European Journal of Inorganic Chemistry

Cover image for Vol. 2014 Issue 4

Special Issue: Water Oxidation Chemistry (Cluster Issue)

February 2014

Volume 2014, Issue 4

Pages 568–790

Issue edited by: Dennis G. H. Hetterscheid, Licheng Sun

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Cover Profile
    4. Editorial
    5. Masthead
    6. Guest Editorial
    7. Essay
    8. Back Cover
    9. Graphical Abstract
    10. News
    11. Further Masthead
    12. Microreviews
    13. Short Communication
    14. Full Papers
    1. You have free access to this content
      N-Heterocyclic Dicarbene Iridium(III) Catalysts Enabling Water Oxidation under Visible Light Irradiation (Eur. J. Inorg. Chem. 4/2014)

      Andrea Volpe, Andrea Sartorel, Cristina Tubaro, Laura Meneghini, Marilena Di Valentin, Claudia Graiff and Marcella Bonchio

      Version of Record online: 3 FEB 2014 | DOI: 10.1002/ejic.201490015

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      The cover picture shows the novel dicarbene iridium(III) complex and oxygen evolution as a result of its catalytic action under visible light irradiation. This is one key goal of the HELIOS strategic project, targeting new molecules and nanomaterials for solar energy schemes, as represented by the fullerene sunflower logo. Dr. Rami Al-Oweini (ITM-CNR Postdoctoral Fellow) is acknowledged for his creative design and for putting together the cover illustration. Details are discussed in the article by C. Tubaro, M. Bonchio et al. on p. 665 ff. For more on the story behind the cover research, see the Cover Profile.

  2. Cover Profile

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    2. Cover Picture
    3. Cover Profile
    4. Editorial
    5. Masthead
    6. Guest Editorial
    7. Essay
    8. Back Cover
    9. Graphical Abstract
    10. News
    11. Further Masthead
    12. Microreviews
    13. Short Communication
    14. Full Papers
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      N-Heterocyclic Dicarbene Iridium(III) Catalysts Enabling Water Oxidation under Visible Light Irradiation (page 568)

      Andrea Volpe, Andrea Sartorel, Cristina Tubaro, Laura Meneghini, Marilena Di Valentin, Claudia Graiff and Marcella Bonchio

      Version of Record online: 3 FEB 2014 | DOI: 10.1002/ejic.201301589

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      Any new progress towards solar fuels is of paramount importance for a possible sustainable future. Our mission is to make it real...

      Read more about the story behind the cover in the Cover Profile and about the research itself on p. 665 ff.

  3. Editorial

    1. Top of page
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    3. Cover Profile
    4. Editorial
    5. Masthead
    6. Guest Editorial
    7. Essay
    8. Back Cover
    9. Graphical Abstract
    10. News
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    12. Microreviews
    13. Short Communication
    14. Full Papers
    1. Water Oxidation

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      Throwing Light on Water Oxidation (page 569)

      Karen J. Hindson

      Version of Record online: 3 FEB 2014 | DOI: 10.1002/ejic.201301597

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      EurJIC brings you a fine collection of studies into the dynamic, stimulating and highly topical field of Water Oxidation. Guest Editors Dennis Hetterscheid and Licheng Sun enthusiastically provided their broad expertise on this topic to compile an issue containing many different points of view on this very important subject.

  4. Masthead

    1. Top of page
    2. Cover Picture
    3. Cover Profile
    4. Editorial
    5. Masthead
    6. Guest Editorial
    7. Essay
    8. Back Cover
    9. Graphical Abstract
    10. News
    11. Further Masthead
    12. Microreviews
    13. Short Communication
    14. Full Papers
  5. Guest Editorial

    1. Top of page
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    4. Editorial
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    6. Guest Editorial
    7. Essay
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    10. News
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    12. Microreviews
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    14. Full Papers
    1. Water Oxidation

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      Water Oxidation (pages 571–572)

      Dennis G. H. Hetterscheid and Licheng Sun

      Version of Record online: 3 FEB 2014 | DOI: 10.1002/ejic.201301408

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      An overview of the papers in this cluster issue is presented.

      “...in recent years, quite some progress has been made in our understanding of the catalytic water oxidation processes. In order to further boost the momentum of the field and to provide tools for new researchers entering the field of catalytic water oxidation, we have guest-edited this Cluster Issue of EurJIC on water oxidation.”

