---
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'
...
---
_id: '13216'
abstract:
- lang: eng
  text: Physical catalysts often have multiple sites where reactions can take place.
    One prominent example is single-atom alloys, where the reactive dopant atoms can
    preferentially locate in the bulk or at different sites on the surface of the
    nanoparticle. However, ab initio modeling of catalysts usually only considers
    one site of the catalyst, neglecting the effects of multiple sites. Here, nanoparticles
    of copper doped with single-atom rhodium or palladium are modeled for the dehydrogenation
    of propane. Single-atom alloy nanoparticles are simulated at 400–600 K, using
    machine learning potentials trained on density functional theory calculations,
    and then the occupation of different single-atom active sites is identified using
    a similarity kernel. Further, the turnover frequency for all possible sites is
    calculated for propane dehydrogenation to propene through microkinetic modeling
    using density functional theory calculations. The total turnover frequencies of
    the whole nanoparticle are then described from both the population and the individual
    turnover frequency of each site. Under operating conditions, rhodium as a dopant
    is found to almost exclusively occupy (111) surface sites while palladium as a
    dopant occupies a greater variety of facets. Undercoordinated dopant surface sites
    are found to tend to be more reactive for propane dehydrogenation compared to
    the (111) surface. It is found that considering the dynamics of the single-atom
    alloy nanoparticle has a profound effect on the calculated catalytic activity
    of single-atom alloys by several orders of magnitude.
acknowledgement: "B.C. acknowledges resources provided by the Cambridge Tier2 system
  operated by the University of Cambridge Research\r\nComputing Service funded by
  EPSRC Tier-2 capital grant EP/\r\nP020259/1."
article_processing_charge: Yes (via OA deal)
article_type: original
author:
- first_name: Rhys
  full_name: Bunting, Rhys
  id: 91deeae8-1207-11ec-b130-c194ad5b50c6
  last_name: Bunting
  orcid: 0000-0001-6928-074X
- first_name: Felix
  full_name: Wodaczek, Felix
  id: 8b4b6a9f-32b0-11ee-9fa8-bbe85e26258e
  last_name: Wodaczek
  orcid: 0009-0000-1457-795X
- first_name: Tina
  full_name: Torabi, Tina
  last_name: Torabi
- first_name: Bingqing
  full_name: Cheng, Bingqing
  id: cbe3cda4-d82c-11eb-8dc7-8ff94289fcc9
  last_name: Cheng
  orcid: 0000-0002-3584-9632
citation:
  ama: 'Bunting R, Wodaczek F, Torabi T, Cheng B. Reactivity of single-atom alloy
    nanoparticles: Modeling the dehydrogenation of propane. <i>Journal of the American
    Chemical Society</i>. 2023;145(27):14894-14902. doi:<a href="https://doi.org/10.1021/jacs.3c04030">10.1021/jacs.3c04030</a>'
  apa: 'Bunting, R., Wodaczek, F., Torabi, T., &#38; Cheng, B. (2023). Reactivity
    of single-atom alloy nanoparticles: Modeling the dehydrogenation of propane. <i>Journal
    of the American Chemical Society</i>. American Chemical Society. <a href="https://doi.org/10.1021/jacs.3c04030">https://doi.org/10.1021/jacs.3c04030</a>'
  chicago: 'Bunting, Rhys, Felix Wodaczek, Tina Torabi, and Bingqing Cheng. “Reactivity
    of Single-Atom Alloy Nanoparticles: Modeling the Dehydrogenation of Propane.”
    <i>Journal of the American Chemical Society</i>. American Chemical Society, 2023.
    <a href="https://doi.org/10.1021/jacs.3c04030">https://doi.org/10.1021/jacs.3c04030</a>.'
  ieee: 'R. Bunting, F. Wodaczek, T. Torabi, and B. Cheng, “Reactivity of single-atom
    alloy nanoparticles: Modeling the dehydrogenation of propane,” <i>Journal of the
    American Chemical Society</i>, vol. 145, no. 27. American Chemical Society, pp.
