Rate and mechanism of the photoreduction of birnessite (MnO 2 ) nanosheets

Marafatto, Francesco Femi; Strader, Matthew L.; Gonzalez-Holguera, Julia; Schwartzberg, Adam; Gilbert, Benjamin; Peña, Jasquelin

doi:10.1073/pnas.1421018112

Title: Rate and mechanism of the photoreduction of birnessite (MnO ₂ ) nanosheets

Abstract

Significance The photoreductive dissolution of Mn oxides governs the biogeochemical cycle of Mn and the fate of organic and inorganic species associated with Mn oxides in the euphotic zones of marine and freshwater systems. Mn oxide minerals also have garnered interest as water oxidation catalysts inspired by the Mn ₄ CaO ₄ cluster of photosystem II. However, the mechanism of water oxidation by MnO ₂ and the rate limiting steps for this reaction are unknown. In this study, we couple flow-through experiments and ultrafast pump–probe optical and X-ray absorption spectroscopy to develop a photoreduction model that includes the mechanism and timescales for the initial electron transfer steps in the oxidation of water by MnO ₂ .

Authors:

Marafatto, Francesco Femi ^[1]; Strader, Matthew L. ^[2]; Gonzalez-Holguera, Julia ^[1]; Schwartzberg, Adam ^[3]; Gilbert, Benjamin ^[4]; Peña, Jasquelin ^[1]

Institute of Earth Surface Dynamics, University of Lausanne, CH-1015 Lausanne, Switzerland, and
Chemical Sciences Division,
Molecular Foundry, and
Earth Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720

Publication Date:: Mon Mar 30 00:00:00 EDT 2015

Research Org.:: Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES); FOREIGNOTHER

OSTI Identifier:: 1235165

Alternate Identifier(s):: OSTI ID: 1182322

Grant/Contract Number:: AC02-05CH11231

Resource Type:: Published Article

Journal Name:: Proceedings of the National Academy of Sciences of the United States of America

Additional Journal Information:: Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Volume: 112 Journal Issue: 15; Journal ID: ISSN 0027-8424

Publisher:: Proceedings of the National Academy of Sciences

Country of Publication:: United States

Language:: English

Citation Formats


                    Marafatto, Francesco Femi, Strader, Matthew L., Gonzalez-Holguera, Julia, Schwartzberg, Adam, Gilbert, Benjamin, and Peña, Jasquelin. Rate and mechanism of the photoreduction of birnessite (MnO 2 ) nanosheets.  United States: N. p., 2015. 
Web.  doi:10.1073/pnas.1421018112.

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                    Marafatto, Francesco Femi, Strader, Matthew L., Gonzalez-Holguera, Julia, Schwartzberg, Adam, Gilbert, Benjamin, & Peña, Jasquelin. Rate and mechanism of the photoreduction of birnessite (MnO 2 ) nanosheets.  United States.  https://doi.org/10.1073/pnas.1421018112

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                    Marafatto, Francesco Femi, Strader, Matthew L., Gonzalez-Holguera, Julia, Schwartzberg, Adam, Gilbert, Benjamin, and Peña, Jasquelin. Mon .  
"Rate and mechanism of the photoreduction of birnessite (MnO 2 ) nanosheets".  United States.  https://doi.org/10.1073/pnas.1421018112.

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@article{osti_1235165,

  title        = {Rate and mechanism of the photoreduction of birnessite (MnO 2 ) nanosheets},

  author       = {Marafatto, Francesco Femi and Strader, Matthew L. and Gonzalez-Holguera, Julia and Schwartzberg, Adam and Gilbert, Benjamin and Peña, Jasquelin},

  abstractNote = {Significance The photoreductive dissolution of Mn oxides governs the biogeochemical cycle of Mn and the fate of organic and inorganic species associated with Mn oxides in the euphotic zones of marine and freshwater systems. Mn oxide minerals also have garnered interest as water oxidation catalysts inspired by the Mn 4 CaO 4 cluster of photosystem II. However, the mechanism of water oxidation by MnO 2 and the rate limiting steps for this reaction are unknown. In this study, we couple flow-through experiments and ultrafast pump–probe optical and X-ray absorption spectroscopy to develop a photoreduction model that includes the mechanism and timescales for the initial electron transfer steps in the oxidation of water by MnO 2 .},

  doi          = {10.1073/pnas.1421018112},

  journal      = {Proceedings of the National Academy of Sciences of the United States of America},

  number       = 15,

  volume       = 112,

  place        = {United States},

  year         = {Mon Mar 30 00:00:00 EDT 2015},

  month        = {Mon Mar 30 00:00:00 EDT 2015}

}

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Title: Rate and mechanism of the photoreduction of birnessite (MnO 2 ) nanosheets

