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

Handle URI:
http://hdl.handle.net/10754/622435
Title:
New Insight into the Hydrogen Evolution Reaction under Buffered Near-Neutral pH Conditions: Enthalpy and Entropy of Activation
Authors:
Shinagawa, Tatsuya ( 0000-0002-5240-7342 ) ; Takanabe, Kazuhiro ( 0000-0001-5374-9451 )
Abstract:
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.
KAUST Department:
KAUST Catalysis Center (KCC); Physical Sciences and Engineering (PSE) Division
Citation:
Shinagawa T, Takanabe K (2016) New Insight into the Hydrogen Evolution Reaction under Buffered Near-Neutral pH Conditions: Enthalpy and Entropy of Activation. The Journal of Physical Chemistry C 120: 24187–24196. Available: http://dx.doi.org/10.1021/acs.jpcc.6b07954.
Publisher:
American Chemical Society (ACS)
Journal:
The Journal of Physical Chemistry C
Issue Date:
6-Oct-2016
DOI:
10.1021/acs.jpcc.6b07954
Type:
Article
ISSN:
1932-7447; 1932-7455
Sponsors:
The research reported in this work was supported by the King Abdullah University of Science and Technology.
Additional Links:
http://pubs.acs.org/doi/full/10.1021/acs.jpcc.6b07954
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; KAUST Catalysis Center (KCC)

Full metadata record

DC FieldValue Language
dc.contributor.authorShinagawa, Tatsuyaen
dc.contributor.authorTakanabe, Kazuhiroen
dc.date.accessioned2017-01-02T09:28:31Z-
dc.date.available2017-01-02T09:28:31Z-
dc.date.issued2016-10-06en
dc.identifier.citationShinagawa T, Takanabe K (2016) New Insight into the Hydrogen Evolution Reaction under Buffered Near-Neutral pH Conditions: Enthalpy and Entropy of Activation. The Journal of Physical Chemistry C 120: 24187–24196. Available: http://dx.doi.org/10.1021/acs.jpcc.6b07954.en
dc.identifier.issn1932-7447en
dc.identifier.issn1932-7455en
dc.identifier.doi10.1021/acs.jpcc.6b07954en
dc.identifier.urihttp://hdl.handle.net/10754/622435-
dc.description.abstractElectrochemical 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.en
dc.description.sponsorshipThe research reported in this work was supported by the King Abdullah University of Science and Technology.en
dc.publisherAmerican Chemical Society (ACS)en
dc.relation.urlhttp://pubs.acs.org/doi/full/10.1021/acs.jpcc.6b07954en
dc.titleNew Insight into the Hydrogen Evolution Reaction under Buffered Near-Neutral pH Conditions: Enthalpy and Entropy of Activationen
dc.typeArticleen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.identifier.journalThe Journal of Physical Chemistry Cen
kaust.authorShinagawa, Tatsuyaen
kaust.authorTakanabe, Kazuhiroen
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