    14894–14902, 2023.'
  ista: 'Bunting R, Wodaczek F, Torabi T, Cheng B. 2023. Reactivity of single-atom
    alloy nanoparticles: Modeling the dehydrogenation of propane. Journal of the American
    Chemical Society. 145(27), 14894–14902.'
  mla: 'Bunting, Rhys, et al. “Reactivity of Single-Atom Alloy Nanoparticles: Modeling
    the Dehydrogenation of Propane.” <i>Journal of the American Chemical Society</i>,
    vol. 145, no. 27, American Chemical Society, 2023, pp. 14894–902, doi:<a href="https://doi.org/10.1021/jacs.3c04030">10.1021/jacs.3c04030</a>.'
  short: R. Bunting, F. Wodaczek, T. Torabi, B. Cheng, Journal of the American Chemical
    Society 145 (2023) 14894–14902.
corr_author: '1'
date_created: 2023-07-12T09:16:40Z
date_published: 2023-06-30T00:00:00Z
date_updated: 2024-10-21T06:01:30Z
day: '30'
ddc:
- '540'
department:
- _id: MaIb
- _id: BiCh
doi: 10.1021/jacs.3c04030
external_id:
  isi:
  - '001020623900001'
  pmid:
  - '37390457'
file:
- access_level: open_access
  checksum: e07d5323f9c0e5cbd1ad6453f29440ab
  content_type: application/pdf
  creator: cchlebak
  date_created: 2023-07-12T10:22:04Z
  date_updated: 2023-07-12T10:22:04Z
  file_id: '13219'
  file_name: 2023_JACS_Bunting.pdf
  file_size: 3155843
  relation: main_file
  success: 1
file_date_updated: 2023-07-12T10:22:04Z
has_accepted_license: '1'
intvolume: '       145'
isi: 1
issue: '27'
keyword:
- Colloid and Surface Chemistry
- Biochemistry
- General Chemistry
- Catalysis
language:
- iso: eng
month: '06'
oa: 1
oa_version: Published Version
page: 14894-14902
pmid: 1
publication: Journal of the American Chemical Society
publication_identifier:
  eissn:
  - 1520-5126
  issn:
  - 0002-7863
publication_status: published
publisher: American Chemical Society
quality_controlled: '1'
scopus_import: '1'
status: public
title: 'Reactivity of single-atom alloy nanoparticles: Modeling the dehydrogenation
  of propane'
tmp:
  image: /images/cc_by.png
  legal_code_url: https://creativecommons.org/licenses/by/4.0/legalcode
  name: Creative Commons Attribution 4.0 International Public License (CC-BY 4.0)
  short: CC BY (4.0)
type: journal_article
user_id: 8b945eb4-e2f2-11eb-945a-df72226e66a9
volume: 145
year: '2023'
...
---
_id: '14663'
abstract:
- lang: eng
  text: As a bottleneck in the direct synthesis of hydrogen peroxide, the development
    of an efficient palladium-based catalyst has garnered great attention. However,
    elusive active centers and reaction mechanism issues inhibit further optimization
    of its performance. In this work, advanced microkinetic modeling with the adsorbate–adsorbate
    interaction and nanoparticle size effect based on first-principles calculations
    is developed. A full mechanism uncovering the significance of adsorbate–adsorbate
    interaction is determined on Pd nanoparticles. We demonstrate unambiguously that
    Pd(100) with main coverage species of O2 and H is beneficial to H2O2 production,
    being consistent with experimental operando observation, while H2O forms on Pd(111)
    covered by O species and Pd(211) covered by O and OH species. Kinetic analyses
    further enable quantitative estimation of the influence of temperature, pressure,
    and particle size. Large-size Pd nanoparticles are found to achieve a high H2O2
    reaction rate when the operating conditions are moderate temperature and higher
    oxygen partial pressure. We reveal that specific facets of the Pd nanoparticles
    are crucial factors for their selectivity and activity. Consistent with the experiment,
    the production of H2O2 is discovered to be more favorable on Pd nanoparticles
    containing Pd(100) facets. The ratio of H2/O2 induces substantial variations in
    the coverage of intermediates of O2 and H on Pd(100), resulting in a change in
    product selectivity.
acknowledgement: The authors acknowledge the financial support from the National Natural
  Science Foundation of China (22008211, 92045303, U21A20298), the National Key Research
  and Development Project of China (2021YFA1500900, 2022YFE0113800), and Zhejiang
  Innovation Team (2017R5203).
article_processing_charge: Yes (in subscription journal)
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: P.
  full_name: Hu, P.
