Uniform, Assembled 4 nm Mn3O4 Nanoparticles as Efficient Water Oxidation Electrocatalysts at Neutral pH

Electrochemical water splitting is one of the ways to produce environmentally‐friendly hydrogen energy. Transition‐metal (TM)‐based catalysts have been attracting attention due to their low cost and abundance, but their insufficient activity still remains a challenge. Here, 4 nm Mn3O4 nanoparticles (NPs) are successfully synthesized and their electrochemical behavior is investigated. Using electrokinetic analyses, an identical water oxidizing mechanism is demonstrated between the 4 and 8 nm Mn3O4 NPs. In addition, it is confirmed that the overall increase in the active surface area is strongly correlated with the superb catalytic activity of the 4 nm Mn3O4 NPs. To further enhance the oxygen evolution reaction (OER) performance, Ni foam substrate is introduced to maximize the entire number of the NPs participating in OER. The 4 nm Mn3O4/Ni foam electrode exhibits outstanding electrocatalytic activity for OER with overpotential of 395 mV at a current density of 10 mA cm−2 under neutral conditions (0.5 m PBS, pH 7).

[1]  J. Jasieniak,et al.  The heat-up synthesis of colloidal nanocrystals , 2015 .

[2]  K. Nam,et al.  Involvement of high-valent manganese-oxo intermediates in oxidation reactions: realisation in nature, nano and molecular systems , 2018, Nano Convergence.

[3]  W. Tremel,et al.  Synthesis and Characterization of Monodisperse Manganese Oxide Nanoparticles−Evaluation of the Nucleation and Growth Mechanism , 2009 .

[4]  N. Bahlawane,et al.  Synthesis of the catalytically active Mn3O4 spinel and its thermal properties , 2013 .

[5]  Sung Tae Kim,et al.  Development of a T1 contrast agent for magnetic resonance imaging using MnO nanoparticles. , 2007, Angewandte Chemie.

[6]  Sunghak Park,et al.  Water Oxidation Mechanism for 3d Transition Metal Oxide Catalysts under Neutral condition , 2017 .

[7]  J. Swierk,et al.  Electrocatalytic water oxidation by single site and small nuclearity clusters of cobalt , 2018 .

[8]  Abdullah M. Asiri,et al.  High-Performance Electrolytic Oxygen Evolution in Neutral Media Catalyzed by a Cobalt Phosphate Nanoarray. , 2017, Angewandte Chemie.

[9]  P. Shumbula,et al.  Analysis of the interaction of surfactants oleic acid and oleylamine with iron oxide nanoparticles through molecular mechanics modeling. , 2015, Langmuir : the ACS journal of surfaces and colloids.

[10]  Jianyin Wang,et al.  Investigation of Fe-Based Integrated Electrodes for Water Oxidation in Neutral and Alkaline Solutions , 2019, The Journal of Physical Chemistry C.

[11]  Matthew W Kanan,et al.  Mechanistic studies of the oxygen evolution reaction by a cobalt-phosphate catalyst at neutral pH. , 2010, Journal of the American Chemical Society.

[12]  Licheng Sun,et al.  Identifying MnVII-oxo Species during Electrochemical Water Oxidation by Manganese Oxide , 2018, iScience.

[13]  P. Bogdanoff,et al.  Evaluation of MnOx, Mn2O3, and Mn3O4 Electrodeposited Films for the Oxygen Evolution Reaction of Water , 2014 .

[14]  Charles C. L. McCrory,et al.  Benchmarking heterogeneous electrocatalysts for the oxygen evolution reaction. , 2013, Journal of the American Chemical Society.

[15]  Licheng Sun,et al.  A Cobalt‐Based Film for Highly Efficient Electrocatalytic Water Oxidation in Neutral Aqueous Solution , 2016 .

[16]  Ki Tae Nam,et al.  Mn5O8 Nanoparticles as Efficient Water Oxidation Catalysts at Neutral pH , 2015 .

