Trends in the electrochemical synthesis of H2O2: enhancing activity and selectivity by electrocatalytic site engineering.

The direct electrochemical synthesis of hydrogen peroxide is a promising alternative to currently used batch synthesis methods. Its industrial viability is dependent on the effective catalysis of the reduction of oxygen at the cathode. Herein, we study the factors controlling activity and selectivity for H2O2 production on metal surfaces. Using this approach, we discover two new catalysts for the reaction, Ag-Hg and Pd-Hg, with unique electrocatalytic properties both of which exhibit performance that far exceeds the current state-of-the art.

[1]  Thomas F. Jaramillo,et al.  Addressing the terawatt challenge: scalability in the supply of chemical elements for renewable energy , 2012 .

[2]  C. Gumiński.  The Hg-Pd (Mercury-Palladium) system , 1990 .

[3]  B. Kasemo,et al.  Transport effects in the oxygen reduction reaction on nanostructured, planar glassy carbon supported Pt/GC model electrodes. , 2008, Physical chemistry chemical physics : PCCP.

[4]  Thomas F. Jaramillo,et al.  New insights into the electrochemical reduction of carbon dioxide on metallic copper surfaces , 2012 .

[5]  Ping Liu,et al.  Core-protected platinum monolayer shell high-stability electrocatalysts for fuel-cell cathodes. , 2010, Angewandte Chemie.

[6]  J. Fierro,et al.  Hydrogen peroxide synthesis: an outlook beyond the anthraquinone process. , 2006, Angewandte Chemie.

[7]  Ib Chorkendorff,et al.  Enabling direct H2O2 production through rational electrocatalyst design. , 2013, Nature materials.

[8]  Jens K Nørskov,et al.  Unifying the 2e(-) and 4e(-) Reduction of Oxygen on Metal Surfaces. , 2012, The journal of physical chemistry letters.

[9]  Shouheng Sun,et al.  FePt and CoPt nanowires as efficient catalysts for the oxygen reduction reaction. , 2013, Angewandte Chemie.

[10]  Jacob Bonde,et al.  Biomimetic hydrogen evolution: MoS2 nanoparticles as catalyst for hydrogen evolution. , 2005, Journal of the American Chemical Society.

[11]  S. Trasatti.  Work function, electronegativity, and electrochemical behaviour of metals: III. Electrolytic hydrogen evolution in acid solutions , 1972 .

[12]  S. Dahl,et al.  The effect of ammonia upon the electrocatalysis of hydrogen oxidation and oxygen reduction on polycrystalline platinum , 2012 .

[13]  G. Öhlmann,et al.  Handbook of Heterogeneous Catalysis , 1999 .

[14]  D. Schiffrin,et al.  Kinetics of electrocatalytic reduction of oxygen and hydrogen peroxide on dispersed gold nanoparticles. , 2010, Physical chemistry chemical physics : PCCP.

[15]  I. Chorkendorff,et al.  Concepts of Modern Catalysis and Kinetics: CHORKEND:CONCEP.CATALYSIS O-BK , 2005 .

[16]  Maria Chan,et al.  Trends in activity for the water electrolyser reactions on 3d M(Ni,Co,Fe,Mn) hydr(oxy)oxide catalysts. , 2012, Nature materials.

[17]  J. Goodenough,et al.  A Perovskite Oxide Optimized for Oxygen Evolution Catalysis from Molecular Orbital Principles , 2011, Science.

[18]  A S Bondarenko,et al.  Alloys of platinum and early transition metals as oxygen reduction electrocatalysts. , 2009, Nature chemistry.

[19]  Bongjin Simon Mun,et al.  Trends in electrocatalysis on extended and nanoscale Pt-bimetallic alloy surfaces. , 2007, Nature materials.

[20]  Piotr Zelenay,et al.  Recent advances in non-precious metal catalysis for oxygen-reduction reaction in polymer electrolyte fuel cells , 2011 .

[21]  M. Shao,et al.  Pd-Fe nanoparticles as electrocatalysts for oxygen reduction. , 2006, Journal of the American Chemical Society.