  last_name: Hu
- first_name: Jianguo
  full_name: Wang, Jianguo
  last_name: Wang
citation:
  ama: Zhao J, Yao Z, Bunting R, Hu P, Wang J. Microkinetic modeling with size-dependent
    and adsorbate-adsorbate interactions for the direct synthesis of H₂O₂ over Pd
    nanoparticles. <i>ACS Catalysis</i>. 2023;13(22):15054-15073. doi:<a href="https://doi.org/10.1021/acscatal.3c03893">10.1021/acscatal.3c03893</a>
  apa: Zhao, J., Yao, Z., Bunting, R., Hu, P., &#38; Wang, J. (2023). Microkinetic
    modeling with size-dependent and adsorbate-adsorbate interactions for the direct
    synthesis of H₂O₂ over Pd nanoparticles. <i>ACS Catalysis</i>. American Chemical
    Society. <a href="https://doi.org/10.1021/acscatal.3c03893">https://doi.org/10.1021/acscatal.3c03893</a>
  chicago: Zhao, Jinyan, Zihao Yao, Rhys Bunting, P. Hu, and Jianguo Wang. “Microkinetic
    Modeling with Size-Dependent and Adsorbate-Adsorbate Interactions for the Direct
    Synthesis of H₂O₂ over Pd Nanoparticles.” <i>ACS Catalysis</i>. American Chemical
    Society, 2023. <a href="https://doi.org/10.1021/acscatal.3c03893">https://doi.org/10.1021/acscatal.3c03893</a>.
  ieee: J. Zhao, Z. Yao, R. Bunting, P. Hu, and J. Wang, “Microkinetic modeling with
    size-dependent and adsorbate-adsorbate interactions for the direct synthesis of
    H₂O₂ over Pd nanoparticles,” <i>ACS Catalysis</i>, vol. 13, no. 22. American Chemical
    Society, pp. 15054–15073, 2023.
  ista: Zhao J, Yao Z, Bunting R, Hu P, Wang J. 2023. Microkinetic modeling with size-dependent
    and adsorbate-adsorbate interactions for the direct synthesis of H₂O₂ over Pd
    nanoparticles. ACS Catalysis. 13(22), 15054–15073.
  mla: Zhao, Jinyan, et al. “Microkinetic Modeling with Size-Dependent and Adsorbate-Adsorbate
    Interactions for the Direct Synthesis of H₂O₂ over Pd Nanoparticles.” <i>ACS Catalysis</i>,
    vol. 13, no. 22, American Chemical Society, 2023, pp. 15054–73, doi:<a href="https://doi.org/10.1021/acscatal.3c03893">10.1021/acscatal.3c03893</a>.
  short: J. Zhao, Z. Yao, R. Bunting, P. Hu, J. Wang, ACS Catalysis 13 (2023) 15054–15073.
corr_author: '1'
date_created: 2023-12-10T23:00:59Z
date_published: 2023-11-06T00:00:00Z
date_updated: 2025-09-09T13:39:57Z
day: '06'
ddc:
- '540'
department:
- _id: MaIb
doi: 10.1021/acscatal.3c03893
external_id:
  isi:
  - '001140495600001'
file:
- access_level: open_access
  checksum: a97c771077af71ddfb2249e34530895c
  content_type: application/pdf
  creator: dernst
  date_created: 2023-12-11T11:55:09Z
  date_updated: 2023-12-11T11:55:09Z
  file_id: '14676'
  file_name: 2023_ACSCatalysis_.pdf
  file_size: 14813812
  relation: main_file
  success: 1
file_date_updated: 2023-12-11T11:55:09Z
has_accepted_license: '1'
intvolume: '        13'
isi: 1
issue: '22'
language:
- iso: eng
month: '11'
oa: 1
oa_version: Published Version
page: 15054-15073
publication: ACS Catalysis
publication_identifier:
  eissn:
  - 2155-5435
publication_status: published
publisher: American Chemical Society
quality_controlled: '1'
scopus_import: '1'
status: public
title: Microkinetic modeling with size-dependent and adsorbate-adsorbate interactions
  for the direct synthesis of H₂O₂ over Pd nanoparticles
tmp:
  image: /images/cc_by.png
  legal_code_url: https://creativecommons.org/licenses/by/4.0/legalcode
  name: Creative Commons Attribution 4.0 International Public License (CC-BY 4.0)
  short: CC BY (4.0)
type: journal_article
user_id: 317138e5-6ab7-11ef-aa6d-ffef3953e345
volume: 13
year: '2023'
...