[17]  S. Mourdikoudis,et al.  Oleylamine in Nanoparticle Synthesis , 2013 .

[18]  Daniel G. Nocera,et al.  In Situ Formation of an Oxygen-Evolving Catalyst in Neutral Water Containing Phosphate and Co2+ , 2008, Science.

[19]  P. Strasser,et al.  Dynamical changes of a Ni-Fe oxide water splitting catalyst investigated at different pH , 2016 .

[20]  G. Polzonetti,et al.  XPS study of MnO oxidation , 1989 .

[21]  Jie-Sheng Chen,et al.  Janus Co/CoP Nanoparticles as Efficient Mott–Schottky Electrocatalysts for Overall Water Splitting in Wide pH Range , 2017 .

[22]  John Kitchin,et al.  Universality in Oxygen Evolution Electrocatalysis on Oxide Surfaces , 2011 .

[23]  Licheng Sun,et al.  Defective and “c-Disordered” Hortensia-like Layered MnOx as an Efficient Electrocatalyst for Water Oxidation at Neutral pH , 2017 .

[24]  Sunghak Park,et al.  Mechanistic Investigation with Kinetic Parameters on Water Oxidation Catalyzed by Manganese Oxide Nanoparticle Film , 2019, ACS Sustainable Chemistry & Engineering.

[25]  Michael P. Brandon,et al.  Redox and electrochemical water splitting catalytic properties of hydrated metal oxide modified electrodes. , 2013, Physical chemistry chemical physics : PCCP.

[26]  Rui Cao,et al.  An Iron-based Film for Highly Efficient Electrocatalytic Oxygen Evolution from Neutral Aqueous Solution. , 2015, ACS applied materials & interfaces.

[27]  Min Gyu Kim,et al.  Mechanistic Investigation of Water Oxidation Catalyzed by Uniform, Assembled MnO Nanoparticles. , 2017, Journal of the American Chemical Society.

[28]  Ki Tae Nam,et al.  Material science lesson from the biological photosystem , 2016, Nano Convergence.

[29]  Colin F. Dickens,et al.  Combining theory and experiment in electrocatalysis: Insights into materials design , 2017, Science.

[30]  G. K. Pradhan,et al.  Hydrated manganese(II) phosphate (Mn₃(PO₄)₂·3H₂O) as a water oxidation catalyst. , 2014, Journal of the American Chemical Society.

[31]  Ho Won Jang,et al.  A new water oxidation catalyst: lithium manganese pyrophosphate with tunable Mn valency. , 2014, Journal of the American Chemical Society.

[32]  M. Dresselhaus,et al.  Alternative energy technologies , 2001, Nature.

[33]  B. Forbush,et al.  COOPERATION OF CHARGES IN PHOTOSYNTHETIC O2 EVOLUTION–I. A LINEAR FOUR STEP MECHANISM , 1970, Photochemistry and photobiology.

[34]  Sunghak Park,et al.  Highly Selective Active Chlorine Generation Electrocatalyzed by Co3O4 Nanoparticles: Mechanistic Investigation through in Situ Electrokinetic and Spectroscopic Analyses. , 2019, The journal of physical chemistry letters.

[35]  P. Menezes,et al.  Active mixed-valent MnO(x) water oxidation catalysts through partial oxidation (corrosion) of nanostructured MnO particles. , 2013, Angewandte Chemie.

[36]  Licheng Sun,et al.  Why nature chose the Mn4CaO5 cluster as water-splitting catalyst in photosystem II: a new hypothesis for the mechanism of O-O bond formation. , 2018, Dalton transactions.

[37]  Sunghak Park,et al.  Importance of Entropic Contribution to Electrochemical Water Oxidation Catalysis , 2019, ACS Energy Letters.

[38]  A. Nazeer,et al.  Surface modification of Fe2O3 and MgO nanoparticles with agrowastes for the treatment of chlorosis in Glycine max , 2018, Nano Convergence.