      Read more by the Guest Editors on p. 571.

  6. Essay

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    1. Oxygen Liberation

      Photo-Oxidation of Water under Ambient Conditions – The Search for Effective Oxygen-Evolving Catalysts (pages 573–580)

      Anthony Harriman

      Version of Record online: 3 FEB 2014 | DOI: 10.1002/ejic.201301540

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      Mimicking natural photosynthesis that leads to CO2 fixation and concomitant O2 liberation from water remains an elusive goal. New (photo)anodes and studies of mechanisms for water oxidation continue to be reported, but there is still no sign of a viable artificial photosynthetic system worthy of scaling up to industrial proportions. This essay explores the underlying reasons for this but seeks to reassure investors that there is both a market and an outstanding chance for profitable returns.

  7. Back Cover

    1. Top of page
    2. Cover Picture
    3. Cover Profile
    4. Editorial
    5. Masthead
    6. Guest Editorial
    7. Essay
    8. Back Cover
    9. Graphical Abstract
    10. News
    11. Further Masthead
    12. Microreviews
    13. Short Communication
    14. Full Papers
    1. You have free access to this content
      Al-Modified Zinc Oxide Nanorods for Photoelectrochemical Water Oxidation (Eur. J. Inorg. Chem. 4/2014)

      Monika Fekete, Wiebke Ludwig, Sophie Gledhill, Jie Chen, Antonio Patti and Leone Spiccia

      Version of Record online: 3 FEB 2014 | DOI: 10.1002/ejic.201490017

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      The back cover picture shows photocatalytic water splitting by zinc oxide nanorod arrays prepared by using a simple, template-free, low-temperature electrochemical deposition process. When tested in borate buffer, the as-deposited ZnO nanostructures exhibit a high and stable water oxidation activity, even without additional surface treatment or coating. Details are discussed in the article by L. Spiccia et al. on p. 750 ff.

  8. Graphical Abstract

    1. Top of page
    2. Cover Picture
    3. Cover Profile
    4. Editorial
    5. Masthead
    6. Guest Editorial
    7. Essay
    8. Back Cover
    9. Graphical Abstract
    10. News
    11. Further Masthead
    12. Microreviews
    13. Short Communication
    14. Full Papers
  9. News

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    4. Editorial
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  10. Further Masthead

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    4. Editorial
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    9. Graphical Abstract
    10. News
    11. Further Masthead
    12. Microreviews
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  11. Microreviews

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    1. Photosynthetic Oxygen Evolution

      Artificial Manganese Center Models for Photosynthetic Oxygen Evolution in Photosystem II (pages 595–606)

      Masanari Hirahara, Akinori Shoji and Masayuki Yagi

      Version of Record online: 7 OCT 2013 | DOI: 10.1002/ejic.201300683

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      To achieve artificial photosynthesis, the development of water oxidation catalysts is key. The photosynthetic oxygen evolving complex (OEC) is composed of a Mn cluster and is an excellent example of such a catalyst. Significant progress has been made in the development of Mn complexes as OEC models. The molecular aspects and activities of Mn complexes toward water oxidation catalysis are reviewed.

    2. Water Oxidation Catalysts

      Mechanistic Approaches to Molecular Catalysts for Water Oxidation (pages 607–618)

      Takashi Kikuchi and Koji Tanaka

      Version of Record online: 29 AUG 2013 | DOI: 10.1002/ejic.201300716

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      Selected current literature on homogeneous molecular catalysts for water oxidation with the use of transition-metal complexes is reviewed. Special attention is paid to the mechanism of O–O bond formation in ruthenium-based catalysts. This review surveys rational approaches to conduct oxygen evolution near the thermodynamic limit.

    3. Water Oxidation Mechanisms

      Application of Pulse Radiolysis to Mechanistic Investigations of Water Oxidation Catalysis (pages 619–634)

      Dmitry E. Polyansky, James K. Hurst and Sergei V. Lymar

      Version of Record online: 18 SEP 2013 | DOI: 10.1002/ejic.201300753

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      The ability of pulse radiolysis to generate strong one-electron oxidants makes it a powerful tool for mechanistic studies of water oxidation catalysis. This assertion is documented by a review of its application to studies of both heterogeneous and homogeneous catalysts from which the optical spectra and redox dynamics of key catalytic intermediates have been determined.

