Online citations, reference lists, and bibliographies.
← Back to Search

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

Save to my Library
Download PDF
Analyze on Scholarcy
Share
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
10.1039/C4TA03788J
Better than crystalline: amorphous vanadium oxide for sodium-ion batteries
E. Uchaker (2014)
10.1038/ismej.2016.146
Redox potential as a master variable controlling pathways of metal reduction by Geobacter sulfurreducens
Caleb E. Levar (2017)
10.1103/PhysRevB.70.235121
Towards more accurate First Principles prediction of redox potentials in transition-metal compounds with LDA+U
F. Zhou (2004)
10.1126/SCIENCE.1098454
Nanoparticles: Strained and Stiff
B. Gilbert (2004)
10.1038/nature01845
Water-driven structure transformation in nanoparticles at room temperature
H. Zhang (2003)
10.1007/S002690050035
Progress and new directions in high temperature calorimetry revisited
A. Navrotsky (1997)
10.1016/j.chemosphere.2008.11.075
Hydrogen peroxide decomposition on manganese oxide (pyrolusite): kinetics, intermediates, and mechanism.
Si-Hyun Do (2009)
10.2138/RMG.2005.59.6
Molecular-Scale Processes Involving Nanoparticulate Minerals in Biogeochemical Systems
B. Gilbert (2005)
10.1016/J.MATTOD.2015.10.009
Understanding electrochemical potentials of cathode materials in rechargeable batteries
C. Liu (2016)
10.1021/JP2120737
Water Oxidation Catalysis using Amorphous Manganese Oxides, Octahedral Molecular Sieves (OMS-2), and Octahedral Layered (OL-1) Manganese Oxide Structures
Aparna Iyer (2012)
10.1039/c1dt00006c
A soluble form of nano-sized colloidal manganese(IV) oxide as an efficient catalyst for water oxidation.
M. M. Najafpour (2011)
10.1021/JA062097G
Manganese oxides: parallels between abiotic and biotic structures.
I. Saratovsky (2006)
10.1021/JA01196A004
Mechanism of decomposition of hydrogen peroxide solutions with manganese dioxide.
D. Broughton (1947)
10.1021/ES802402M
Atom exchange between aqueous Fe(II) and goethite: an Fe isotope tracer study.
Robert M. Handler (2009)
10.1021/JP971016N
QUANTUM CONFINEMENT EFFECTS ENABLE PHOTOCATALYZED NITRATE REDUCTION AT NEUTRAL PH USING CDS NANOCRYSTALS
B. Korgel (1997)
10.1021/JA00086A026
EXTENDED X-RAY ABSORPTION FINE STRUCTURE (EXAFS) ANALYSIS OF DISORDER AND MULTIPLE-SCATTERING IN COMPLEX CRYSTALLINE SOLIDS
P. O'Day (1994)
10.1016/J.GCA.2006.06.1548
Reaction of MnIII,IV (hydr)oxides with oxalic acid, glyoxylic acid, phosphonoformic acid, and structurally-related organic compounds
Y. Wang (2006)
10.1073/pnas.1711836114
Self-healing catalysis in water
C. Costentin (2017)
10.1021/jacs.5b06382
Nature of Activated Manganese Oxide for Oxygen Evolution.
M. Huynh (2015)
10.1073/pnas.1306623110
Energetic basis of catalytic activity of layered nanophase calcium manganese oxides for water oxidation
Nancy Birkner (2013)
10.1006/JCAT.1998.2061
Studies of Decomposition of H2O2over Manganese Oxide Octahedral Molecular Sieve Materials
Hua Zhou (1998)
10.1039/C4EE03004D
Water oxidation by amorphous cobalt-based oxides: in situ tracking of redox transitions and mode of catalysis
M. Risch (2015)
10.1021/JP0039868
Defects and Disorder: Probing the Surface Chemistry of Heterogenite (CoOOH) by Dissolution Using Hydroquinone and Iminodiacetic Acid
R. L. Penn (2001)
10.1038/nchem.1049
Water-oxidation catalysis by manganese in a geochemical-like cycle.
R. Hocking (2011)
10.1021/ja205647m
Electrochemical water oxidation with cobalt-based electrocatalysts from pH 0-14: the thermodynamic basis for catalyst structure, stability, and activity.
James B. Gerken (2011)
10.1021/JA01269A023
ADSORPTION OF GASES IN MULTIMOLECULAR LAYERS
S. Brunauer (1938)
10.1007/128_2015_634
Biomimetic Water-Oxidation Catalysts: Manganese Oxides.
P. Kurz (2016)