[39]  D. Pantazis,et al.  A five-coordinate Mn(iv) intermediate in biological water oxidation: spectroscopic signature and a pivot mechanism for water binding , 2015, Chemical science.

[40]  Ki Tae Nam,et al.  Partially Oxidized Sub-10 nm MnO Nanocrystals with High Activity for Water Oxidation Catalysis , 2015, Scientific Reports.

[41]  R. Schlögl,et al.  Nanostructured Manganese Oxide Supported on Carbon Nanotubes for Electrocatalytic Water Splitting , 2012 .

[42]  Christian Limberg,et al.  The Mechanism of Water Oxidation: From Electrolysis via Homogeneous to Biological Catalysis , 2010 .

[43]  Yi Xie,et al.  Co3O4 nanocrystals on single-walled carbon nanotubes as a highly efficient oxygen-evolving catalyst , 2012, Nano Research.

[44]  Tatsuya Shinagawa,et al.  Insight on Tafel slopes from a microkinetic analysis of aqueous electrocatalysis for energy conversion , 2015, Scientific Reports.

[45]  S. Choi,et al.  Synthesis of Uniformly Sized Manganese Oxide Nanocrystals with Various Sizes and Shapes and Characterization of Their T1 Magnetic Resonance Relaxivity , 2012 .

[46]  Yan-Gu Lin,et al.  Calcium containing iron oxide as an efficient and robust catalyst in (photo-)electrocatalytic water oxidation at neutral pH , 2018 .

[47]  D. Nocera,et al.  Highly active cobalt phosphate and borate based oxygen evolving catalysts operating in neutral and natural waters , 2011 .

[48]  K. Hashimoto,et al.  Inhibition of charge disproportionation of MnO2 electrocatalysts for efficient water oxidation under neutral conditions. , 2012, Journal of the American Chemical Society.

[49]  Sunghak Park,et al.  Methylamine Treated Mn3O4 Nanoparticles as a Highly Efficient Water Oxidation Catalyst under Neutral Condition , 2019, ChemCatChem.

[50]  Chem. , 2020, Catalysis from A to Z.

[51]  Yunyong Li,et al.  Callistemon-like Zn and S codoped CoP nanorod clusters as highly efficient electrocatalysts for neutral-pH overall water splitting , 2019, Journal of Materials Chemistry A.

[52]  P. Strasser,et al.  Electrochemical water splitting by layered and 3D cross-linked manganese oxides: correlating structural motifs and catalytic activity , 2013 .

[53]  G. Ceder,et al.  Electrochemical trapping of metastable Mn3+ ions for activation of MnO2 oxygen evolution catalysts , 2018, Proceedings of the National Academy of Sciences.

[54]  A. Yamaguchi,et al.  Evidence that Crystal Facet Orientation Dictates Oxygen Evolution Intermediates on Rutile Manganese Oxide , 2018 .

[55]  Keisuke Kawakami,et al.  Crystal structure of oxygen-evolving photosystem II at a resolution of 1.9 Å , 2011, Nature.

[56]  Jing Li,et al.  Core–Shell MoS2@CoO Electrocatalyst for Water Splitting in Neural and Alkaline Solutions , 2019, The Journal of Physical Chemistry C.

[57]  A. Yamaguchi,et al.  Electrochemical characterization of manganese oxides as a water oxidation catalyst in proton exchange membrane electrolysers , 2019, Royal Society Open Science.

[58]  Kazuhito Hashimoto,et al.  Mechanisms of pH-dependent activity for water oxidation to molecular oxygen by MnO2 electrocatalysts. , 2012, Journal of the American Chemical Society.

[59]  Jae-yong Lee,et al.  ITO nanoparticles reused from ITO scraps and their applications to sputtering target for transparent conductive electrode layer , 2017, Nano Convergence.