# Countercation Manipulation Enables Selective Electrochemical CO                    <sub>2</sub>                    ‐to‐Formate Conversion Over Bi‐Polyoxometalate‐Derived Catalysts

https://mdr.nims.go.jp/datasets/303ecaf0-9cb2-4fd8-83d9-c067b265a976

## File

- [Chemistry A European J - 2026 - Kawakami.pdf](https://mdr.nims.go.jp/filesets/5c1a28ba-3df6-468c-9232-0981a16d8c51/download) ([Detail](https://mdr.nims.go.jp/filesets/5c1a28ba-3df6-468c-9232-0981a16d8c51.md))

## Id

303ecaf0-9cb2-4fd8-83d9-c067b265a976

## Local identifier



## Visibility

open_to_public

## State

published

## Created at

2026-10-29T00:40:10.889284Z

## Updated at

2026-10-29T01:06:21.411537Z

## Published at

2026-10-29T03:27:40.099260Z

## Doi



## First published url

https://doi.org/10.1002/chem.71437

## Date published

2026-10-27

## Recorded date published

2026-10-27

## Resource type

journal_article

## Manuscript type

vor

## Collection



## Title

- title: |-
    Countercation Manipulation Enables Selective Electrochemical CO
                        <sub>2</sub>
                        ‐to‐Formate Conversion Over Bi‐Polyoxometalate‐Derived Catalysts
  title_type: original
  lang: en

## Description

- description: "Electrochemical conversion of CO<sub>2</sub> into formate (HCOO<sup>&minus;</sup>)
    represents a promising strategy for mitigating global warming while producing
    an industrially important chemical. Polyoxometalates (POMs), anionic molecular
    metal-oxo clusters, offer unique opportunities as catalysts and catalyst precursors
    for the electrochemical CO<sub>2</sub> reduction reaction (CO<sub>2</sub>RR) owing
    to their structural diversity, compositional tunability, and flexibility in countercation
    selection. Despite these advantages, effective strategies for developing POM-based
    CO<sub>2</sub>RR catalysts with high selectivity toward HCOO<sup>&minus;</sup>
    remain limited. In this study, we demonstrate countercation manipulation as a
    powerful approach to achieving selective HCOO<sup>&minus;</sup> production using
    a bismuth (Bi)-incorporated POM, [Bi<sub>4</sub>O(&gamma;-SiW<sub>10</sub>O<sub>36</sub>)<sub>2</sub>(OAc)]<sup>7&minus;</sup>
    <b>(Bi4)</b>. Under gas-diffusion CO<sub>2</sub>RR conditions with a 2 M KHCO<sub>3</sub>
    aqueous electrolyte, the Ba<sup>2+</sup> salt of <b>Bi4</b> immobilized on carbon
    (Ba-<b>Bi4</b>/C) exhibited high HCOO<sup>&minus;</sup> selectivity with a Faradaic
    efficiency of 84.3&#37; at &minus;0.79 V<sub>RHE</sub>, whereas the corresponding
    tetra-n-butylammonium (TBA<sup>+</sup>) salt (TBA-<b>Bi4</b>/C) exhibited substantially
    lower selectivity (26.6&#37; at &minus;0.79 V<sub>RHE</sub>). Post-reaction analyses
    revealed that both catalysts transformed into highly dispersed Bi species protected
    by WO<sub>x</sub> nanoaggregates. Control experiments and detailed characterizations
    indicated that the countercations, in conjunction with the POM-derived catalyst
    structure, play a crucial role in governing CO<sub>2</sub>RR performance.\r\n\r\n"
  description_type: abstract
  lang: und

## Creator

- name: Kimitake Kawakami
  role: author
- name: Kentaro Yonesato
  role: author
  orcid: https://orcid.org/0000-0001-9143-6691
- name: Shimon Akino
  role: author
- name: Soichi Kikkawa
  role: author
  orcid: https://orcid.org/0000-0002-8193-6374
- name: Seiji Yamazoe
  role: author
  orcid: https://orcid.org/0000-0002-8382-8078
- name: Takuma Kaneko
  role: author
- name: Tomoya Uruga
  role: author
- name: Fumiaki Amano
  role: author
  orcid: https://orcid.org/0000-0003-2812-5799
- name: Yoshiaki Honjo
  role: author
- name: Takaki Hatsui
  role: author
- name: Koji Harano
  role: author
  orcid: https://orcid.org/0000-0001-6800-8023
- name: Kazuya Yamaguchi
  role: author
  orcid: https://orcid.org/0000-0002-7661-4936
- name: Kosuke Suzuki
  role: author
  orcid: https://orcid.org/0000-0002-8123-1462

## Contact agent



## Publisher

organization: Wiley

## Managing organization



## Keyword

- subject: bismuth
  schema: not_defined
- subject: electrochemical CO2 reduction reaction
  schema: not_defined
- subject: electrode catalysis
  schema: not_defined
- subject: nanocatalysts
  schema: not_defined
- subject: polyoxometalates
  schema: not_defined

## Rights

- identifier: https://creativecommons.org/licenses/by/4.0/

## Other identifier(s)



## Data origin



## Embargo



## Journal

- title: Chemistry – A European Journal
  issn: '09476539'
  volume: '32'
  issue: '40'
  article_number: e71437

## Conference



## Related item



## Funding

- funder_name: Japan Science and Technology Agency
- funder_name: Japan Society for the Promotion of Science

## Instrument



## Instrument operator



## Instrument managing organization



## Measurement method



## Specimen



## Chemical composition



## Structure for specimen



## Structural feature for specimen



## Specific property for specimen



## Process for specimen treatment



## Computational method



## Energy level/transition state



## Software



## Custom property



## Fileset

- id: 5c1a28ba-3df6-468c-9232-0981a16d8c51
  filename: Chemistry A European J - 2026 - Kawakami.pdf
  content_type: application/pdf
  size: 3406164
  md5: 7527f3097e74feff2d3b0fa220ec9e2c

## Thumbnail

fileset_id: 5c1a28ba-3df6-468c-9232-0981a16d8c51
filename: Chemistry A European J - 2026 - Kawakami.pdf