New Insight into the Hydrogen Evolution Reaction under Buffered Near-Neutral pH Conditions: Enthalpy and Entropy of Activation

Tatsuya Shinagawa, Kazuhiro Takanabe

Research output: Contribution to journalArticlepeer-review

37 Scopus citations


Electrochemical conversion of thermodynamically stable chemicals of water and carbon dioxide is regarded as a core technology for achieving sustainability in our society. In both cases, the electrochemical hydrogen evolution reaction (HER) is a key reaction, particularly at near-neutral pH. This study addresses the kinetic aspects of the HER in buffered near-neutral pH conditions using a variety of electrode materials (W, Ni, Pt, Au, and Cu) over a wide temperature range (299–346 K). When the overall performance was summarized with respect to the binding energy of the reaction intermediate species, a classic volcano-shaped relationship was obtained. Interestingly, the temperature sensitivity analysis disclosed that smaller activation energies did not always lead to higher performance in 1.5 mol L–1 K-phosphate solution (pH 5.8). Detailed analysis of the temperature- and potential-dependent parameters revealed that smaller activation energies coincided with smaller values of the pre-exponential factor in the Arrhenius’ equation (associated with the entropy of activation). Due to the trade-off relationship of enthalpy–entropy compensation in the current system, the conventional approach of mixing elements of lower and higher binding energies to the intermediate species failed: even though Ni–Cu showed lower apparent activation energy, its activity toward the HER was between that of Ni and Cu due to the lowered entropy of activation. This study demonstrates the unrevealed fundamental aspects of the HER in buffered near-neutral condition, which contributes to the rational development of efficient energy and material conversion systems.
Original languageEnglish (US)
Pages (from-to)24187-24196
Number of pages10
JournalThe Journal of Physical Chemistry C
Issue number42
StatePublished - Oct 14 2016

Bibliographical note

KAUST Repository Item: Exported on 2020-10-01
Acknowledgements: The research reported in this work was supported by the King Abdullah University of Science and Technology.


Dive into the research topics of 'New Insight into the Hydrogen Evolution Reaction under Buffered Near-Neutral pH Conditions: Enthalpy and Entropy of Activation'. Together they form a unique fingerprint.

Cite this