Abstract

Citation Formats

Abundant Porewater Mn(III) Is a Major Component of the Sedimentary Redox System journal, August 2013

Terephthalic acid: A dosimeter for the detection of hydroxyl radicals in vitro journal, December 1994

Photochemical Water Oxidation by Crystalline Polymorphs of Manganese Oxides: Structural Requirements for Catalysis journal, February 2013

Photocurrent Generation from Semiconducting Manganese Oxide Nanosheets in Response to Visible Light journal, May 2005

Water in the interlayer region of birnessite: Importance in cation exchange and structural stability journal, April 2006

Structure of Synthetic K-rich Birnessite Obtained by High-Temperature Decomposition of KMnO 4 . I. Two-Layer Polytype from 800 °C Experiment journal, December 2003

Diel cycles in microbial manganese oxidation and manganese redox speciation in coastal waters of the Bahama Islands journal, March 1990

Optical properties of the clearest natural waters (200–800 nm) journal, January 1981

Why did Nature choose manganese to make oxygen? journal, October 2007

Manganese(II) Oxidation and Mn(IV) Reduction in the Environment—Two One-Electron Transfer Steps Versus a Single Two-Electron Step journal, April 2005

Mechanisms of pH-Dependent Activity for Water Oxidation to Molecular Oxygen by MnO 2 Electrocatalysts journal, January 2012

Energetic basis of catalytic activity of layered nanophase calcium manganese oxides for water oxidation journal, May 2013

Mn(II) oxidation by an ascomycete fungus is linked to superoxide production during asexual reproduction journal, July 2012

Ultrafast electron and energy transfer in dye-sensitized iron oxide and oxyhydroxide nanoparticles journal, January 2013

Ultrafast optical probes of polaron dynamics in La0.7Ca0.3MnO3 thin films journal, February 2009

Enhanced Dissolution of Manganese Oxide in Ice Compared to Aqueous Phase under Illuminated and Dark Conditions journal, December 2012

Molecular models of birnessite and related hydrated layered minerals journal, August 2012

Manganese-oxidizing photosynthesis before the rise of cyanobacteria journal, June 2013

Electron Small Polarons and Their Mobility in Iron (Oxyhydr)oxide Nanoparticles journal, September 2012

What Are the Oxidation States of Manganese Required To Catalyze Photosynthetic Water Oxidation? journal, July 2012

Photodissolution of iron oxides. IV. A comparative study on the photodissolution of hematite, magnetite, and maghemite in EDTA media journal, September 1992

Photoreductive Dissolution of Iron(III) (Hydr)oxides in the Absence and Presence of Organic Ligands: Experimental Studies and Kinetic Modeling journal, March 2009

On the role of Mn(IV) vacancies in the photoreductive dissolution of hexagonal birnessite journal, July 2009

Characterization of the manganese oxide produced by pseudomonas putida strain MnB1 journal, July 2003

Visible-light-induced photodissolution of α-Fe2O3 powder in the presence of chloride anions journal, January 1985

Charge carrier trapping, recombination and transfer in hematite (α-Fe2O3) water splitting photoanodes journal, January 2013

Photocatalytic Water Oxidation Using Manganese Compounds Immobilized in Nafion Polymer Membranes journal, January 2011

Layered manganese oxides for water-oxidation: alkaline earth cations influence catalytic activity in a photosystem II-like fashion journal, January 2012

Phosphonate- and Carboxylate-Based Chelating Agents that Solubilize (Hydr)oxide-Bound Mn III journal, June 2008

Mechanism of Photocatalytic Water Splitting in TiO 2 . Reaction of Water with Photoholes, Importance of Charge Carrier Dynamics, and Evidence for Four-Hole Chemistry journal, October 2008

Photoassisted dissolution of a colloidal manganese oxide in the presence of fulvic acid journal, July 1988

Water-oxidation catalysis by manganese in a geochemical-like cycle journal, May 2011

Short-range and long-range order of phyllomanganate nanoparticles determined using high-energy X-ray scattering journal, January 2013

Photoreduction of manganese oxides in seawater journal, April 1994

Substructure and superstructure of four-layer Ca-exchanged birnessite journal, February 1998

Bacteriogenic Manganese Oxides journal, January 2010

Electronic structures of iron(III) and manganese(IV) (hydr)oxide minerals: Thermodynamics of photochemical reductive dissolution in aquatic environments journal, July 2005

