Superiority of the (100) Over the (111) Facets of the Nitrides for Hydrogen Evolution Reaction

Abghoui, Younes

doi:10.1007/s11244-021-01474-5

Cited by 10 publications

(8 citation statements)

References 46 publications

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“…This would promote the Volmer reaction, resulting in an increase of H coverage . In another theoretical study, Abghoui et al found that the Volmer reaction barrier tends to decrease with higher working potential. That is, a higher working potential promotes HER by lowering the Volmer reaction barrier, which results in an increase in H coverage.…”

Section: Resultsmentioning

confidence: 98%

First-Principles-Based Kinetic Monte Carlo Model of Hydrogen Evolution Reaction under Realistic Conditions: Solvent, Hydrogen Coverage and Electric Field Effects

Luo,

Guan,

Liu

et al. 2024

ACS Catal.

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The hydrogen evolution reaction (HER) plays an important role in electrocatalytic water splitting. Despite the progress on the development of HER catalysts, the dynamic evolution of HER reaction under realistic electrochemical conditions considering the electric field, solvent, and hydrogen coverage effects is still unclear. In this study, a first-principles-based H surface coverage and potential-dependent kinetic Monte Carlo (KMC) HER model on the Pt (111)/Pt (100) surface is presented. The reaction kinetics and electronic structure analysis of HER on Pt surfaces in the presence of dihydrated proton (H 5 O 2 + ) and H surface coverage is investigated using density functional theory (DFT). The HER KMC model was developed based on the DFT-calculated energetics. The KMC simulation results showed that consideration of H 5 O 2 + species and dynamic evolution of H coverage is essential for accurate description of HER reaction on the Pt catalyst, which fits well with HER polarization data. Moreover, sensitivity analysis shows that HER on Pt ( 111) is mainly affected by the Tafel step. On the Pt(100) surface, HER is primarily governed by the Heyrovsky pathway. Surface species evolution analysis demonstrates that the high working potential accelerated the formation of [Pt-2H] species, leading to increased H coverage and accelerating the HER process. The predicted weakened H binding strength and increased H coverage at high HER working potential was verified by in situ attenuated total reflection Fourier transformed infrared spectroscopy analysis. Overall, the proposed DFT-KMC model represents the state-of-art dynamic simulation of catalytic HER reaction, providing important insights into the evolution of HER under realistic operation conditions.

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Section: Resultsmentioning

confidence: 98%

First-Principles-Based Kinetic Monte Carlo Model of Hydrogen Evolution Reaction under Realistic Conditions: Solvent, Hydrogen Coverage and Electric Field Effects

Luo,

Guan,

Liu

et al. 2024

ACS Catal.

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“…47−54 Moreover, other strategies such as altering electrolytes, improving mass transfer rates, and devising specific electrolytic systems can also contribute to achieving high NRR performance. 55−57 Over the past few decades, these strategies have been successfully applied in the design of heterogeneous electrocatalysts for various applications including the HER, 58,59 oxygen evolution reaction (OER), 60,61 oxygen reduction reaction (ORR), 62,63 and carbon dioxide reduction reaction (CO 2 RR). 64−67 In this investigation, we utilize theoretical calculations to sift through a spectrum of rock salt (RS) (110) TMCN surfaces, aiming to identify a stable and efficacious catalyst for electrochemical nitrogen activation and subsequent ammonia production.…”

Section: Introductionmentioning

confidence: 99%

Catalytic Nitrogen Reduction on the Transition Metal Carbonitride (110) Facet: DFT Predictions and Mechanistic Insights

Iqbal,

Skúlason,

Abghoui

2024

J. Phys. Chem. C

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“…In catalysis, the utilization of nitrogen-rich transition metals is particularly promising where transition metal nitrides (TMNs) were predicted to be good for making ammonia chemically (Michalsky et al, 2015a;Zeinalipour-Yazdi et al, 2015) and electrochemically (Abghoui et al, 2015;Michalsky et al, 2015b;Abghoui et al, 2016;Abghoui and Skúlason, 2017a;Abghoui, 2017;Abghoui and Skúlason, 2017b;Garden et al, 2018;Gudmundsson et al, 2022) through a Mars-van Krevelen mechanism. We explored a wide range of TMN surfaces via density functional theory (DFT) calculations for the possibility of catalyzing NRR where ZrN, VN, CrN, and NbN were nominated as promising material (Abghoui et al, 2015;Abghoui et al, 2016;Abghoui and Skúlason, 2017a;Abghoui and Skúlason, 2017b;Abghoui and Skúlason, 2017c), and TiN along with other earlier TMNs found inactive for NRR (Abghoui and Skúlason, 2017d;Abghoui, 2022), all in the (100) facets of the rocksalt structure. We tested some of these candidates experimentally in our laboratory and agreement was found between our theory and experiment demonstrating stronger nitrogen adsorption for ZrN and NbN and the earliest reaction onset potential for VN (Hanifpour et al, 2022b).…”

Section: Introductionmentioning

confidence: 99%

The role of overlayered nitride electro-materials for N2 reduction to ammonia

Abghoui

Iqbal²,

Skúlason³

2023

Front. Catal.

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Following our previous report on N2 reduction reaction (NRR) on the surface of nitrides, we investigated the influence of incorporation of titanium nitride as a stable and inactive-NRR material into the structure of DFT-predicted NRR-active surfaces of chromium, vanadium, niobium, and zirconium nitrides. The outcome of our density functional theory (DFT) based analyses suggests that combination of titanium nitride with vanadium nitride can enhance the potential-determining step of the reaction with up to 20% compared to pure vanadium nitride while maintaining similar number of proton-electron transfer steps for formation of two ammonia molecules. The influence of titanium nitride on chromium nitride is expected to be more pronounced as rate-determining step associated with nitrogen adsorption on the vacancy and regeneration of the catalyst improves by around 90% compared to the pure chromium nitride. This effect on niobium and zirconium nitride is, however, negative as the potential-determining step becomes larger for the case of niobium nitride, and the reaction pathway changes from nitrogen reduction to hydrogen evolution for the case of zirconium nitride. These results not only encourage experimentalists to explore these overlayered structures further in experiments, but it also opens up the avenue for considering the alloys and dopants of these nitrides via both density functional theory modelling and experiments.

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Superiority of the (100) Over the (111) Facets of the Nitrides for Hydrogen Evolution Reaction

Cited by 10 publications

References 46 publications

First-Principles-Based Kinetic Monte Carlo Model of Hydrogen Evolution Reaction under Realistic Conditions: Solvent, Hydrogen Coverage and Electric Field Effects

First-Principles-Based Kinetic Monte Carlo Model of Hydrogen Evolution Reaction under Realistic Conditions: Solvent, Hydrogen Coverage and Electric Field Effects

Catalytic Nitrogen Reduction on the Transition Metal Carbonitride (110) Facet: DFT Predictions and Mechanistic Insights

The role of overlayered nitride electro-materials for N2 reduction to ammonia

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