Ramallo-López JM, Lede EJ, Requejo FG, Rodriguez JA, Kim J, Rosas-Salas R, et al. XANES characterization of extremely nanosized metal-carbonyl subspecies (Me = Cr, Mn, Fe, and Co) confined into the mesopores of MCM-41 materials. J Phys Chem B 2004;108:20005–10.10.1021/jp049241+Search in Google Scholar

130. Orlov A, Klinowski J. Oxidation of volatile organic compounds on SBA-15 mesoporous molecular sieves modified with manganese. Chemosphere 2009;74:344–8.10.1016/j.chemosphere.2008.08.049Search in Google Scholar PubMed

131. Pérez H, Navarro P, Delgado JJ, Montes M. Mn-SBA15 catalysts prepared by impregnation: Influence of the manganese precursor. Appl Catal A 2011;400:238–48.10.1016/j.apcata.2011.05.002Search in Google Scholar

132. Zhang FM, Liu BS, Zhang Y, Guo YH, Wan ZY, Subhan F. Highly stable and regenerable Mn-based/SBA-15 sorbents for desulfurization of hot coal gas. J Hazard Mater 2012;233–234:219–27.10.1016/j.jhazmat.2012.07.023Search in Google Scholar PubMed

133. Han Y, Chen F, Zhong Z, Ramesh K, Widjaja E, Chen L. Synthesis and characterization of Mn3O4 and Mn2O3 nanocrystals on SBA-15: Novel combustion catalysts at low reaction temperatures. Catal Commun 2006;7:739–44.10.1016/j.catcom.2006.08.006Search in Google Scholar

134. Han YF, Chen F, Ramesh K, Zhong Z, Widjaja E, Chen L. Preparation of nanosized Mn3O4/SBA-15 catalyst for complete oxidation of low concentration EtOH in aqueous solution with H2O2. Appl Catal B 2007;76:227–34.10.1016/j.apcatb.2007.05.031Search in Google Scholar

135. Yonemitsu M, Tanaka Y, Iwamoto M. Metal ion-planted MCM-41. 1. Planting of Manganese(II) ion into MCM-41 by a newly developed template-ion exchange method. Chem Mater 1997;9:2679–81.10.1021/cm970334wSearch in Google Scholar

136. Zhang Q, Wang Y, Itsuki S, Shishido T, Takehira K. Manganese-containing MCM-41 for epoxidation of styrene and stilbene. J Mol Catal A Chem 2002;188:189–200.10.1016/S1381-1169(02)00323-0Search in Google Scholar

137. Qi B, Lou L, Wang Y, Yu K, Yang Y, Liu S. Comparison of different prepared Mn-MCM-41 catalysts in the catalytic epoxidation of alkenes with 30% H2O2. Microporous Mesoporous Mater 2014;190:275–83.10.1016/j.micromeso.2014.02.018Search in Google Scholar

138. Derylo-Marczewska A, Gac W, Popivnyak N, Zukocinski G, Pasieczna S. The influence of preparation method on the structure and redox properties of mesoporous Mn-MCM-41 materials. Catal Today 2006;114:293–306.10.1016/j.cattod.2006.02.066Search in Google Scholar

139. Tang Q, Hu S, Chen Y, Guo Z, Hu Y, Chen Y, et al. Highly dispersed manganese oxide catalysts grafted on SBA-15: synthesis, characterization and catalytic application in trans-stilbene epoxidation. Microporous Mesoporous Mater 2010;132:501–9.10.1016/j.micromeso.2010.03.033Search in Google Scholar

140. Fernandes Ta, Nunes CD, Vaz PD, Calhorda MJ, Brandão P, Rocha J, et al. Synthesis and catalytic properties of manganese(II) and oxovanadium(IV) complexes anchored to mesoporous MCM-41. Microporous Mesoporous Mater 2008;112:14–25.10.1016/j.micromeso.2007.09.009Search in Google Scholar

141. Mahdavi V, Mardani M. Preparation of manganese oxide immobilized on SBA-15 by atomic layer deposition as an efficient and reusable catalyst for selective oxidation of benzyl alcohol in the liquid phase. Mater Chem Phys 2015;155:136–46.10.1016/j.matchemphys.2015.02.011Search in Google Scholar

142. Pickrahn KL, Park SW, Gorlin Y, Lee HB, Jaramillo TF, Bent SF. Active MnO x electrocatalysts prepared by atomic layer deposition for oxygen evolution and oxygen reduction reactions. Adv Energy Mater 2012;2:1269–77.10.1002/aenm.201200230Search in Google Scholar

143. Pickrahn KL, Gorlin Y, Seitz LC, Garg A, Nordlund D, Jaramillo TF, et al. Applications of ALD MnO to electrochemical water splitting. Phys Chem Chem Phys: PCCP 2015;17:14003–11.10.1039/C5CP00843CSearch in Google Scholar PubMed

144. Satish Kumar G, Palanichamy M, Hartmann M, Murugesan V. Hydrothermal incorporation of manganese in the framework of SBA-15. Catal Commun 2007;8:493–7.10.1016/j.catcom.2006.07.027Search in Google Scholar

145. Kumar GS, Palanichamy M, Hartmann M, Murugesan V. A new route for the synthesis of manganese incorporated SBA-15. Microporous Mesoporous Mater 2008;112:53–60.10.1016/j.micromeso.2007.09.012Search in Google Scholar

146. Selvaraj M, Lee TG. Direct synthesis of well-ordered and unusually reactive MnSBA-15 mesoporous molecular sieves with high manganese content. J Phys Chem B 2006;110:21793–802.10.1021/jp063957iSearch in Google Scholar PubMed

147. Chuang K, Liu Z, Chang Y, Lu C, Wey M. Study of SBA-15 supported catalysts for toluene and NO removal: the effect of promoters (Co, Ni, Mn, Ce). Reac Kinet Mech Cat 2010;99:409–420.10.1007/s11144-009-0140-zSearch in Google Scholar

148. Tomer VK, Duhan S, Adhyapak PV, Mulla IS, Gouma P. Mn-Loaded mesoporous silica nanocomposite: a highly efficient humidity sensor. J Am Ceram Soc 2015;98:741–7.10.1111/jace.13383Search in Google Scholar

149. Selvaraj M, Seshadri KS, Pandurangan A, Lee TG. Highly selective synthesis of trans-stilbene oxide over mesoporous Mn-MCM-41 and Zr–Mn-MCM-41 molecular sieves. Microporous Mesoporous Mater 2005;79:261–8.10.1016/j.micromeso.2004.11.009Search in Google Scholar

150. Selvaraj M, Sinha PK, Lee K, Ahn I, Pandurangan A, Lee TG. Synthesis and characterization of Mn–MCM-41and Zr–Mn-MCM-41. Microporous Mesoporous Mater 2005;78:139–49.10.1016/j.micromeso.2004.10.004Search in Google Scholar

151. Stoerzinger KA, Risch M, Han B, Shao-Horn Y. Recent insights into manganese oxides in catalyzing oxygen reduction kinetics. ACS Catal 2015;5:6021–31.10.1021/acscatal.5b01444Search in Google Scholar

152. Harriman A, Pickering IJ, Thomas JM, Christensen PA. Metal oxides as heterogeneous catalysts for oxygen evolution under photochemical conditions. J Chem Soc, Faraday Trans 1 1988;84:2795.10.1039/f19888402795Search in Google Scholar

Received: 2015-8-7
Accepted: 2015-11-13
Published Online: 2015-12-16
Published in Print: 2015-12-1

©2015 by De Gruyter Mouton

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