Title: Rate and mechanism of the photoreduction of birnessite (MnO ₂ ) nanosheets

Abundant Porewater Mn(III) Is a Major Component of the Sedimentary Redox System
journal, August 2013

Terephthalic acid: A dosimeter for the detection of hydroxyl radicals in vitro
journal, December 1994

Photochemical Water Oxidation by Crystalline Polymorphs of Manganese Oxides: Structural Requirements for Catalysis
journal, February 2013

Photocurrent Generation from Semiconducting Manganese Oxide Nanosheets in Response to Visible Light
journal, May 2005

Water in the interlayer region of birnessite: Importance in cation exchange and structural stability
journal, April 2006

Structure of Synthetic K-rich Birnessite Obtained by High-Temperature Decomposition of KMnO ₄ . I. Two-Layer Polytype from 800 °C Experiment
journal, December 2003

Diel cycles in microbial manganese oxidation and manganese redox speciation in coastal waters of the Bahama Islands
journal, March 1990

Optical properties of the clearest natural waters (200–800 nm)
journal, January 1981

Why did Nature choose manganese to make oxygen?
journal, October 2007

Manganese(II) Oxidation and Mn(IV) Reduction in the Environment—Two One-Electron Transfer Steps Versus a Single Two-Electron Step
journal, April 2005

Mechanisms of pH-Dependent Activity for Water Oxidation to Molecular Oxygen by MnO ₂ Electrocatalysts
journal, January 2012

Energetic basis of catalytic activity of layered nanophase calcium manganese oxides for water oxidation
journal, May 2013

Mn(II) oxidation by an ascomycete fungus is linked to superoxide production during asexual reproduction
journal, July 2012

Ultrafast electron and energy transfer in dye-sensitized iron oxide and oxyhydroxide nanoparticles
journal, January 2013

Ultrafast optical probes of polaron dynamics in La0.7Ca0.3MnO3 thin films
journal, February 2009

Enhanced Dissolution of Manganese Oxide in Ice Compared to Aqueous Phase under Illuminated and Dark Conditions
journal, December 2012

Molecular models of birnessite and related hydrated layered minerals
journal, August 2012

Manganese-oxidizing photosynthesis before the rise of cyanobacteria
journal, June 2013

Electron Small Polarons and Their Mobility in Iron (Oxyhydr)oxide Nanoparticles
journal, September 2012

What Are the Oxidation States of Manganese Required To Catalyze Photosynthetic Water Oxidation?
journal, July 2012

Photodissolution of iron oxides. IV. A comparative study on the photodissolution of hematite, magnetite, and maghemite in EDTA media
journal, September 1992

Photoreductive Dissolution of Iron(III) (Hydr)oxides in the Absence and Presence of Organic Ligands: Experimental Studies and Kinetic Modeling
journal, March 2009

On the role of Mn(IV) vacancies in the photoreductive dissolution of hexagonal birnessite
journal, July 2009

Characterization of the manganese oxide produced by pseudomonas putida strain MnB1
journal, July 2003

Visible-light-induced photodissolution of α-Fe2O3 powder in the presence of chloride anions
journal, January 1985

Charge carrier trapping, recombination and transfer in hematite (α-Fe2O3) water splitting photoanodes
journal, January 2013

Photocatalytic Water Oxidation Using Manganese Compounds Immobilized in Nafion Polymer Membranes
journal, January 2011

Layered manganese oxides for water-oxidation: alkaline earth cations influence catalytic activity in a photosystem II-like fashion
journal, January 2012

Phosphonate- and Carboxylate-Based Chelating Agents that Solubilize (Hydr)oxide-Bound Mn ^III
journal, June 2008

Mechanism of Photocatalytic Water Splitting in TiO ₂ . Reaction of Water with Photoholes, Importance of Charge Carrier Dynamics, and Evidence for Four-Hole Chemistry
journal, October 2008

Photoassisted dissolution of a colloidal manganese oxide in the presence of fulvic acid
journal, July 1988

Water-oxidation catalysis by manganese in a geochemical-like cycle
journal, May 2011

Short-range and long-range order of phyllomanganate nanoparticles determined using high-energy X-ray scattering
journal, January 2013

Photoreduction of manganese oxides in seawater
journal, April 1994

Substructure and superstructure of four-layer Ca-exchanged birnessite
journal, February 1998

Bacteriogenic Manganese Oxides
journal, January 2010

Electronic structures of iron(III) and manganese(IV) (hydr)oxide minerals: Thermodynamics of photochemical reductive dissolution in aquatic environments
journal, July 2005