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Research output: Contribution to Journal/Magazine › Journal article › peer-review
Research output: Contribution to Journal/Magazine › Journal article › peer-review
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TY - JOUR
T1 - Electrochemical kinetics
T2 - a surface-science supported picture of hydrogen electrochemistry on Ru(0001) and Pt/Ru(0001)
AU - Mercer, Michael
AU - Hoster, Harry Ernst
N1 - The final publication is available at Springer via http://dx.doi.org/10.1007/s12678-017-0381-y
PY - 2017/11
Y1 - 2017/11
N2 - In this short review, we compare the kinetics of hydrogen desorption in vacuum to those involved in the electrochemical hydrogen evolution/oxidation reactions (HER/HOR) at two types of atomically smooth model surfaces: bare Ru(0001), and the same surface covered by a 1.1 atomic layer thick Pt film. Low/high H2 (D2) desorption rates at room temperature in vacuum quantitatively correspond to low/high exchange current densities for the HOR/HER in electrochemistry. In view of the “volcano plot” concept, these represent two surfaces that adsorb hydrogen atoms, Had, too strongly and too weakly, respectively. Atomically smooth, vacuum annealed model surfaces are the closest approximation to the idealised slab geometries typically studied by density functional theory (DFT). A predictive volcano plot based on DFT-based adsorption energies for the Had intermediates agrees well with the experiments if two things are considered: (i) the steady-state coverage of Had intermediates and (ii)local variations in film thickness. The sluggish HER/HOR kinetics of Ru(0001) allows for excellent visibility of cyclic voltammetry (CV) features even in H2 saturated solution. The CV switches between a Had and a OHad/Oad dominated regime, but the presence of H2 in the electrolyte increases the Had dominated potential window by a factor of two. Whereas in plain electrolyte two electrochemical adsorption processes compete in forming adlayers, it is one electrochemical and one chemical one in the case of H2 saturated electrolyte. We demonstrate and quantitatively explain that dissociative H2 adsorption is more important than H+ discharge for Had formation in the low potential regime on Ru(0001).
AB - In this short review, we compare the kinetics of hydrogen desorption in vacuum to those involved in the electrochemical hydrogen evolution/oxidation reactions (HER/HOR) at two types of atomically smooth model surfaces: bare Ru(0001), and the same surface covered by a 1.1 atomic layer thick Pt film. Low/high H2 (D2) desorption rates at room temperature in vacuum quantitatively correspond to low/high exchange current densities for the HOR/HER in electrochemistry. In view of the “volcano plot” concept, these represent two surfaces that adsorb hydrogen atoms, Had, too strongly and too weakly, respectively. Atomically smooth, vacuum annealed model surfaces are the closest approximation to the idealised slab geometries typically studied by density functional theory (DFT). A predictive volcano plot based on DFT-based adsorption energies for the Had intermediates agrees well with the experiments if two things are considered: (i) the steady-state coverage of Had intermediates and (ii)local variations in film thickness. The sluggish HER/HOR kinetics of Ru(0001) allows for excellent visibility of cyclic voltammetry (CV) features even in H2 saturated solution. The CV switches between a Had and a OHad/Oad dominated regime, but the presence of H2 in the electrolyte increases the Had dominated potential window by a factor of two. Whereas in plain electrolyte two electrochemical adsorption processes compete in forming adlayers, it is one electrochemical and one chemical one in the case of H2 saturated electrolyte. We demonstrate and quantitatively explain that dissociative H2 adsorption is more important than H+ discharge for Had formation in the low potential regime on Ru(0001).
KW - Model surfaces
KW - Hydrogen evolution
KW - Hydrogen adsorption
KW - Single crystal
KW - Temperature programmed desorption
KW - Density functional theory
U2 - 10.1007/s12678-017-0381-y
DO - 10.1007/s12678-017-0381-y
M3 - Journal article
VL - 8
SP - 518
EP - 529
JO - Electrocatalysis
JF - Electrocatalysis
SN - 1868-2529
IS - 6
ER -