Impact of nanoparticle size and lattice oxygen on water oxidation on NiFeOxHy

NiFeOxHy are the most active catalysts for oxygen evolution in a base. For this reason, they are used widely in alkaline electrolysers. Several open questions remain as to the reason for their exceptionally high catalytic activity. Here we use a model system of mass-selected NiFe nanoparticles and isotope labelling experiments to show that oxygen evolution in 1 M KOH does not proceed via lattice exchange. We complement our activity measurements with electrochemistry–mass spectrometry, taken under operando conditions, and transmission electron microscopy and low-energy ion-scattering spectroscopy, taken ex situ. Together with the trends in particle size, the isotope results indicate that oxygen evolution is limited to the near-surface region. Using the surface area of the particles, we determined that the turnover frequency was 6.2 ± 1.6 s−1 at an overpotential of 0.3 V, which is, to the best of our knowledge, the highest reported for oxygen evolution in alkaline solution.The reason for the high water-oxidation activity of Ni(Fe)OxHy catalysts in alkaline electrolyte is not yet well understood. Now, Chorkendorff and co-workers report that oxygen evolution is limited to the near-surface region by measuring the activity trends of mass-selected NiFe nanoparticles.

[1]  D. Wilkinson,et al.  The Stability Challenges of Oxygen Evolving Catalysts: Towards a Common Fundamental Understanding and Mitigation of Catalyst Degradation. , 2017, Angewandte Chemie.

[2]  Thomas J. Kempa,et al.  Influence of iron doping on tetravalent nickel content in catalytic oxygen evolving films , 2017, Proceedings of the National Academy of Sciences.

[3]  Jiang Deng,et al.  Reactive Fe-Sites in Ni/Fe (Oxy)hydroxide Are Responsible for Exceptional Oxygen Electrocatalysis Activity. , 2017, Journal of the American Chemical Society.

[4]  Rosaria Ciriminna,et al.  Solar hydrogen: fuel of the near future , 2010 .

[5]  R. Palmer,et al.  A new high transmission infinite range mass selector for cluster and nanoparticle beams , 1999 .

[6]  W. Goddard,et al.  Synergy between Fe and Ni in the optimal performance of (Ni,Fe)OOH catalysts for the oxygen evolution reaction , 2018, Proceedings of the National Academy of Sciences.

[7]  H. Gasteiger,et al.  New insights into the electrochemical hydrogen oxidation and evolution reaction mechanism , 2014 .

[8]  Bryan M. Hunter,et al.  Iron Is the Active Site in Nickel/Iron Water Oxidation Electrocatalysts , 2018, Molecules.

[9]  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.

[10]  A. Bleloch,et al.  Three-dimensional atomic-scale structure of size-selected gold nanoclusters , 2008, Nature.

[11]  S. Boettcher,et al.  Nickel-iron oxyhydroxide oxygen-evolution electrocatalysts: the role of intentional and incidental iron incorporation. , 2014, Journal of the American Chemical Society.

[12]  Andrea R. Gerson,et al.  Resolving surface chemical states in XPS analysis of first row transition metals, oxides and hydroxides: Sc, Ti, V, Cu and Zn , 2010 .

[13]  O. Wolter,et al.  Does the Oxide Layer Take Part in the Oxygen Evolution Reaction on Platinum? A DEMS Study. , 1985 .

[14]  S. Boettcher,et al.  Effects of Intentionally Incorporated Metal Cations on the Oxygen Evolution Electrocatalytic Activity of Nickel (Oxy)hydroxide in Alkaline Media , 2016 .

[15]  Thomas F. Jaramillo,et al.  Gold-supported cerium-doped NiOx catalysts for water oxidation , 2016, Nature Energy.

[16]  M. Biesinger,et al.  The role of the Auger parameter in XPS studies of nickel metal, halides and oxides. , 2012, Physical chemistry chemical physics : PCCP.