    4. Solar Fuel Catalysts

      Polyoxometalate Multi-Electron-Transfer Catalytic Systems for Water Splitting (pages 635–644)

      Jordan M. Sumliner, Hongjin Lv, John Fielden, Yurii V. Geletii and Craig L. Hill

      Version of Record online: 17 JAN 2014 | DOI: 10.1002/ejic.201301573

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      Polyoxometalates (POMs) have enjoyed recent success as catalysts in the multi-electron water oxidation and reduction reactions. They have also been incorporated into photoanodes for heterogeneous water oxidation. We address the challenges that remain and highlight upcoming advances in the field.

    5. Water Oxidation

      Homogeneous versus Heterogeneous Catalysts in Water Oxidation (pages 645–659)

      Shunichi Fukuzumi and Dachao Hong

      Version of Record online: 23 AUG 2013 | DOI: 10.1002/ejic.201300684

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      Comparison of homogeneous and heterogeneous catalysts in water oxidation is described by focusing on the conversion of various metal complexes into nanoparticles, which act as the actual reactive catalysts in water oxidation.

  12. Short Communication

    1. Top of page
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    3. Cover Profile
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    14. Full Papers
    1. Binary Metal Oxide Film Catalysts

      Water Oxidation Catalysis: Survey of Amorphous Binary Metal Oxide Films Containing Lanthanum and Late 3d Transition Metals (pages 660–664)

      Cuijuan Zhang, Simon Trudel and Curtis P. Berlinguette

      Version of Record online: 25 SEP 2013 | DOI: 10.1002/ejic.201300765

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      Amorphous binary LaMOx (M = Cr, Mn, Fe, Co, and Ni) films, prepared by a photochemical decomposition process, show superior electrocatalytic activity towards the oxygen evolution reaction (OER) relative to related crystalline materials. The trend in the activity follows the M–OH bond strengths, akin to crystalline materials.

  13. Full Papers

    1. Top of page
    2. Cover Picture
    3. Cover Profile
    4. Editorial
    5. Masthead
    6. Guest Editorial
    7. Essay
    8. Back Cover
    9. Graphical Abstract
    10. News
    11. Further Masthead
    12. Microreviews
    13. Short Communication
    14. Full Papers
    1. Water Oxidation Catalysts

      N-Heterocyclic Dicarbene Iridium(III) Catalysts Enabling Water Oxidation under Visible Light Irradiation (pages 665–675)

      Andrea Volpe, Andrea Sartorel, Cristina Tubaro, Laura Meneghini, Marilena Di Valentin, Claudia Graiff and Marcella Bonchio

      Version of Record online: 28 AUG 2013 | DOI: 10.1002/ejic.201300703

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      The dicarbene iridium(III) complex [IrClCp*(di-NHC)](PF6) (2) is an efficient catalyst for the oxidation of water both in the dark (CeIV or NaIO4 as sacrificial oxidants) and under photoirradiation conditions {[Ru(bpy)3]2+ as photosensitizer and persulfate as sacrificial electron acceptor}.

    2. Water Oxidation

      How Do Proximal Hydroxy or Methoxy Groups on the Bidentate Ligand Affect [(2,2′;6′,2"-Terpyridine)Ru(N,N)X] Water-Oxidation Catalysts? Synthesis, Characterization, and Reactivity at Acidic and Near-Neutral pH (pages 676–689)

      David C. Marelius, Salome Bhagan, David J. Charboneau, Kristine M. Schroeder, Jayneil M. Kamdar, Amanda R. McGettigan, Benjamin J. Freeman, Curtis E. Moore, Arnold L. Rheingold, Andrew L. Cooksy, Diane K. Smith, Jared J. Paul, Elizabeth T. Papish and Douglas B. Grotjahn

      Version of Record online: 18 OCT 2013 | DOI: 10.1002/ejic.201300826

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      Oxygenated substituents (protic OH and aprotic OMe) are compared at positions near to (figure, left) and far from (figure, right) the active site of water-oxidation catalysts. Facile aquation promoted by a proximal substituent, hydrogen bonding, and pH-sensitive redox and UV/Vis spectra are seen, along with either enhanced or reduced catalytic rates.

