---
OA_type: free access
_id: '15114'
abstract:
- lang: eng
  text: As a key liquid organic hydrogen carrier, investigating the decomposition
    of formic acid (HCOOH) on the Pd (1 1 1) transition metal surface is imperative
    for harnessing hydrogen energy. Despite a multitude of studies, the major mechanisms
    and key intermediates involved in the dehydrogenation process of formic acid remain
    a great topic of debate due to ambiguous adsorbate interactions. In this research,
    we develop an advanced microkinetic model based on first-principles calculations,
    accounting for adsorbate–adsorbate interactions. Our study unveils a comprehensive
    mechanism for the Pd (1 1 1) surface, highlighting the significance of coverage
    effects in formic acid dehydrogenation. Our findings unequivocally demonstrate
    that H coverage on the Pd (1 1 1) surface renders formic acid more susceptible
    to decompose into H2 and CO2 through COOH intermediates. Consistent with experimental
    results, the selectivity of H2 in the decomposition of formic acid on the Pd (1
    1 1) surface approaches 100 %. Considering the influence of H coverage, our kinetic
    analysis aligns perfectly with experimental values at a temperature of 373 K.
acknowledgement: The authors acknowledge the financial support from the National Key
  Research and Development Project of China (2021YFA1500900, 2022YFE0113800), the
  National Natural Science Foundation of China (22141001, U21A20298), Zhejiang Innovation
  Team (2017R5203).
article_number: '119959'
article_processing_charge: No
article_type: original
author:
- first_name: Zihao
  full_name: Yao, Zihao
  last_name: Yao
- first_name: Xu
  full_name: Liu, Xu
  last_name: Liu
- first_name: Rhys
  full_name: Bunting, Rhys
  id: 91deeae8-1207-11ec-b130-c194ad5b50c6
  last_name: Bunting
  orcid: 0000-0001-6928-074X
- first_name: Jianguo
  full_name: Wang, Jianguo
  last_name: Wang
citation:
  ama: 'Yao Z, Liu X, Bunting R, Wang J. Unravelling the reaction mechanism for H2
    production via formic acid decomposition over Pd: Coverage-dependent microkinetic
    modeling. <i>Chemical Engineering Science</i>. 2024;291. doi:<a href="https://doi.org/10.1016/j.ces.2024.119959">10.1016/j.ces.2024.119959</a>'
  apa: 'Yao, Z., Liu, X., Bunting, R., &#38; Wang, J. (2024). Unravelling the reaction
    mechanism for H2 production via formic acid decomposition over Pd: Coverage-dependent
    microkinetic modeling. <i>Chemical Engineering Science</i>. Elsevier. <a href="https://doi.org/10.1016/j.ces.2024.119959">https://doi.org/10.1016/j.ces.2024.119959</a>'
  chicago: 'Yao, Zihao, Xu Liu, Rhys Bunting, and Jianguo Wang. “Unravelling the Reaction
    Mechanism for H2 Production via Formic Acid Decomposition over Pd: Coverage-Dependent
    Microkinetic Modeling.” <i>Chemical Engineering Science</i>. Elsevier, 2024. <a
    href="https://doi.org/10.1016/j.ces.2024.119959">https://doi.org/10.1016/j.ces.2024.119959</a>.'
  ieee: 'Z. Yao, X. Liu, R. Bunting, and J. Wang, “Unravelling the reaction mechanism
    for H2 production via formic acid decomposition over Pd: Coverage-dependent microkinetic
    modeling,” <i>Chemical Engineering Science</i>, vol. 291. Elsevier, 2024.'
  ista: 'Yao Z, Liu X, Bunting R, Wang J. 2024. Unravelling the reaction mechanism
    for H2 production via formic acid decomposition over Pd: Coverage-dependent microkinetic
    modeling. Chemical Engineering Science. 291, 119959.'
  mla: 'Yao, Zihao, et al. “Unravelling the Reaction Mechanism for H2 Production via
    Formic Acid Decomposition over Pd: Coverage-Dependent Microkinetic Modeling.”
    <i>Chemical Engineering Science</i>, vol. 291, 119959, Elsevier, 2024, doi:<a
    href="https://doi.org/10.1016/j.ces.2024.119959">10.1016/j.ces.2024.119959</a>.'
  short: Z. Yao, X. Liu, R. Bunting, J. Wang, Chemical Engineering Science 291 (2024).
date_created: 2024-03-17T23:00:57Z
date_published: 2024-06-05T00:00:00Z
date_updated: 2025-09-04T13:02:40Z
day: '05'
department:
- _id: MaIb
doi: 10.1016/j.ces.2024.119959
external_id:
  isi:
  - '001203872000001'
intvolume: '       291'
isi: 1
language:
- iso: eng
main_file_link:
- open_access: '1'
  url: https://doi.org/10.1016/j.ces.2024.119959
month: '06'
oa: 1
oa_version: None
publication: Chemical Engineering Science
publication_identifier:
  issn:
  - 0009-2509
publication_status: published
publisher: Elsevier
quality_controlled: '1'
scopus_import: '1'
status: public
title: 'Unravelling the reaction mechanism for H2 production via formic acid decomposition
  over Pd: Coverage-dependent microkinetic modeling'
type: journal_article
user_id: 317138e5-6ab7-11ef-aa6d-ffef3953e345
volume: 291
year: '2024'
...
