---
_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.
date_created: 2023-12-10T23:00:59Z
date_published: 2023-11-06T00:00:00Z
date_updated: 2023-12-11T11:55:35Z
day: '06'
ddc:
- '540'
department:
- _id: MaIb
doi: 10.1021/acscatal.3c03893
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'
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: 2DF688A6-F248-11E8-B48F-1D18A9856A87
volume: 13
year: '2023'
...
---
_id: '12923'
abstract:
- lang: eng
  text: Photoredox-mediated Ni-catalyzed cross-couplings are powerful transformations
    to form carbon–heteroatom bonds and are generally photocatalyzed by noble metal
    complexes. Low-cost and easy-to-prepare carbon dots (CDs) are attractive quasi-homogeneous
    photocatalyst alternatives, but their applicability is limited by their short
    photoluminescence (PL) lifetimes. By tuning the surface and PL properties of CDs,
    we designed colloidal CD nano-photocatalysts for a broad range of Ni-mediated
    cross-couplings between aryl halides and nucleophiles. In particular, a CD decorated
    with amino groups permitted coupling to a wide range of aryl halides and thiols
    under mild, base-free conditions. Mechanistic studies suggested dynamic quenching
    of the CD excited state by the Ni co-catalyst and identified that pyridinium iodide
    (pyHI), a previously used additive in metallaphotocatalyzed cross-couplings, can
    also act as a photocatalyst in such transformations.
article_processing_charge: No
article_type: original
author:
- first_name: Zhouxiang
  full_name: Zhao, Zhouxiang
  last_name: Zhao
- first_name: Bartholomäus
  full_name: Pieber, Bartholomäus
  id: 93e5e5b2-0da6-11ed-8a41-af589a024726
  last_name: Pieber
  orcid: 0000-0001-8689-388X
- first_name: Martina
  full_name: Delbianco, Martina
  last_name: Delbianco
citation:
  ama: Zhao Z, Pieber B, Delbianco M. Modulating the surface and photophysical properties
    of carbon dots to access colloidal photocatalysts for cross-couplings. <i>ACS
    Catalysis</i>. 2022;12(22):13831-13837. doi:<a href="https://doi.org/10.1021/acscatal.2c04025">10.1021/acscatal.2c04025</a>
  apa: Zhao, Z., Pieber, B., &#38; Delbianco, M. (2022). Modulating the surface and
    photophysical properties of carbon dots to access colloidal photocatalysts for
    cross-couplings. <i>ACS Catalysis</i>. American Chemical Society. <a href="https://doi.org/10.1021/acscatal.2c04025">https://doi.org/10.1021/acscatal.2c04025</a>
  chicago: Zhao, Zhouxiang, Bartholomäus Pieber, and Martina Delbianco. “Modulating
    the Surface and Photophysical Properties of Carbon Dots to Access Colloidal Photocatalysts
    for Cross-Couplings.” <i>ACS Catalysis</i>. American Chemical Society, 2022. <a
    href="https://doi.org/10.1021/acscatal.2c04025">https://doi.org/10.1021/acscatal.2c04025</a>.
  ieee: Z. Zhao, B. Pieber, and M. Delbianco, “Modulating the surface and photophysical
    properties of carbon dots to access colloidal photocatalysts for cross-couplings,”
    <i>ACS Catalysis</i>, vol. 12, no. 22. American Chemical Society, pp. 13831–13837,
    2022.
  ista: Zhao Z, Pieber B, Delbianco M. 2022. Modulating the surface and photophysical
    properties of carbon dots to access colloidal photocatalysts for cross-couplings.
    ACS Catalysis. 12(22), 13831–13837.
  mla: Zhao, Zhouxiang, et al. “Modulating the Surface and Photophysical Properties
    of Carbon Dots to Access Colloidal Photocatalysts for Cross-Couplings.” <i>ACS
    Catalysis</i>, vol. 12, no. 22, American Chemical Society, 2022, pp. 13831–37,
    doi:<a href="https://doi.org/10.1021/acscatal.2c04025">10.1021/acscatal.2c04025</a>.
  short: Z. Zhao, B. Pieber, M. Delbianco, ACS Catalysis 12 (2022) 13831–13837.
date_created: 2023-05-08T08:28:54Z
date_published: 2022-10-27T00:00:00Z
date_updated: 2023-05-15T08:30:13Z
day: '27'
doi: 10.1021/acscatal.2c04025
extern: '1'
intvolume: '        12'
issue: '22'
keyword:
- Catalysis
- General Chemistry
language:
- iso: eng
main_file_link:
- open_access: '1'
  url: https://doi.org/10.1021/acscatal.2c04025
month: '10'
oa: 1
oa_version: Published Version
page: 13831-13837
publication: ACS Catalysis
publication_identifier:
  eissn:
  - 2155-5435
publication_status: published
publisher: American Chemical Society
quality_controlled: '1'
scopus_import: '1'
status: public
title: Modulating the surface and photophysical properties of carbon dots to access
  colloidal photocatalysts for cross-couplings
type: journal_article
user_id: 2DF688A6-F248-11E8-B48F-1D18A9856A87
volume: 12
year: '2022'
...
