Interfacial water reorganization as a pH-dependent descriptor of the hydrogen evolution rate on platinum electrodes


Hydrogen evolution on platinum is a key reaction for electrocatalysis and sustainable energy storage, yet its pH-dependent kinetics are not fully understood. Here we present a detailed kinetic study of hydrogen adsorption and evolution on Pt(111) in a wide pH range. Electrochemical measurements show that hydrogen adsorption and hydrogen evolution are both slow in alkaline media, consistent with the observation of a shift in the rate-determining step for hydrogen evolution. Adding nickel to the Pt(111) surface lowers the barrier for hydrogen adsorption in alkaline solutions and thereby enhances the hydrogen evolution rate. We explain these observations with a model that highlights the role of the reorganization of interfacial water to accommodate charge transfer through the electric double layer, the energetics of which are controlled by how strongly water interacts with the interfacial field. The model is supported by laser-induced temperature-jump measurements. Our model sheds light on the origin of the slow kinetics for the hydrogen evolution reaction in alkaline media.

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Figure 1: Comparison of cyclic voltammetries for Pt(111) at various pH.
Figure 2: Impedance spectroscopy of the kinetics of H adsorption on Pt(111) at various pH.
Figure 3: Kinetics of hydrogen evolution and hydrogen adsorption on Pt(111) in the presence of Ni(OH)2.
Figure 4: Cyclic voltammetry and laser-induced temperature-jump measurements at pH 10.
Figure 5: Cyclic voltammetry and laser-induced temperature-jump measurements at pH 13.


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This work was supported by a TOP grant from the Netherlands Organization for Scientific Research (NWO). Support from MINECO (Spain) through project CTQ2013-44083-P is acknowledged.

Author information




I.L.-Y., V.C., J.M.F. and M.T.M.K. designed the experiments. I.L.-Y. and W.D.Z.W. carried out the electrochemical experiments. I.L.-Y. and P.S.-P. carried out the laser-induced temperature-jump experiments. I.L.-Y. and M.T.M.K. co-wrote the manuscript and all authors edited the manuscript.

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Correspondence to Marc T. M. Koper.

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The authors declare no competing financial interests.

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Ledezma-Yanez, I., Wallace, W., Sebastián-Pascual, P. et al. Interfacial water reorganization as a pH-dependent descriptor of the hydrogen evolution rate on platinum electrodes. Nat Energy 2, 17031 (2017).

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