Universal dependence of hydrogen oxidation and evolution reaction activity of platinum-group metals on pH and hydrogen binding energy

A universal correlation is established between HOR/HER activity and hydrogen binding energy on platinum-group metals. Understanding how pH affects the activity of hydrogen oxidation reaction (HOR) and hydrogen evolution reaction (HER) is key to developing active, stable, and affordable HOR/HER catalysts for hydroxide exchange membrane fuel cells and electrolyzers. A common linear correlation between hydrogen binding energy (HBE) and pH is observed for four supported platinum-group metal catalysts (Pt/C, Ir/C, Pd/C, and Rh/C) over a broad pH range (0 to 13), suggesting that the pH dependence of HBE is metal-independent. A universal correlation between exchange current density and HBE is also observed on the four metals, indicating that they may share the same elementary steps and rate-determining steps and that the HBE is the dominant descriptor for HOR/HER activities. The onset potential of CO stripping on the four metals decreases with pH, indicating a stronger OH adsorption, which provides evidence against the promoting effect of adsorbed OH on HOR/HER.

[1]  Yushan Yan,et al.  Correlating Hydrogen Oxidation/Evolution Reaction Activity with the Minority Weak Hydrogen-Binding Sites on Ir/C Catalysts , 2015 .

[2]  Jingguang G. Chen,et al.  Correlating hydrogen oxidation and evolution activity on platinum at different pH with measured hydrogen binding energy , 2015, Nature Communications.

[3]  Hubert A. Gasteiger,et al.  Hydrogen Oxidation and Evolution Reaction Kinetics on Carbon Supported Pt, Ir, Rh, and Pd Electrocatalysts in Acidic Media , 2015 .

[4]  Jing Pan,et al.  Pt–Ru catalyzed hydrogen oxidation in alkaline media: oxophilic effect or electronic effect? , 2015 .

[5]  Yushan Yan,et al.  Correcting the Hydrogen Diffusion Limitation in Rotating Disk Electrode Measurements of Hydrogen Evolution Reaction Kinetics , 2015 .

[6]  Jakob Kibsgaard,et al.  Molybdenum phosphosulfide: an active, acid-stable, earth-abundant catalyst for the hydrogen evolution reaction. , 2014, Angewandte Chemie.

[7]  H. Gasteiger,et al.  (Invited) Hydrogen Oxidation and Evolution Reaction (HOR/HER) on Pt Electrodes in Acid vs. Alkaline Electrolytes: Mechanism, Activity and Particle Size Effects , 2014 .

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

[9]  Nathan S Lewis,et al.  Highly active electrocatalysis of the hydrogen evolution reaction by cobalt phosphide nanoparticles. , 2014, Angewandte Chemie.

[10]  Yao Zheng,et al.  Hydrogen evolution by a metal-free electrocatalyst , 2014, Nature Communications.

[11]  Jingguang G. Chen,et al.  Non-precious metal electrocatalysts with high activity for hydrogen oxidation reaction in alkaline electrolytes , 2014 .

[12]  Yi Cui,et al.  CoSe2 nanoparticles grown on carbon fiber paper: an efficient and stable electrocatalyst for hydrogen evolution reaction. , 2014, Journal of the American Chemical Society.

[13]  H. Gasteiger,et al.  Kinetics of the Hydrogen Oxidation/Evolution Reaction on Polycrystalline Platinum in Alkaline Electrolyte Reaction Order with Respect to Hydrogen Pressure , 2014 .

[14]  Micheál D. Scanlon,et al.  A nanoporous molybdenum carbide nanowire as an electrocatalyst for hydrogen evolution reaction , 2014 .

[15]  James R. McKone,et al.  Nanostructured nickel phosphide as an electrocatalyst for the hydrogen evolution reaction. , 2013, Journal of the American Chemical Society.

[16]  Jingguang G. Chen,et al.  Correlating the hydrogen evolution reaction activity in alkaline electrolytes with the hydrogen binding energy on monometallic surfaces , 2013 .