[22]  S. Yau,et al.  Crystalline alloys produced by mercury electrodeposition on Pt(1 1 1) electrode at room temperature , 2008 .

[23]  D. Muller,et al.  Structurally ordered intermetallic platinum-cobalt core-shell nanoparticles with enhanced activity and stability as oxygen reduction electrocatalysts. , 2013, Nature materials.

[24]  Peter Strasser,et al.  Tandem cathode for proton exchange membrane fuel cells. , 2013, Physical chemistry chemical physics : PCCP.

[25]  M. Arenz,et al.  Adsorbate-induced surface segregation for core-shell nanocatalysts. , 2009, Angewandte Chemie.

[26]  Anthony Kucernak,et al.  Electrocatalysis under Conditions of High Mass Transport Rate: Oxygen Reduction on Single Submicrometer-Sized Pt Particles Supported on Carbon , 2004 .

[27]  Ib Chorkendorff,et al.  Tuning the activity of Pt(111) for oxygen electroreduction by subsurface alloying. , 2011, Journal of the American Chemical Society.

[28]  J. Ross.  Ullman's encyclopedia of industrial chemistry , 1986 .

[29]  H. Gasteiger,et al.  Just a Dream—or Future Reality? , 2009, Science.

[30]  T. Hibino,et al.  Direct oxidation of methane to methanol at low temperature and pressure in an electrochemical fuel cell. , 2008, Angewandte Chemie.

[31]  M. Arenz,et al.  The particle size effect on the oxygen reduction reaction activity of Pt catalysts: influence of electrolyte and relation to single crystal models. , 2011, Journal of the American Chemical Society.

[32]  Matthew W Kanan,et al.  CO2 reduction at low overpotential on Cu electrodes resulting from the reduction of thick Cu2O films. , 2012, Journal of the American Chemical Society.

[33]  M. Baren.  The Ag-Hg (Silver-Mercury) system , 1996 .

[34]  Alloy Phase Diagrams , 1987 .

[35]  Lin Gan,et al.  Compositional segregation in shaped Pt alloy nanoparticles and their structural behaviour during electrocatalysis. , 2013, Nature materials.

[36]  Rees B Rankin,et al.  Trends in Selective Hydrogen Peroxide Production on Transition Metal Surfaces from First Principles , 2012 .

[37]  Markus Antonietti,et al.  Mesoporous nitrogen-doped carbon for the electrocatalytic synthesis of hydrogen peroxide. , 2012, Journal of the American Chemical Society.

[38]  R. Parsons.  The rate of electrolytic hydrogen evolution and the heat of adsorption of hydrogen , 1958 .

[39]  T. Laitinen,et al.  Adsorption of mercury on gold and silver surfaces , 1999 .

[40]  H. Gasteiger,et al.  Characterization of High‐Surface‐Area Electrocatalysts Using a Rotating Disk Electrode Configuration , 1998 .

[41]  R. Potter,et al.  Electroreduction of oxygen on carbon-supported gold catalysts , 2009 .

[42]  Ib Chorkendorff,et al.  Design of an active site towards optimal electrocatalysis: overlayers, surface alloys and near-surface alloys of Cu/Pt(111). , 2012, Angewandte Chemie.

[43]  C. Samanta.  Direct synthesis of hydrogen peroxide from hydrogen and oxygen: An overview of recent developments in the process , 2008 .

[44]  M. Pourbaix.  Atlas of Electrochemical Equilibria in Aqueous Solutions , 1974 .

[45]  Philip N. Ross,et al.  Improved Oxygen Reduction Activity on Pt3Ni(111) via Increased Surface Site Availability , 2007, Science.

[46]  Itai Panas,et al.  Single atom hot-spots at Au-Pd nanoalloys for electrocatalytic H2O2 production. , 2011, Journal of the American Chemical Society.

[47]  G. Hutchings,et al.  Switching Off Hydrogen Peroxide Hydrogenation in the Direct Synthesis Process , 2009, Science.