---
OA_type: free access
_id: '15356'
abstract:
- lang: eng
  text: Identifying efficient active sites for the direct synthesis of hydrogen peroxide
    over Pd-based catalysts has been a subject of considerable debate. In this study,
    we employ particle swarm optimization method and density functional theory to
    explore the H2O2 synthesis mechanism on Pd, PdO, and the partially oxidized surface
    (Pd9OX). A comprehensive mechanism for Pd9OX is elucidated, and subsequent coverage-dependent
    kinetic analysis allows for a quantitative assessment of catalytic performance
    at the interphase. Our findings conclusively establish that the interphase between
    Pd and PdO represents the optimal active site. Phase diagram analysis further
    aids in determining stable structures under reaction conditions. At 298.15 K and
    under oxygen balance, the Pd9O6 surface remains stable throughout the reaction,
    demonstrating high activity and selectivity. This work underscores the significance
    of the interphase in comprehending catalytic performance and unveils promising
    avenues for optimizing catalyst performance by controlling reaction conditions
    and surface composition.
acknowledgement: The authors acknowledge the financial support from the National Key
  Research and Development Project of China (2021YFA1500900, 2022YFE0113800), the
  National Natural Science Foundation of China (22141001, U21A20298), Zhejiang Innovation
  Team (2017R5203).
article_number: '120199'
article_processing_charge: No
article_type: original
author:
- first_name: Jinyan
  full_name: Zhao, Jinyan
  last_name: Zhao
- first_name: Zihao
  full_name: Yao, Zihao
  last_name: Yao
- first_name: Rhys
  full_name: Bunting, Rhys
  id: 91deeae8-1207-11ec-b130-c194ad5b50c6
  last_name: Bunting
  orcid: 0000-0001-6928-074X
- first_name: Yaqiu
  full_name: Wang, Yaqiu
  last_name: Wang
- first_name: Jianguo
  full_name: Wang, Jianguo
  last_name: Wang
citation:
  ama: Zhao J, Yao Z, Bunting R, Wang Y, Wang J. Identifying Pd9OX as the optimum
    catalyst for the direct synthesis of H2O2 through microkinetic modeling with coverage
    effects. <i>Chemical Engineering Science</i>. 2024;295. doi:<a href="https://doi.org/10.1016/j.ces.2024.120199">10.1016/j.ces.2024.120199</a>
  apa: Zhao, J., Yao, Z., Bunting, R., Wang, Y., &#38; Wang, J. (2024). Identifying
    Pd9OX as the optimum catalyst for the direct synthesis of H2O2 through microkinetic
    modeling with coverage effects. <i>Chemical Engineering Science</i>. Elsevier.
    <a href="https://doi.org/10.1016/j.ces.2024.120199">https://doi.org/10.1016/j.ces.2024.120199</a>
  chicago: Zhao, Jinyan, Zihao Yao, Rhys Bunting, Yaqiu Wang, and Jianguo Wang. “Identifying
    Pd9OX as the Optimum Catalyst for the Direct Synthesis of H2O2 through Microkinetic
    Modeling with Coverage Effects.” <i>Chemical Engineering Science</i>. Elsevier,
    2024. <a href="https://doi.org/10.1016/j.ces.2024.120199">https://doi.org/10.1016/j.ces.2024.120199</a>.
  ieee: J. Zhao, Z. Yao, R. Bunting, Y. Wang, and J. Wang, “Identifying Pd9OX as the
    optimum catalyst for the direct synthesis of H2O2 through microkinetic modeling
    with coverage effects,” <i>Chemical Engineering Science</i>, vol. 295. Elsevier,
    2024.
  ista: Zhao J, Yao Z, Bunting R, Wang Y, Wang J. 2024. Identifying Pd9OX as the optimum
    catalyst for the direct synthesis of H2O2 through microkinetic modeling with coverage
    effects. Chemical Engineering Science. 295, 120199.
  mla: Zhao, Jinyan, et al. “Identifying Pd9OX as the Optimum Catalyst for the Direct
    Synthesis of H2O2 through Microkinetic Modeling with Coverage Effects.” <i>Chemical
    Engineering Science</i>, vol. 295, 120199, Elsevier, 2024, doi:<a href="https://doi.org/10.1016/j.ces.2024.120199">10.1016/j.ces.2024.120199</a>.
  short: J. Zhao, Z. Yao, R. Bunting, Y. Wang, J. Wang, Chemical Engineering Science
    295 (2024).
date_created: 2024-05-05T22:01:02Z
date_published: 2024-08-05T00:00:00Z
date_updated: 2025-09-04T13:54:17Z
day: '05'
department:
- _id: MaIb
doi: 10.1016/j.ces.2024.120199
external_id:
  isi:
  - '001236643300001'
intvolume: '       295'
isi: 1
language:
- iso: eng
main_file_link:
- open_access: '1'
  url: https://doi.org/10.1016/j.ces.2024.120199
month: '08'
oa: 1
oa_version: None
publication: Chemical Engineering Science
publication_identifier:
  issn:
  - 0009-2509
publication_status: published
publisher: Elsevier
quality_controlled: '1'
scopus_import: '1'
status: public
title: Identifying Pd9OX as the optimum catalyst for the direct synthesis of H2O2
  through microkinetic modeling with coverage effects
type: journal_article
user_id: 317138e5-6ab7-11ef-aa6d-ffef3953e345
volume: 295
year: '2024'
...