10.1021/nl302819f
Porous amorphous FePO4 nanoparticles connected by single-wall carbon nanotubes for sodium ion battery cathodes.
Y. Liu (2012)
10.2138/am.2012.3982
Thermodynamics of manganese oxides: Effects of particle size and hydration on oxidation-reduction equilibria among hausmannite, bixbyite, and pyrolusite
Nancy Birkner (2012)
10.1039/C2SC20226C
Layered manganese oxides for water-oxidation: alkaline earth cations influence catalytic activity in a photosystem II-like fashion
Mathias Wiechen (2012)
10.1002/cssc.201301019
Water oxidation by amorphous cobalt-based oxides: volume activity and proton transfer to electrolyte bases.
Katharina Klingan (2014)
10.1021/IC060438L
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)
10.1021/ACSCATAL.7B00420
Defective and “c-Disordered” Hortensia-like Layered MnOx as an Efficient Electrocatalyst for Water Oxidation at Neutral pH
B. Zhang (2017)
10.1071/CH15412
Engineering Disorder at a Nanoscale: A Combined TEM and XAS Investigation of Amorphous versus Nanocrystalline Sodium Birnessite
R. Hocking (2015)
10.1021/ja206511w
Mechanisms of pH-dependent activity for water oxidation to molecular oxygen by MnO2 electrocatalysts.
Toshihiro Takashima (2012)
10.1039/C2EE21191B
Electrosynthesis, functional, and structural characterization of a water-oxidizing manganese oxide
I. Zaharieva (2012)
10.1021/ja900023k
A self-healing oxygen-evolving catalyst.
D. A. Lutterman (2009)
10.1002/cctc.201600983
Engineering Disorder into Heterogenite‐Like Cobalt Oxides by Phosphate Doping: Implications for the Design of Water‐Oxidation Catalysts
H. J. King (2017)
10.1016/0021-9517(68)90085-7
Catalytic decomposition of hydrogen peroxide on some oxide catalysts
C. Roy (1968)
10.2138/RMG.2001.44.01
Nanoparticles in the Environment
J. Banfield (2001)
10.1016/0013-4686(81)85093-1
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)
10.1002/ADMA.200300381
Taking Advantage of Disorder: Amorphous Calcium Carbonate and Its Roles in Biomineralization
L. Addadi (2003)
10.1007/s00894-012-1694-7
Simple and accurate correlation of experimental redox potentials and DFT-calculated HOMO/LUMO energies of polycyclic aromatic hydrocarbons
Dalvin D. Méndez-Hernández (2012)
10.1021/ES980362V
Reaction of EDTA and Related Aminocarboxylate Chelating Agents with CoIIIOOH (Heterogenite) and MnIIIOOH (Manganite)
C. McArdell (1998)
10.1021/acs.est.5b00006
Electrochemical analyses of redox-active iron minerals: a review of nonmediated and mediated approaches.
M. Sander (2015)
10.1126/science.1148614
Size-Driven Structural and Thermodynamic Complexity in Iron Oxides
A. Navrotsky (2008)
10.2136/SSSAJ1992.03615995005600060021X
Catalytic Decomposition Kinetics of Aqueous Hydrogen Peroxide and Solid Magnesium Peroxide By Birnessite
A. M. Elprince (1992)
10.1073/pnas.132266199
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)
10.1002/anie.200906745
Calcium manganese(III) oxides (CaMn2O4.xH2O) as biomimetic oxygen-evolving catalysts.
M. M. Najafpour (2010)
10.1073/pnas.1421018112
Rate and mechanism of the photoreduction of birnessite (MnO2) nanosheets
F. F. Marafatto (2015)
10.1002/ANGE.200906745
Calcium‐Mangan(III)‐Oxide (CaMn2O4⋅x H2O) als biomimetische Katalysatoren für die Sauerstoffbildung
M. M. Najafpour (2010)
10.1021/CM9801643
Preparation of Layered MnO2 via Thermal Decomposition of KMnO4 and Its Electrochemical Characterizations
S. Kim (1999)
10.1126/science.1162018
In Situ Formation of an Oxygen-Evolving Catalyst in Neutral Water Containing Phosphate and Co2+
M. Kanan (2008)
10.1002/cctc.201000126
The Mechanism of Water Oxidation: From Electrolysis via Homogeneous to Biological Catalysis
H. Dau (2010)



This paper is referenced by
Semantic Scholar Logo Some data provided by SemanticScholar