Theoretical study on the co-adsorption effect of H atoms on NH3 decomposition over Pt(100) and Pt(111) surfaces

Huanhuan Wang; Long Qin; Fanggang Zhang; Zaiqing Que; Ran Sui

doi:10.1016/j.jaecs.2025.100358

Theoretical study on the co-adsorption effect of H atoms on NH₃ decomposition over Pt(100) and Pt(111) surfaces

Huanhuan Wang
, Long Qin
, Fanggang Zhang
, Zaiqing Que
, Ran Sui^*

^*Corresponding author for this work

BA4509 Advanced materials for nuclear energy

Tsinghua University

Research output: Contribution to journal › Article › Scientific › peer-review

3 Citations (Scopus)

Abstract

The influence of co-adsorbed hydrogen (H) atoms on the decomposition of ammonia (NH₃) over two representative crystalline facets of platinum catalyst, i.e., Pt(100) and Pt(111), is investigated using density functional theory (DFT) and microkinetic modeling. The results reveal that NH₃ preferentially adsorbs on top sites, with its binding strength decreasing at higher coverages due to intermolecular repulsion. Although NH₃ adsorption is progressively unfavored on both facets with increased coverage by co-adsorbed H atoms, facet-dependent effects are observed: while Pt(100) maintains stable NH₃ decomposition energetics even at high H coverages, Pt(111) shows significant inhibition effect with increased reaction barriers and destabilized intermediates. Microkinetic simulations further confirm that Pt(100) exhibits superior catalytic activity, particularly in N–N coupling and N₂ desorption, compared to Pt(111). These findings highlight the critical role of surface structure and hydrogen coverage in modulating NH₃ decomposition kinetics, providing insights for optimizing Pt-based catalysts in NH₃-based energy systems.

Original language	English
Article number	100358
Journal	Applications in Energy and Combustion Science
Volume	23
DOIs	https://doi.org/10.1016/j.jaecs.2025.100358
Publication status	Published - Sept 2025
MoE publication type	A1 Journal article-refereed

Funding

This work was supported by Grant 52206157 and a National Talent Program of the National Natural Science Foundation of China (NSFC), and Dushi Project of Tsinghua University. The numerical calculations in this paper were done at Hefei Advanced Computing Center. We further acknowledge Dr. Xiaoli Zhang of Guangxi University for her insightful disscussion with us.

Keywords

Ammonia decomposition
Density functional theory
Hydrogen co-adsorption effects
Microkinetic modeling
Platinum catalyst

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10.1016/j.jaecs.2025.100358Licence: CC BY-NC

Cite this

@article{d8fb4ff2c6f84b3584f18363cff406e2,

title = "Theoretical study on the co-adsorption effect of H atoms on NH3 decomposition over Pt(100) and Pt(111) surfaces",

abstract = "The influence of co-adsorbed hydrogen (H) atoms on the decomposition of ammonia (NH3) over two representative crystalline facets of platinum catalyst, i.e., Pt(100) and Pt(111), is investigated using density functional theory (DFT) and microkinetic modeling. The results reveal that NH₃ preferentially adsorbs on top sites, with its binding strength decreasing at higher coverages due to intermolecular repulsion. Although NH3 adsorption is progressively unfavored on both facets with increased coverage by co-adsorbed H atoms, facet-dependent effects are observed: while Pt(100) maintains stable NH3 decomposition energetics even at high H coverages, Pt(111) shows significant inhibition effect with increased reaction barriers and destabilized intermediates. Microkinetic simulations further confirm that Pt(100) exhibits superior catalytic activity, particularly in N–N coupling and N2 desorption, compared to Pt(111). These findings highlight the critical role of surface structure and hydrogen coverage in modulating NH3 decomposition kinetics, providing insights for optimizing Pt-based catalysts in NH3-based energy systems.",

keywords = "Ammonia decomposition, Density functional theory, Hydrogen co-adsorption effects, Microkinetic modeling, Platinum catalyst",

author = "Huanhuan Wang and Long Qin and Fanggang Zhang and Zaiqing Que and Ran Sui",

year = "2025",

month = sep,

doi = "10.1016/j.jaecs.2025.100358",

language = "English",

volume = "23",

journal = "Applications in Energy and Combustion Science",

issn = "2666-352X",

publisher = "Elsevier",

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TY - JOUR

T1 - Theoretical study on the co-adsorption effect of H atoms on NH3 decomposition over Pt(100) and Pt(111) surfaces

AU - Wang, Huanhuan

AU - Qin, Long

AU - Zhang, Fanggang

AU - Que, Zaiqing

AU - Sui, Ran

PY - 2025/9

Y1 - 2025/9

N2 - The influence of co-adsorbed hydrogen (H) atoms on the decomposition of ammonia (NH3) over two representative crystalline facets of platinum catalyst, i.e., Pt(100) and Pt(111), is investigated using density functional theory (DFT) and microkinetic modeling. The results reveal that NH₃ preferentially adsorbs on top sites, with its binding strength decreasing at higher coverages due to intermolecular repulsion. Although NH3 adsorption is progressively unfavored on both facets with increased coverage by co-adsorbed H atoms, facet-dependent effects are observed: while Pt(100) maintains stable NH3 decomposition energetics even at high H coverages, Pt(111) shows significant inhibition effect with increased reaction barriers and destabilized intermediates. Microkinetic simulations further confirm that Pt(100) exhibits superior catalytic activity, particularly in N–N coupling and N2 desorption, compared to Pt(111). These findings highlight the critical role of surface structure and hydrogen coverage in modulating NH3 decomposition kinetics, providing insights for optimizing Pt-based catalysts in NH3-based energy systems.

AB - The influence of co-adsorbed hydrogen (H) atoms on the decomposition of ammonia (NH3) over two representative crystalline facets of platinum catalyst, i.e., Pt(100) and Pt(111), is investigated using density functional theory (DFT) and microkinetic modeling. The results reveal that NH₃ preferentially adsorbs on top sites, with its binding strength decreasing at higher coverages due to intermolecular repulsion. Although NH3 adsorption is progressively unfavored on both facets with increased coverage by co-adsorbed H atoms, facet-dependent effects are observed: while Pt(100) maintains stable NH3 decomposition energetics even at high H coverages, Pt(111) shows significant inhibition effect with increased reaction barriers and destabilized intermediates. Microkinetic simulations further confirm that Pt(100) exhibits superior catalytic activity, particularly in N–N coupling and N2 desorption, compared to Pt(111). These findings highlight the critical role of surface structure and hydrogen coverage in modulating NH3 decomposition kinetics, providing insights for optimizing Pt-based catalysts in NH3-based energy systems.

KW - Ammonia decomposition

KW - Density functional theory

KW - Hydrogen co-adsorption effects

KW - Microkinetic modeling

KW - Platinum catalyst

UR - https://www.scopus.com/pages/publications/105011765029

U2 - 10.1016/j.jaecs.2025.100358

DO - 10.1016/j.jaecs.2025.100358

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SN - 2666-352X

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JO - Applications in Energy and Combustion Science

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