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The Oxidation Of Peroxide By Disordered Metal Oxides: A Measurement Of Thermodynamic Stability "By Proxy".
M. Sabri, H. J. King, R. Gummow, F. Malherbe, R. Hocking
Published 2018 · Chemistry, Medicine
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It is often noted that disordered materials have different chemical properties to their more "ordered" cousins. Quantifying these effects in terms of thermodynamics is challenging in part because disordered materials can be difficult to characterise and are frequently relatively unstable. During the course of our experiments to understand the effects of disorder in catalysts for water oxidation we observed that many disordered manganese and cobalt oxide water oxidation catalysts directly oxidised peroxide in contrast to their more ordered analogues which catalysed its disproportionation, that is, MnO2 +2 H+ +H2 O2 →Mn2+ +2 H2 O+O2 (oxidation) versus H2 O2 →H2 O+ 1 / 2 O2 (disproportionation). By measuring the efficiency for one reaction over the other as a function of pH, we were able to quantify the relative stability of materials in two series of metal oxides and thereby quantify their relative thermodynamic stability, "by proxy". We found that for the series of catalysts investigated the disorder made the materials stronger chemical oxidants and worse catalysts for the disproportionation of peroxide.
This paper references
Better than crystalline: amorphous vanadium oxide for sodium-ion batteries
E. Uchaker (2014)
Redox potential as a master variable controlling pathways of metal reduction by Geobacter sulfurreducens
Caleb E. Levar (2017)
Towards more accurate First Principles prediction of redox potentials in transition-metal compounds with LDA+U
F. Zhou (2004)
Nanoparticles: Strained and Stiff
B. Gilbert (2004)
Water-driven structure transformation in nanoparticles at room temperature
H. Zhang (2003)
Progress and new directions in high temperature calorimetry revisited
A. Navrotsky (1997)
Hydrogen peroxide decomposition on manganese oxide (pyrolusite): kinetics, intermediates, and mechanism.
Si-Hyun Do (2009)
Molecular-Scale Processes Involving Nanoparticulate Minerals in Biogeochemical Systems
B. Gilbert (2005)
Understanding electrochemical potentials of cathode materials in rechargeable batteries
C. Liu (2016)
Water Oxidation Catalysis using Amorphous Manganese Oxides, Octahedral Molecular Sieves (OMS-2), and Octahedral Layered (OL-1) Manganese Oxide Structures
Aparna Iyer (2012)
A soluble form of nano-sized colloidal manganese(IV) oxide as an efficient catalyst for water oxidation.
M. M. Najafpour (2011)
Manganese oxides: parallels between abiotic and biotic structures.
I. Saratovsky (2006)
Mechanism of decomposition of hydrogen peroxide solutions with manganese dioxide.
D. Broughton (1947)
Atom exchange between aqueous Fe(II) and goethite: an Fe isotope tracer study.
Robert M. Handler (2009)
QUANTUM CONFINEMENT EFFECTS ENABLE PHOTOCATALYZED NITRATE REDUCTION AT NEUTRAL PH USING CDS NANOCRYSTALS
B. Korgel (1997)
EXTENDED X-RAY ABSORPTION FINE STRUCTURE (EXAFS) ANALYSIS OF DISORDER AND MULTIPLE-SCATTERING IN COMPLEX CRYSTALLINE SOLIDS
P. O'Day (1994)
Reaction of MnIII,IV (hydr)oxides with oxalic acid, glyoxylic acid, phosphonoformic acid, and structurally-related organic compounds
Y. Wang (2006)
Self-healing catalysis in water
C. Costentin (2017)
Nature of Activated Manganese Oxide for Oxygen Evolution.
M. Huynh (2015)
Energetic basis of catalytic activity of layered nanophase calcium manganese oxides for water oxidation
Nancy Birkner (2013)
Studies of Decomposition of H2O2over Manganese Oxide Octahedral Molecular Sieve Materials
Hua Zhou (1998)
Water oxidation by amorphous cobalt-based oxides: in situ tracking of redox transitions and mode of catalysis
M. Risch (2015)
Defects and Disorder: Probing the Surface Chemistry of Heterogenite (CoOOH) by Dissolution Using Hydroquinone and Iminodiacetic Acid
R. L. Penn (2001)
Water-oxidation catalysis by manganese in a geochemical-like cycle.