[17]  Nemanja Danilovic,et al.  Improving the hydrogen oxidation reaction rate by promotion of hydroxyl adsorption. , 2013, Nature chemistry.

[18]  M. Koper.  Hydrogen electrocatalysis: a basic solution. , 2013, Nature chemistry.

[19]  M. Koper,et al.  Water dissociation on well-defined platinum surfaces: The electrochemical perspective , 2013 .

[20]  K. Mayrhofer,et al.  Near-surface ion distribution and buffer effects during electrochemical reactions. , 2011, Physical chemistry chemical physics : PCCP.

[21]  M. Koper,et al.  Oxidation of carbon monoxide on poly-oriented and single-crystalline platinum electrodes over a wide range of pH , 2011 .

[22]  Hubert A. Gasteiger,et al.  Handbook of Fuel Cells , 2010 .

[23]  M. Koper,et al.  Adsorption of phosphate species on poly-oriented Pt and Pt(1 1 1) electrodes over a wide range of pH , 2010 .

[24]  M. Koper,et al.  Impedance spectroscopy of H and OH adsorption on stepped single-crystal platinum electrodes in alkaline and acidic media. , 2010, Physical chemistry chemical physics : PCCP.

[25]  H. Gasteiger,et al.  Hydrogen Oxidation and Evolution Reaction Kinetics on Platinum: Acid vs Alkaline Electrolytes , 2010 .

[26]  Jiujun Zhang,et al.  Electrocatalysis of Direct Methanol Fuel Cells , 2009 .

[27]  H. Abruña,et al.  Direct observation of electrocatalytic synergy. , 2007, Journal of the American Chemical Society.

[28]  Thomas F. Jaramillo,et al.  Identification of Active Edge Sites for Electrochemical H2 Evolution from MoS2 Nanocatalysts , 2007, Science.

[29]  J. Jorné,et al.  Study of the Exchange Current Density for the Hydrogen Oxidation and Evolution Reactions , 2007 .

[30]  Thomas Bligaard,et al.  Trends in the exchange current for hydrogen evolution , 2005 .

[31]  B. Conway,et al.  Relation of energies and coverages of underpotential and overpotential deposited H at Pt and other metals to the ‘volcano curve’ for cathodic H2 evolution kinetics , 2000 .

[32]  A. Zolfaghari,et al.  Temperature-dependent research on Pt(111) and Pt(100) electrodes in aqueous H2SO4☆ , 1999 .

[33]  B. Conway,et al.  Structural specificity of the kinetics of the hydrogen evolution reaction on the low-index surfaces of Pt single-crystal electrodes in 0.5 M dm −3 NaOH 1 Dedicated to Professor W. Vielstich on the occasion of his 75th birthday. 1 , 1999 .

[34]  Philip N. Ross,et al.  TEMPERATURE-DEPENDENT HYDROGEN ELECTROCHEMISTRY ON PLATINUM LOW-INDEX SINGLE-CRYSTAL SURFACES IN ACID SOLUTIONS , 1997 .

[35]  A. Zolfaghari,et al.  Comparison of Hydrogen Electroadsorption from the Electrolyte with Hydrogen Adsorption from the Gas Phase , 1996 .

[36]  P. Strevens.  Iii , 1985 .

[37]  P. Stonehart,et al.  Effect of electrolyte environment and Pt crystallite size on hydrogen adsorption—V , 1978 .

[38]  R. Woods.  Hydrogen adsorption on platinum, iridium and rhodium electrodes at reduced temperatures and the determination of real surface area , 1974 .

[39]  Allen J. Bard,et al.  Electroanalytical Chemistry: A Series of Advances , 1974 .

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

[41]  D. Rand,et al.  The nature of adsorbed oxygen on rhodium, palladium and gold electrodes , 1971 .

[42]  Ronald Woods,et al.  Limiting oxygen coverage on platinized platinum; Relevance to determination of real platinum area by hydrogen adsorption , 1971 .

[43]  E. Gileadi,et al.  The Potential of Zero Charge of Platinum and Its pH Dependence , 1966 .