# B-site substitution-induced band edge shifts in perovskite-type Cu(Nb,Ta)O<sub>3</sub> solid solutions for visible-light-driven hydrogen evolution

https://mdr.nims.go.jp/datasets/e6db09e5-49d6-4fea-bab3-81790eb4665a

## File

- [Wang_JMC_2025.pdf](https://mdr.nims.go.jp/filesets/6d5be9fc-8c66-479d-9807-eb77b40559f4/download) ([Detail](https://mdr.nims.go.jp/filesets/6d5be9fc-8c66-479d-9807-eb77b40559f4.md))

## Id

e6db09e5-49d6-4fea-bab3-81790eb4665a

## Local identifier



## Visibility

open_to_public

## State

published

## Created at

2025-12-12T02:08:04.002199Z

## Updated at

2025-12-12T07:30:04.568608Z

## Published at

2025-12-12T07:26:08.610639Z

## Doi

https://doi.org/10.48505/nims.6001

## First published url

https://doi.org/10.1039/d5tc02066b

## Date published

2025-08-14

## Recorded date published

2025-10-9

## Resource type

journal_article

## Manuscript type

authors_original

## Collection



## Title

- title: B-site substitution-induced band edge shifts in perovskite-type Cu(Nb,Ta)O<sub>3</sub>
    solid solutions for visible-light-driven hydrogen evolution
  title_type: original
  lang: en

## Description

- description: The rational design of photocatalysts with precise bandgap and band-edge
    control is crucial for achieving the visible-light-driven conversion of solar
    to hydrogen. This study demonstrates a novel strategy for band-edge engineering
    through B-site cation substitution and symmetry evolution in Cu (3d10)-based perovskites.
    Substitution of Ta5+ (5d0) for Nb5+ (4d0) in CuNbO3 induces sequential phase transitions
    (Pc–R3c–R[3 with combining macron]c), accompanied by systematic bandgap modulation
    from 1.57 to 2.23 eV. The R[3 with combining macron]c CuTaO3 phase exhibits a
    much higher conduction band (−0.90 V vs. standard hydrogen electrode) than the
    H+/H2 potential and a slightly lower valence band than the O2/H2O potential. Visible-light-driven
    hydrogen evolution occurs efficiently on CuTaO3 with Ru cocatalyst, in the presence
    of S2−/SO32− sacrificial agents. Our experiments and first-principles calculations
    reveal that the Ta-for-Nb-substitution widens the bandgap by lowering the valence
    band maximum via weakened Cu–O hybridization, while simultaneously elevating the
    conduction band minimum via Ta 5d orbital contributions. The inherent bandgap-narrowing
    tendency of structural evolution from polar Pc to centrosymmetric R[3 with combining
    macron]c symmetry is attenuated by Ta substitution-induced elongation of Cu–O
    bonds. The interplay between B-site cation engineering and symmetry-induced electronic
    degeneration establishes a materials design paradigm for visible-light-driven
    photocatalysis, demonstrating how to enable targeted bandgap optimization by coupling
    orbital-level modifications and phase transition.
  description_type: abstract
  lang: und

## Creator

- name: Haocong Wang
  role: author
- name: Chihiro Takahashi
  role: author
- name: Xuemeng Guo
  role: author
- name: Shunya Okada
  role: author
- name: Hajime Suzuki
  role: author
  orcid: https://orcid.org/0000-0002-8891-2033
- name: Daiming Tang
  role: author
  orcid: https://orcid.org/0000-0001-7136-7481
- name: Wei Yi
  role: author
  orcid: https://orcid.org/0000-0001-5040-8416
- name: Ikuya Yamada
  role: author
- name: Xiaojuan Liu
  role: author
  orcid: https://orcid.org/0000-0002-9215-7616
- name: Ryu Abe
  role: author
  orcid: https://orcid.org/0000-0001-8592-076X
- name: Koji Fujita
  role: author
  orcid: https://orcid.org/0000-0002-1700-0889

## Contact agent



## Publisher

organization: Royal Society of Chemistry (RSC)

## Managing organization



## Keyword

- subject: hydrogen evolution
  schema: not_defined
- subject: perovskite
  schema: not_defined
- subject: substitution-induced band edge shifts
  schema: not_defined

## Rights

- identifier: http://rightsstatements.org/vocab/InC/1.0/

## Other identifier(s)



## Data origin



## Embargo



## Journal

- title: Journal of Materials Chemistry C
  issn: '20507526'
  volume: '13'
  issue: '39'
  start_page: 20146
  end_page: 20155

## Conference



## Related item



## Funding

- funder_name: Mitsubishi Foundation
- funder_name: Izumi Science and Technology Foundation
- identifier: F21750
  funder_name: Japan Society for the Promotion of Science
- identifier: JP21H04619
  funder_name: Japan Society for the Promotion of Science
- identifier: JP22K04686
  funder_name: Japan Society for the Promotion of Science
- identifier: JP22KF0195
  funder_name: Japan Society for the Promotion of Science
- identifier: JP23K23043
  funder_name: Japan Society for the Promotion of Science
- identifier: JP24K21688
  funder_name: Japan Society for the Promotion of Science
- funder_name: Iwatani Naoji Foundation
- funder_name: Nippon Sheet Glass Foundation for Materials Science and Engineering

## 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: 6d5be9fc-8c66-479d-9807-eb77b40559f4
  filename: Wang_JMC_2025.pdf
  content_type: application/pdf
  size: 971788
  md5: fd52a6d16a1118f68a39dd7284ddc429

## Thumbnail

fileset_id: 6d5be9fc-8c66-479d-9807-eb77b40559f4
filename: Wang_JMC_2025.pdf