# Feeble Single-Atom Pd Catalysts for H<sub>2</sub> Production from Formic Acid

https://mdr.nims.go.jp/datasets/ed936f9d-7b56-4afb-bcc7-50ada60a88ff

## File

- [2024A00282G_MDR - コピー.pdf](https://mdr.nims.go.jp/filesets/6b7f5c69-5501-48d4-ac90-4dc7ef5c978e/download) ([Detail](https://mdr.nims.go.jp/filesets/6b7f5c69-5501-48d4-ac90-4dc7ef5c978e.md))

## Id

ed936f9d-7b56-4afb-bcc7-50ada60a88ff

## Local identifier



## Visibility

open_to_public

## State

published

## Created at

2024-03-04T10:28:28.182057Z

## Updated at

2025-01-19T07:31:14.066645Z

## Published at

2025-01-19T07:31:14.211970Z

## Doi

https://doi.org/10.48505/nims.4438

## First published url

https://doi.org/10.1021/acsami.3c18709

## Date published

2024-02-28

## Recorded date published

2024-2-28

## Resource type

journal_article

## Manuscript type

accepted_manuscript

## Collection



## Title

- title: Feeble Single-Atom Pd Catalysts for H<sub>2</sub> Production from Formic
    Acid
  title_type: original
  lang: en

## Description

- description: Single-atom catalysts are thought to be the pinnacle of catalysis.
    However, for many reactions, their suitability has yet to be unequivocally proven.
    Here, we demonstrate why single Pd atoms (PdSA) are not catalytically ideal for
    generating H2 from formic acid as a H2 carrier. We loaded PdSA on three silica
    substrates, mesoporous silicas functionalized with thiol, amine, and dithiocarbamate
    functional groups. The Pd catalytic activity on aminofunctionalized silica (SiO2−NH2/PdSA)
    was far higher than that of the thiolbased catalysts (SiO2−S−PdSA and SiO2−NHCS2−PdSA),
    while the single-atom stability of SiO2−NH2/PdSA against aggregation after the
    first catalytic cycle was the weakest. In this case, Pd aggregation boosted the
    reaction yield. Our experiments and calculations demonstrate that PdSA in SiO2−NH2/PdSA
    loosely binds with amine groups. This leads to a limited charge transfer from
    Pd to the amine groups and causes high aggregability and catalytic activity. According
    to the density functional calculations, the loose binding between Pd and N causes
    most of Pd’s 4d electrons in amino-functionalized SiO2 to remain close to the
    Fermi level and labile for catalysis. However, PdSA chemically binds to the thiol
    group, resulting in strong hybridization between Pd and S, pulling Pd’s 4d states
    deeper into the conduction band and away from the Fermi level. Consequently, fewer
    4d electrons were available for catalysis.
  description_type: abstract
  lang: und

## Creator

- name: Esmail Doustkhah
  role: author
  orcid: https://orcid.org/0000-0003-1459-1756
  organization: National Institute for Materials Science
- name: Nao Tsunoji
  role: author
  orcid: https://orcid.org/0000-0003-4919-702X
- name: Shinya Mine
  role: author
  orcid: https://orcid.org/0000-0002-8339-0301
- name: Takashi Toyao
  role: author
  orcid: https://orcid.org/0000-0002-6062-5622
- name: Ken-ichi Shimizu
  role: author
  orcid: https://orcid.org/0000-0003-0501-0294
- name: Tetsuro Morooka
  role: author
  orcid: https://orcid.org/0000-0003-3436-7030
  organization: National Institute for Materials Science
  ror: https://ror.org/026v1ze26
- name: Takuya Masuda
  role: author
  orcid: https://orcid.org/0000-0001-7462-2177
  organization: National Institute for Materials Science
  ror: https://ror.org/026v1ze26
- name: M. Hussein N. Assadi
  role: author
  orcid: https://orcid.org/0000-0002-1559-3211
- name: Yusuke Ide
  role: author
  orcid: https://orcid.org/0000-0002-6901-6954
  organization: National Institute for Materials Science
  ror: https://ror.org/026v1ze26

## Contact agent



## Publisher

organization: American Chemical Society (ACS)

## Managing organization



## Keyword

- subject: single-atom catalysis (SAC)
  schema: not_defined
- subject: Pd nanocluster
  schema: not_defined
- subject: silica-supported Pd
  schema: not_defined
- subject: Pd DOS
  schema: not_defined
- subject: metal−support interaction
  schema: not_defined
- subject: catalyst reconstruction
  schema: not_defined
- subject: ligand−metal charge transfer
  schema: not_defined

## Rights

- description: This document is the Accepted Manuscript version of a Published Work
    that appeared in final form in ACS Applied Materials & Interfaces, copyright ©
    2024 American Chemical Society after peer review and technical editing by the
    publisher. To access the final edited and published work see https://doi.org/10.1021/acsami.3c18709
  identifier: http://rightsstatements.org/vocab/InC/1.0/

## Other identifier(s)



## Data origin

- data_origin_type: other

## Embargo

start_date: 2024-01-19
end_date: 2025-01-19

## Journal

- title: ACS Applied Materials & Interfaces
  issn: '19448244'
  volume: '16'
  issue: '8'
  start_page: 10251
  end_page: 10259

## Conference



## Related item



## Funding

- identifier: 120C057
  funder_name: HORIZON EUROPE Marie Sklodowska-Curie Actions
- identifier: 21H02034
  funder_name: Japan Society for the Promotion of Science
- identifier: 120C057
  funder_name: T?rkiye Bilimsel ve Teknolojik Arastirma Kurumu

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## Fileset

- id: 6b7f5c69-5501-48d4-ac90-4dc7ef5c978e
  filename: 2024A00282G_MDR - コピー.pdf
  content_type: application/pdf
  size: 1008461
  md5: 8cc6e0f76e35dfabe281cfe6345ce95f

## Thumbnail

fileset_id: 6b7f5c69-5501-48d4-ac90-4dc7ef5c978e
filename: 2024A00282G_MDR - コピー.pdf