An Unusual Exchange Mechanism in the Tafel Reaction on Pt(110)‐(1×1) Surfaces

He, Zhengda; Chen, Yan‐Xia; Juárez, Fernanda; Santos, Elizabeth; Schmickler, Wolfgang

doi:10.1002/celc.201900681

Cited by 4 publications

(1 citation statement)

References 25 publications

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“…Compared to previous studies on Pt(111), ,, we find that our Tafel barriers (0.77–0.83 eV) are within the ranges proposed by other DFT methods. Likewise, Skúlason et al report a Volmer barrier of 0.69 eV on Pt(111), whereas we measured a similar barrier of 0.61 eV.…”

Section: Resultssupporting

confidence: 84%

Modeling Hydrogen Evolution Reaction Kinetics through Explicit Water–Metal Interfaces

Tang

et al. 2020

J. Phys. Chem. C

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Despite the apparent simplicity of the hydrogen evolution reaction (HER) and the decades of research into it, controversy remains in the literature regarding the identity of the active site and the competition between the Heyrovsky and Tafel steps. In this work, we use chargeextrapolated ab initio simulations with explicit water in conjunction with mean-field microkinetic modeling to explore the mechanism for HER on both close-packed (111) and stepped (211) transition metals. First, we show that atop H*, beyond a monolayer of hollow H*, is unlikely to play a role in the HER mechanism, given its very positive adsorption energies. The energetics suggests the Volmer−Heyrovsky mechanism to predominate on fcc transition metals under typical operating conditions. We evaluate our theoretical results vs several experimental observations. We show that the Volmer−Heyrovsky mechanism predicts an activity volcano with its peak at a H* binding ΔG H* ≈ 0 eV, consistent with experiment. In contrast, the Volmer−Tafel volcano shows a broad rate plateau between ΔG H* ≈ 0 eV and ΔG H* ≈ − 0.4 eV. We find our theoretical Tafel slopes to be consistent with experimental ones on a range of transition metals. We show that, in line with experimental observations, the introduction of a CO(g) atmosphere shifts the strong binding metals toward the weak binding leg. Our study suggests that the simple thermodynamic approach to HER activity still holds, even when a detailed kinetic picture is considered.

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Section: Resultssupporting

confidence: 84%

Modeling Hydrogen Evolution Reaction Kinetics through Explicit Water–Metal Interfaces

Tang

et al. 2020

J. Phys. Chem. C

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Can hydrogen anion be a possible intermediate of the hydrogen electrode reaction?

Huang

Attard

2021

Journal of Electroanalytical Chemistry

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Bond Exchange Mechanism: Unveiling the Volmer–Tafel Pathway and an Electronic Descriptor for Predicting Hydrogen Evolution Reaction Activity of Borophene

Siddharthan,

Ghosh,

Thapa

2023

ACS Appl. Energy Mater.

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Hydrogen as a fuel is a promising alternative to harmful fossil fuels, thereby its production by electrocatalytic hydrogen evolution reaction (HER) is an important research problem. Using density functional theory, H 2 evolution through the Volmer−Tafel (V−T) pathway is studied on borophene sheets. The results reveal that the sheets exhibit high activity, comparable to platinum. A better theoretical understanding of the mechanism that explains the experimental results is an existing issue. To address this issue, we have proposed that H 2 evolves through a bond-exchange mechanism in the Tafel step. The activation energy through this mechanism is drastically reduced, compared to the existing model of direct H 2 evolution and matches well with the experimental results in terms of activation energy for HER. It is also tested and observed on other HER catalysts, such as nitrogen-doped graphene, 2H-MoS 2 , and Pt(111), which proves the proposed mechanism is correct for HER. An electronic property-based descriptor is proposed that shows a good correlation with HER activity on the borophene sheets. This work sheds insights into theoretical modeling of HER and can further lead to better methods toward the understanding of the reaction. Also the electronic descriptor can be tested on similar boron allotropes and reactions.

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An Unusual Exchange Mechanism in the Tafel Reaction on Pt(110)‐(1×1) Surfaces

Cited by 4 publications

References 25 publications

Modeling Hydrogen Evolution Reaction Kinetics through Explicit Water–Metal Interfaces

Modeling Hydrogen Evolution Reaction Kinetics through Explicit Water–Metal Interfaces

Can hydrogen anion be a possible intermediate of the hydrogen electrode reaction?

Bond Exchange Mechanism: Unveiling the Volmer–Tafel Pathway and an Electronic Descriptor for Predicting Hydrogen Evolution Reaction Activity of Borophene

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