R. Hocking (2011)
Electrochemical water oxidation with cobalt-based electrocatalysts from pH 0-14: the thermodynamic basis for catalyst structure, stability, and activity.
James B. Gerken (2011)
ADSORPTION OF GASES IN MULTIMOLECULAR LAYERS
S. Brunauer (1938)
Biomimetic Water-Oxidation Catalysts: Manganese Oxides.
P. Kurz (2016)
Porous amorphous FePO4 nanoparticles connected by single-wall carbon nanotubes for sodium ion battery cathodes.
Y. Liu (2012)
Thermodynamics of manganese oxides: Effects of particle size and hydration on oxidation-reduction equilibria among hausmannite, bixbyite, and pyrolusite
Nancy Birkner (2012)
Layered manganese oxides for water-oxidation: alkaline earth cations influence catalytic activity in a photosystem II-like fashion
Mathias Wiechen (2012)
Water oxidation by amorphous cobalt-based oxides: volume activity and proton transfer to electrolyte bases.
Katharina Klingan (2014)
The correlation of redox potential, HOMO energy, and oxidation state in metal sulfide clusters and its application to determine the redox level of the FeMo-co active-site cluster of nitrogenase.
I. Dance (2006)
Defective and “c-Disordered” Hortensia-like Layered MnOx as an Efficient Electrocatalyst for Water Oxidation at Neutral pH
B. Zhang (2017)
Engineering Disorder at a Nanoscale: A Combined TEM and XAS Investigation of Amorphous versus Nanocrystalline Sodium Birnessite
R. Hocking (2015)
Mechanisms of pH-dependent activity for water oxidation to molecular oxygen by MnO2 electrocatalysts.
Toshihiro Takashima (2012)
Electrosynthesis, functional, and structural characterization of a water-oxidizing manganese oxide
I. Zaharieva (2012)
A self-healing oxygen-evolving catalyst.
D. A. Lutterman (2009)
Engineering Disorder into Heterogenite‐Like Cobalt Oxides by Phosphate Doping: Implications for the Design of Water‐Oxidation Catalysts
H. J. King (2017)
Catalytic decomposition of hydrogen peroxide on some oxide catalysts
C. Roy (1968)
Nanoparticles in the Environment
J. Banfield (2001)
Studies on MnO2—III. The kinetics and the mechanism for the catalytic decomposition of H2O2 over different crystalline modifications of MnO2
S. B. Kanungo (1981)
Taking Advantage of Disorder: Amorphous Calcium Carbonate and Its Roles in Biomineralization
L. Addadi (2003)
Simple and accurate correlation of experimental redox potentials and DFT-calculated HOMO/LUMO energies of polycyclic aromatic hydrocarbons
Dalvin D. Méndez-Hernández (2012)
Reaction of EDTA and Related Aminocarboxylate Chelating Agents with CoIIIOOH (Heterogenite) and MnIIIOOH (Manganite)
C. McArdell (1998)
Electrochemical analyses of redox-active iron minerals: a review of nonmediated and mediated approaches.
M. Sander (2015)
Size-Driven Structural and Thermodynamic Complexity in Iron Oxides
A. Navrotsky (2008)
Catalytic Decomposition Kinetics of Aqueous Hydrogen Peroxide and Solid Magnesium Peroxide By Birnessite
A. M. Elprince (1992)
A possible evolutionary origin for the Mn4 cluster of the photosynthetic water oxidation complex from natural MnO2 precipitates in the early ocean
K. Sauer (2002)
Calcium manganese(III) oxides (CaMn2O4.xH2O) as biomimetic oxygen-evolving catalysts.
M. M. Najafpour (2010)
Rate and mechanism of the photoreduction of birnessite (MnO2) nanosheets
F. F. Marafatto (2015)
Calcium‐Mangan(III)‐Oxide (CaMn2O4⋅x H2O) als biomimetische Katalysatoren für die Sauerstoffbildung
M. M. Najafpour (2010)
Preparation of Layered MnO2 via Thermal Decomposition of KMnO4 and Its Electrochemical Characterizations
S. Kim (1999)
In Situ Formation of an Oxygen-Evolving Catalyst in Neutral Water Containing Phosphate and Co2+
M. Kanan (2008)
The Mechanism of Water Oxidation: From Electrolysis via Homogeneous to Biological Catalysis
H. Dau (2010)
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