[17]  N. Lewis,et al.  Powering the planet: Chemical challenges in solar energy utilization , 2006, Proceedings of the National Academy of Sciences.

[18]  P. Strasser,et al.  NiFe‐Based (Oxy)hydroxide Catalysts for Oxygen Evolution Reaction in Non‐Acidic Electrolytes , 2016 .

[19]  Benjamin Paul,et al.  Oxygen Evolution Reaction Dynamics, Faradaic Charge Efficiency, and the Active Metal Redox States of Ni-Fe Oxide Water Splitting Electrocatalysts. , 2016, Journal of the American Chemical Society.

[20]  Xunyu Lu,et al.  Electrodeposition of hierarchically structured three-dimensional nickel–iron electrodes for efficient oxygen evolution at high current densities , 2015, Nature Communications.

[21]  M. Cifrain,et al.  Hydrogen/oxygen (air) fuel cells with alkaline electrolytes , 2010 .

[22]  Jens K Nørskov,et al.  Identification of highly active Fe sites in (Ni,Fe)OOH for electrocatalytic water splitting. , 2015, Journal of the American Chemical Society.

[23]  O. Hansen,et al.  Enabling real-time detection of electrochemical desorption phenomena with sub-monolayer sensitivity , 2018 .

[24]  Shannon W. Boettcher,et al.  Oxygen Evolution Reaction Electrocatalysis on Transition Metal Oxides and (Oxy)hydroxides: Activity Trends and Design Principles , 2015 .

[25]  I. Chorkendorff,et al.  Synthesis and characterization of Fe–Ni/ɣ-Al2O3 egg-shell catalyst for H2 generation by ammonia decomposition , 2015 .

[26]  Yang Shao-Horn,et al.  Toward the rational design of non-precious transition metal oxides for oxygen electrocatalysis , 2015 .

[27]  S. Boettcher,et al.  Pulse-Electrodeposited Ni–Fe (Oxy)hydroxide Oxygen Evolution Electrocatalysts with High Geometric and Intrinsic Activities at Large Mass Loadings , 2015 .

[28]  Strong Metal Support Interaction of Pt and Ru Nanoparticles Deposited on HOPG Probed by the H-D Exchange Reaction , 2012 .

[29]  F. Calle‐Vallejo,et al.  Electrochemical water splitting by gold: evidence for an oxide decomposition mechanism , 2013 .

[30]  M. Wohlfahrt‐Mehrens,et al.  Oxygen evolution on Ru and RuO2 electrodes studied using isotope labelling and on-line mass spectrometry , 1987 .

[31]  K. Mayrhofer,et al.  Design criteria for stable Pt/C fuel cell catalysts , 2014, Beilstein journal of nanotechnology.

[32]  Tom Regier,et al.  An advanced Ni-Fe layered double hydroxide electrocatalyst for water oxidation. , 2013, Journal of the American Chemical Society.

[33]  Yang Shao-Horn,et al.  Orientation-Dependent Oxygen Evolution on RuO2 without Lattice Exchange , 2017 .

[34]  S. Boettcher,et al.  Solution-cast metal oxide thin film electrocatalysts for oxygen evolution. , 2012, Journal of the American Chemical Society.

[35]  I. Chorkendorff,et al.  Oxygen evolution on well-characterized mass-selected Ru and RuO2 nanoparticles† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c4sc02685c Click here for additional data file. , 2014, Chemical science.

[36]  Xile Hu,et al.  Oxidatively Electrodeposited Thin-Film Transition Metal (Oxy)hydroxides as Oxygen Evolution Catalysts. , 2016, Journal of the American Chemical Society.

[37]  H. Baltruschat,et al.  How many surface atoms in Co3O4 take part in oxygen evolution? Isotope labeling together with differential electrochemical mass spectrometry. , 2017, Physical chemistry chemical physics : PCCP.