    3. Mechanistic Aspects of Water Oxidation Catalyzed by Organometallic Iridium Complexes (pages 690–697)

      Arianna Savini, Alberto Bucci, Gianfranco Bellachioma, Luca Rocchigiani, Cristiano Zuccaccia, Antoni Llobet and Alceo Macchioni

      Version of Record online: 19 JUL 2013 | DOI: 10.1002/ejic.201300530

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      Mechanistic studies for [Cp*IrLn]c+ water-oxidation catalysts allowed the interception of an intermediate IrIV–OH species. The latter decays with second-order kinetics in Ir, probably because of disproportion into IrIII–OH and IrV=O. The rate-determining step of the cycle seems to be the last oxidative step in which IrIV(O–O) is transformed into IrV(O–O).

    4. The Effects of Electron-Donating Substituents on [Ir(bpy)Cp*Cl]+: Water Oxidation versus Ligand Oxidative Modifications (pages 698–707)

      Teng Zhang, Kathryn E. deKrafft, Jin-Liang Wang, Cheng Wang and Wenbin Lin

      Version of Record online: 5 NOV 2013 | DOI: 10.1002/ejic.201300882

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      A series of [Ir(bpy)Cp*Cl]Cl complexes with 4,4′- and 6,6′-substituents on the bipyridine ring were examined for water oxidation. These complexes are oxidized electrochemically or with Ru(bpy)33+ without producing oxygen, but can generate oxygen with NaIO4 and Ce4+ as oxidants.

    5. Bimetallic Iridium–Carbene Complexes with Mesoionic Triazolylidene Ligands for Water Oxidation Catalysis (pages 708–714)

      Ana Petronilho, James A. Woods, Stefan Bernhard and Martin Albrecht

      Version of Record online: 30 AUG 2013 | DOI: 10.1002/ejic.201300843

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      Ditopic triazolylidene–iridium complexes were evaluated as water oxidation catalysts; the bimetallic arrangement enhances the maximum turnover frequency considerably in catalytic experiments that use low catalyst loadings.

    6. Water Oxidation by Mononuclear Ruthenium Complex with a Pentadentate Isoquinoline–Bipyridyl Ligand (pages 715–721)

      Manohar Vennampalli, Guangchao Liang, Charles Edwin Webster and Xuan Zhao

      Version of Record online: 8 JAN 2014 | DOI: 10.1002/ejic.201301393

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      Mononuclear Ru complexes with a pentadentate ligand, N,N-bis[(isoquinolin-1-yl)methyl][6-(pyridin-2-yl)pyridin-2-yl]methanamine (DIQ-Bpy), were synthesized and characterized. The effects of isoquinoline groups on the electrochemistry and the activity of [Ru(DIQ-Bpy)(H2O)]2+ on water oxidation are discussed.

    7. Mixed-Valent Compounds

      Synthesis and Structures of Mixed-Valence Oxido-Bridged Diruthenium Complexes Bearing Ethylbis(2-pyridylmethyl)amine (pages 722–727)

      Tomoyo Suzuki, Kazuhiro Matsuya, Tatsuya Kawamoto and Hirotaka Nagao

      Version of Record online: 5 NOV 2013 | DOI: 10.1002/ejic.201301070

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      Mixed-valence oxido-bridged halogeno (Cl and Br) diruthenium complexes bearing ethylbis(2-pyridylmethyl)amine (ebpma) ligands, for which the oxidation state of the ruthenium centers is RuIII–RuIV, have been synthesized by reduction of a trihalogenoruthenium(III) complex in acetone/water under air.

    8. Water Oxidation

      Reaction Mechanism of Water Oxidation Catalyzed by Iron Tetraamido Macrocyclic Ligand Complexes – A DFT Study (pages 728–741)

      Rong-Zhen Liao, Xi-Chen Li and Per E. M. Siegbahn

      Version of Record online: 24 SEP 2013 | DOI: 10.1002/ejic.201300710

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      The mechanism of water oxidation catalyzed by iron tetraamido macrocyclic ligand (TAML) complexes and catalyst deactivation are investigated by DFT calculations.

