Facet Modulation of Interfacial Water Structure Tunes Electrocatalytic Hydrogen Reaction Kinetics.
4 affiliations
- 1Department of Chemistry and Chemical Biology, Baker Lab, Cornell University, Ithaca, New York14853, United States.
- 2Department of Chemistry, Princeton University, Princeton, New Jersey08544, United States.
- 3Instituto de Electroquímica, Universidad de Alicante, Apdo. 99, E-03080Alicante, Spain.
- 4Kavli Institute at Cornell for Nanoscale Science, Cornell University, Ithaca, New York14853, United States.
Abstract
Interfacial water structure is theoretically envisioned as the master regulator of electrocatalytic reaction kinetics, but the direct experimental validation of this role has remained a formidable challenge. Probing kinetic isotope effects (KIEs) is paramount to deciphering the elusive proton-coupled electron transfer (PCET) mechanisms in alkaline media, a long-standing enigma in electrocatalysis. Such precision, however, demands the uncompromising rigor of atomic-level-precise single-crystal electrodes and ultrapure D2O to ensure definitive results. Here, we uncover a hydrogen evolution reaction KIE that varies sharply with the surface structure: ∼6 for Pt(100), ∼1 for Pt(111), and intermediate values for Pt(110). Through a combination of nuclear-electronic orbital density functional theory (NEO-DFT) and in situ laser-induced temperature-jump (LITJ) experiments, we propose that this disparity originates from the difference between a rigid, hexagonal H-bonded network on Pt(111) and a more disordered, flexible interfacial layer on Pt(100) that would be more sensitive to isotopic substitution, as well as from differences in H/D adsorption sites, which would influence the effective proton transfer distances. Furthermore, measurements with stepped surfaces show that step density acts as a critical dial to tune these water environments. Finally, to bridge the knowledge gap between bulk single-crystals and practical nanoparticles, {100}-oriented Pt nanocubes and {111}-oriented Pt nanotetrahedrons reveal a facet-dependent KIE trend comparable to their single-crystal counterparts. These insights provide a transformative framework for the rational design of high-performance interfaces for green hydrogen production.
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BibTeX
@article{briegamartos2026facet,
title = {{Facet Modulation of Interfacial Water Structure Tunes Electrocatalytic Hydrogen Reaction Kinetics.}},
author = {Valentin Briega-Martos and Wenqi Li and Logan E Smith and Natalia García Rey and Haichuan Zhang and Rafael Guzman-Soriano and Ruben Rizo and Enrique Herrero and Victor Climent and Sharon Hammes-Schiffer and Yao Yang},
journal = {Journal of the American Chemical Society},
year = {2026},
month = oct,
doi = {10.1021/jacs.6c11313},
url = {https://europepmc.org/article/MED/42912264},
note = {CC BY-NC-ND},
}
RIS
TY - JOUR
TI - Facet Modulation of Interfacial Water Structure Tunes Electrocatalytic Hydrogen Reaction Kinetics.
AU - Valentin Briega-Martos
AU - Wenqi Li
AU - Logan E Smith
AU - Natalia García Rey
AU - Haichuan Zhang
AU - Rafael Guzman-Soriano
AU - Ruben Rizo
AU - Enrique Herrero
AU - Victor Climent
AU - Sharon Hammes-Schiffer
AU - Yao Yang
PY - 2026
DA - 2026/10/01
JO - Journal of the American Chemical Society
DO - 10.1021/jacs.6c11313
UR - https://europepmc.org/article/MED/42912264
AB - Interfacial water structure is theoretically envisioned as the master regulator of electrocatalytic reaction kinetics, but the direct experimental validation of this role has remained a formidable challenge. Probing kinetic isotope effects (KIEs) is paramount to deciphering the elusive proton-coupled electron transfer (PCET) mechanisms in alkaline media, a long-standing enigma in electrocatalysis. Such precision, however, demands the uncompromising rigor of atomic-level-precise single-crystal electrodes and ultrapure D2O to ensure definitive results. Here, we uncover a hydrogen evolution reaction KIE that varies sharply with the surface structure: ∼6 for Pt(100), ∼1 for Pt(111), and intermediate values for Pt(110). Through a combination of nuclear-electronic orbital density functional theory (NEO-DFT) and in situ laser-induced temperature-jump (LITJ) experiments, we propose that this disparity originates from the difference between a rigid, hexagonal H-bonded network on Pt(111) and a more disordered, flexible interfacial layer on Pt(100) that would be more sensitive to isotopic substitution, as well as from differences in H/D adsorption sites, which would influence the effective proton transfer distances. Furthermore, measurements with stepped surfaces show that step density acts as a critical dial to tune these water environments. Finally, to bridge the knowledge gap between bulk single-crystals and practical nanoparticles, {100}-oriented Pt nanocubes and {111}-oriented Pt nanotetrahedrons reveal a facet-dependent KIE trend comparable to their single-crystal counterparts. These insights provide a transformative framework for the rational design of high-performance interfaces for green hydrogen production.
SN - 0002-7863
SN - 1520-5126
ER -