---
_id: '11954'
abstract:
- lang: eng
  text: The combination of nickel and photocatalysis has unlocked a variety of cross-couplings.
    These protocols rely on a few photocatalysts that can only convert a small portion
    of visible light (<500 nm) into chemical energy. The high-energy photons that
    excite the photocatalyst can result in unwanted side reactions. Dyes that absorb
    a much broader spectrum of light are not applicable because of their short-lived
    singlet excited states. Here, we describe a self-assembling catalyst system that
    overcomes this limitation. Immobilization of a nickel catalyst on dye-sensitized
    titanium dioxide results in a material that catalyzes carbon–heteroatom and carbon–carbon
    bond formations. The modular approach of dye-sensitized metallaphotocatalysts
    accesses the entire visible light spectrum and allows tackling selectivity issues
    resulting from low wavelengths strategically. The concept overcomes current limitations
    of metallaphotocatalysis by unlocking the potential of dyes that were previously
    unsuitable.
article_processing_charge: No
article_type: original
author:
- first_name: Susanne
  full_name: Reischauer, Susanne
  last_name: Reischauer
- first_name: Volker
  full_name: Strauss, Volker
  last_name: Strauss
- first_name: Bartholomäus
  full_name: Pieber, Bartholomäus
  id: 93e5e5b2-0da6-11ed-8a41-af589a024726
  last_name: Pieber
  orcid: 0000-0001-8689-388X
citation:
  ama: Reischauer S, Strauss V, Pieber B. Modular, self-assembling metallaphotocatalyst
    for cross-couplings using the full visible-light spectrum. <i>ACS Catalysis</i>.
    2020;10(22):13269–13274. doi:<a href="https://doi.org/10.1021/acscatal.0c03950">10.1021/acscatal.0c03950</a>
  apa: Reischauer, S., Strauss, V., &#38; Pieber, B. (2020). Modular, self-assembling
    metallaphotocatalyst for cross-couplings using the full visible-light spectrum.
    <i>ACS Catalysis</i>. American Chemical Society. <a href="https://doi.org/10.1021/acscatal.0c03950">https://doi.org/10.1021/acscatal.0c03950</a>
  chicago: Reischauer, Susanne, Volker Strauss, and Bartholomäus Pieber. “Modular,
    Self-Assembling Metallaphotocatalyst for Cross-Couplings Using the Full Visible-Light
    Spectrum.” <i>ACS Catalysis</i>. American Chemical Society, 2020. <a href="https://doi.org/10.1021/acscatal.0c03950">https://doi.org/10.1021/acscatal.0c03950</a>.
  ieee: S. Reischauer, V. Strauss, and B. Pieber, “Modular, self-assembling metallaphotocatalyst
    for cross-couplings using the full visible-light spectrum,” <i>ACS Catalysis</i>,
    vol. 10, no. 22. American Chemical Society, pp. 13269–13274, 2020.
  ista: Reischauer S, Strauss V, Pieber B. 2020. Modular, self-assembling metallaphotocatalyst
    for cross-couplings using the full visible-light spectrum. ACS Catalysis. 10(22),
    13269–13274.
  mla: Reischauer, Susanne, et al. “Modular, Self-Assembling Metallaphotocatalyst
    for Cross-Couplings Using the Full Visible-Light Spectrum.” <i>ACS Catalysis</i>,
    vol. 10, no. 22, American Chemical Society, 2020, pp. 13269–13274, doi:<a href="https://doi.org/10.1021/acscatal.0c03950">10.1021/acscatal.0c03950</a>.
  short: S. Reischauer, V. Strauss, B. Pieber, ACS Catalysis 10 (2020) 13269–13274.
date_created: 2022-08-24T10:40:46Z
date_published: 2020-11-02T00:00:00Z
date_updated: 2023-02-21T10:09:09Z
day: '02'
doi: 10.1021/acscatal.0c03950
extern: '1'
intvolume: '        10'
issue: '22'
language:
- iso: eng
main_file_link:
- open_access: '1'
  url: https://doi.org/10.26434/chemrxiv.12444908
month: '11'
oa: 1
oa_version: Preprint
page: 13269–13274
publication: ACS Catalysis
publication_identifier:
  eissn:
  - 2155-5435
publication_status: published
publisher: American Chemical Society
quality_controlled: '1'
scopus_import: '1'
status: public
title: Modular, self-assembling metallaphotocatalyst for cross-couplings using the
  full visible-light spectrum
type: journal_article
user_id: 2DF688A6-F248-11E8-B48F-1D18A9856A87
volume: 10
year: '2020'
...