[38]  Fang Song,et al.  A nickel iron diselenide-derived efficient oxygen-evolution catalyst , 2016, Nature Communications.

[39]  Hubert A. Gasteiger,et al.  Handbook of fuel cells : fundamentals technology and applications , 2003 .

[40]  A. Vojvodić,et al.  Theoretical Insights to Bulk Activity Towards Oxygen Evolution in Oxyhydroxides , 2017, Catalysis Letters.

[41]  M. Biesinger,et al.  New interpretations of XPS spectra of nickel metal and oxides , 2006 .

[42]  S. Boettcher,et al.  Revised Oxygen Evolution Reaction Activity Trends for First-Row Transition-Metal (Oxy)hydroxides in Alkaline Media. , 2015, The journal of physical chemistry letters.

[43]  Dusan Strmcnik,et al.  Energy and fuels from electrochemical interfaces. , 2016, Nature materials.

[44]  Jens K Nørskov,et al.  Materials for solar fuels and chemicals. , 2016, Nature materials.

[45]  Alexis T. Bell,et al.  Effects of Fe Electrolyte Impurities on Ni(OH)2/NiOOH Structure and Oxygen Evolution Activity , 2015 .

[46]  A. Vojvodić,et al.  Homogeneously dispersed multimetal oxygen-evolving catalysts , 2016, Science.

[47]  R. Kötz,et al.  Thermodynamic explanation of the universal correlation between oxygen evolution activity and corrosion of oxide catalysts , 2015, Scientific Reports.

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

[49]  Mark K. Debe,et al.  Electrocatalyst approaches and challenges for automotive fuel cells , 2012, Nature.

[50]  A. Bard,et al.  Surface Interrogation Scanning Electrochemical Microscopy of Ni(1-x)Fe(x)OOH (0 < x < 0.27) Oxygen Evolving Catalyst: Kinetics of the "fast" Iron Sites. , 2016, Journal of the American Chemical Society.

[51]  P. Notten,et al.  Electrochemical Quartz Microbalance characterization of Ni(OH)2-based thin film electrodes , 2006 .

[52]  Yang Shao-Horn,et al.  Activating lattice oxygen redox reactions in metal oxides to catalyse oxygen evolution. , 2017, Nature chemistry.

[53]  Fang Song,et al.  Exfoliation of layered double hydroxides for enhanced oxygen evolution catalysis , 2014, Nature Communications.

[54]  Shuang Xiao,et al.  A strongly coupled graphene and FeNi double hydroxide hybrid as an excellent electrocatalyst for the oxygen evolution reaction. , 2014, Angewandte Chemie.

[55]  P. Krtil,et al.  Oxygen evolution on nanocrystalline RuO2 and Ru0.9Ni0.1O2―δ electrodes ― DEMS approach to reaction mechanism determination , 2009 .

[56]  O. Wolter,et al.  Does the oxide layer take part in the oxygen evolution reaction on platinum , 1985 .

[57]  M. Streun,et al.  Size-selected cluster beam source based on radio frequency magnetron plasma sputtering and gas condensation , 2005 .

[58]  Yi Li,et al.  Correction: Corrigendum: MicroRNA-302b augments host defense to bacteria by regulating inflammatory responses via feedback to TLR/IRAK4 circuits , 2015, Nature Communications.

[59]  Nenad M. Markovic,et al.  The road from animal electricity to green energy: combining experiment and theory in electrocatalysis , 2012 .

[60]  H. Baltruschat,et al.  Investigation of the oxygen evolution reaction on Ti/IrO2 electrodes using isotope labelling and on-line mass spectrometry , 2007 .

[61]  Hubert A. Gasteiger,et al.  Instability of Pt ∕ C Electrocatalysts in Proton Exchange Membrane Fuel Cells A Mechanistic Investigation , 2005 .

[62]  M. Arenz,et al.  IL-TEM investigations on the degradation mechanism of Pt/C electrocatalysts with different carbon supports , 2011 .