    9. Periodate as an Oxidant for Catalytic Water Oxidation: Oxidation via Electron Transfer or O-Atom Transfer? (pages 742–749)

      Dennis G. H. Hetterscheid and Joost N. H. Reek

      Version of Record online: 31 MAY 2013 | DOI: 10.1002/ejic.201300249

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      Treatment of water with periodate in the presence of [IrCp*(Me2NHC)(OH)2] results in formation of O2. DFT calculations and in situ mass spectrometry experiments point to a mechanism involving one or two O-atom-transfer steps, rather than electron-transfer steps only. Results must thus be interpreted cautiously when periodate is used as an oxidant in the study of catalytic water oxidation.

    10. Al-Modified Zinc Oxide Nanorods for Photoelectrochemical Water Oxidation (pages 750–759)

      Monika Fekete, Wiebke Ludwig, Sophie Gledhill, Jie Chen, Antonio Patti and Leone Spiccia

      Version of Record online: 7 OCT 2013 | DOI: 10.1002/ejic.201300668

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      Pristine and aluminium-modified zinc oxide nanorod arrays, prepared by low-temperature electrodeposition, have been tested as water oxidation photoanodes under 1 Sun illumination and exhibited high photocurrents even at low applied potentials. Long-term stability was improved by using phosphate and borate buffers.

    11. The Effect of the Hydrogenation Temperature on TiO2 Nanostructures for Photoelectrochemical Water Oxidation (pages 760–766)

      Yi Yang, Yichuan Ling, Gongming Wang and Yat Li

      Version of Record online: 19 SEP 2013 | DOI: 10.1002/ejic.201300760

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      We report the effect of the hydrogenation temperature on TiO2 nanowires grown on Ti foil as photoanodes for the photoelectrochemical water oxidation. Hydrogenated rutile and anatase TiO2 photoanodes achieved their optimal performance at a hydrogenation temperature of 350 and 550 °C, respectively. The photoanode performance is closely related to the enhancement of the carrier density of TiO2.

    12. GaN:ZnO Activity Modulation

      Effect of Hydrogen and Oxygen Evolution Cocatalysts on Photocatalytic Activity of GaN:ZnO (pages 767–772)

      Anke Xiong, Taizo Yoshinaga, Takahiro Ikeda, Masaki Takashima, Takashi Hisatomi, Kazuhiko Maeda, Toru Setoyama, Toshiharu Teranishi and Kazunari Domen

      Version of Record online: 16 JUL 2013 | DOI: 10.1002/ejic.201300439

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      The effects of coloading H2 and O2 evolution co-catalysts on the photocatalytic activity of GaN:ZnO for overall water splitting were studied. The activity of GaN:ZnO was more potently limited by H2 evolution reactions whereas coloading of O2 evolution cocatalysts modestly improved photocatalytic performance.

    13. Solar Water Splitting

      Quantum-Dot-Sensitized Nitrogen-Doped ZnO for Efficient Photoelectrochemical Water Splitting (pages 773–779)

      Chih Kai Chen, Yen-Ping Shen, Hao Ming Chen, Chih-Jung Chen, Ting-Shan Chan, Jyh-Fu Lee and Ru-Shi Liu

      Version of Record online: 14 NOV 2013 | DOI: 10.1002/ejic.201301310

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      We have prepared a photoelectrode by sensitization of a ZnO:N nanowire array by CdTe quantum dots. The photoelectrode improves the harvest of visible light significantly and, thus, enhances the photoelectrochemical cell performance.

    14. Biogenic Water-Oxidation Catalysts

      Biogenic Manganese–Calcium Oxides on the Cell Walls of the Algae Chara Corallina: Elemental Composition, Atomic Structure, and Water-Oxidation Catalysis (pages 780–790)

      Andreas Schöler, Ivelina Zaharieva, Sebastian Zimmermann, Mathias Wiechen, Anne-Marie Manke, Philipp Kurz, Christoph Plieth and Holger Dau

      Version of Record online: 25 SEP 2013 | DOI: 10.1002/ejic.201300697

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      The algae Chara corallina produce brown deposits on their cell walls when grown in manganese-rich media. By an unusual combination of normal and space-resolved X-ray absorption spectroscopy, it could be shown that the material belongs to the birnessite family of layered MnCa oxides. Furthermore, it was observed that the deposits act as biogenic water-oxidation catalysts.

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