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PreprintCC BYChemRxiv

TRMC and NEXAFS Reveal Fast Electron Transfer to Ce3+/Oxygen-Vacancy Traps in Non-Covalent CexOy/C3N4 Interface for Photocatalytic H2

  • Ingrid F. Silva1,2
  • Heer Shah3
  • Christian Kupfer4,5
  • Asia Patriarchi6,7
  • Erwan Paineau8
  • Maria Rita Cicconi9
  • Linda Rockmann10,11
  • Kevin Sivula12,13
  • Marcus Halik10,11
  • David C. Grinter14
  • Robert Palgrave15,16
  • Michael Grätzel17,18
7 more authors
  • Paolo Fornasiero19
  • Michele Melchionna19,20,21
  • Dennis Friedrich22
  • Nieves Lopez-Salas23,24
  • Miguel Ángel Muñoz-Márquez6,7
  • Mark Isaacs15,16
  • Pablo Jiménez-Calvo3,25
25 affiliations
  1. 1Departamento de Quimica, ICEx
  2. 2Universidade Federal de Minas Gerais
  3. 3Chair 'Chemistry of Thin Film Materials', Materials Chemistry section, Department of Chemistry and Pharmacy, IZNF, Cauerstraße 3, Erlangen, Germany, 91058
  4. 4Institute of Materials for Electronics and Energy Technology (i-MEET
  5. 5Friedrich-Alexander-Universität Erlangen-Nürnberg
  6. 6Chemistry Division, School of Science and Technology
  7. 7University of Camerino
  8. 8Laboratoire de Physique des Solides, Université Paris Saclay, 1 rue Nicolas Appert, Orsay, France, 91405
  9. 9Department of Materials Science and Engineering, Friedrich-Alexander-Universität Erlangen-, 15 Nürnberg, Martensstraße 5, Erlangen, Germany, D-91058
  10. 10Institute of Polymer Materials
  11. 11Friedrich-Alexander-University Erlangen-Nürnberg
  12. 12Laboratory for Molecular Engineering of Optoelectronic Nanomaterials (LIMNO
  13. 13Institute of Chemical Sciences
  14. 14Harwell Science and Innovation Campus
  15. 15HarwellXPS, Research Complex at Harwell, Rutherford Appleton Lab, Didcot, United Kingdom, OX11 0FA
  16. 16Department of Chemistry, University College London, 20 Gower Street, London, United Kingdom, WC1H 0AJ
  17. 17Institute of Chemical Sciences and Engineering
  18. 18École Polytechnique Fédérale de
  19. 19Department of Chemical and Pharmaceutical Sciences, University of Trieste, via Licio Giorgieri 1, Trieste, Italy, 34127
  20. 20Centre for Energy and Environmental Technologies
  21. 21VŠB–Technical University of Ostrava
  22. 22Institute for Solar Fuels, Helmholtz-Zentrum Berlin für Materialien und Energy GmbH, Hahn-Meitner-Platz 1, Berlin, Germany, 14109
  23. 23Faculty of Science,
  24. 24Paderborn University
  25. 25Profile Center Solar (FAU Solar, Freyeslebenstraße 1, Erlangen, Germany, 91058
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Abstract

Earth-abundant photocatalysts for solar H₂ struggle to absorb deep visible light and separate charges at the same time. Here we show that a small amount of reduced ceria on carbon nitride achieves both. Non covalent CexOy/C3N4 heterostructures with 4% and 7% cerium oxide were compared with CeO2 and C3N4 references for H₂ evolution at 410 and 465 nm. The key turns out to be not how much ceria is added, but in which state and how well it is spread. At 4%, ceria forms finely dispersed, oxygen-deficient nanoparticles rich in Ce3+/oxygen-vacancy (Ov) defects, as revealed by Ce M4,5- and O K-edge NEXAFS and supported by XPS, which shows reduced cerium, no fluorite lattice oxygen and the highest surface exposure of Ce. At 7%, the particles agglomerate. These defects extend light absorption into the visible range and act as electron traps: time-resolved microwave conductivity and photoluminescence reveal faster, productive electron transfer from C3N4 to ceria at 4%. As a result, the 4% composite delivers ~682 µmol g-1 h -1 (AQY ~0.57% at 410 nm), outperforming all other samples at both wavelengths. With a surface area similar to C3N4, the gain is electronic and defect-driven, not textural.

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Cite

BibTeXRIS
BibTeX
@misc{silva2026trmc,
  title = {{TRMC and NEXAFS Reveal Fast Electron Transfer to Ce3+/Oxygen-Vacancy Traps in Non-Covalent CexOy/C3N4 Interface for Photocatalytic H2}},
  author = {Ingrid F. Silva and Heer Shah and Christian Kupfer and Asia Patriarchi and Erwan Paineau and Maria Rita Cicconi and Linda Rockmann and Kevin Sivula and Marcus Halik and David C. Grinter and Robert Palgrave and Michael Grätzel and Paolo Fornasiero and Michele Melchionna and Dennis Friedrich and Nieves Lopez-Salas and Miguel Ángel Muñoz-Márquez and Mark Isaacs and Pablo Jiménez-Calvo},
  howpublished = {ChemRxiv},
  year = {2026},
  month = oct,
  doi = {10.26434/chemrxiv.15010119/v1},
  url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010119/v1},
  note = {CC BY},
}
RIS
TY  - UNPB
TI  - TRMC and NEXAFS Reveal Fast Electron Transfer to Ce3+/Oxygen-Vacancy Traps in Non-Covalent CexOy/C3N4 Interface for Photocatalytic H2
AU  - Ingrid F. Silva
AU  - Heer Shah
AU  - Christian Kupfer
AU  - Asia Patriarchi
AU  - Erwan Paineau
AU  - Maria Rita Cicconi
AU  - Linda Rockmann
AU  - Kevin Sivula
AU  - Marcus Halik
AU  - David C. Grinter
AU  - Robert Palgrave
AU  - Michael Grätzel
AU  - Paolo Fornasiero
AU  - Michele Melchionna
AU  - Dennis Friedrich
AU  - Nieves Lopez-Salas
AU  - Miguel Ángel Muñoz-Márquez
AU  - Mark Isaacs
AU  - Pablo Jiménez-Calvo
PY  - 2026
DA  - 2026/10/08
PB  - ChemRxiv
DO  - 10.26434/chemrxiv.15010119/v1
UR  - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010119/v1
AB  - Earth-abundant photocatalysts for solar H₂ struggle to absorb deep visible light and separate charges at the same time. Here we show that a small amount of reduced ceria on carbon nitride achieves both. Non covalent CexOy/C3N4 heterostructures with 4% and 7% cerium oxide were compared with CeO2 and C3N4 references for H₂ evolution at 410 and 465 nm. The key turns out to be not how much ceria is added, but in which state and how well it is spread. At 4%, ceria forms finely dispersed, oxygen-deficient nanoparticles rich in Ce3+/oxygen-vacancy (Ov) defects, as revealed by Ce M4,5- and O K-edge NEXAFS and supported by XPS, which shows reduced cerium, no fluorite lattice oxygen and the highest surface exposure of Ce. At 7%, the particles agglomerate. These defects extend light absorption into the visible range and act as electron traps: time-resolved microwave conductivity and photoluminescence reveal faster, productive electron transfer from C3N4 to ceria at 4%. As a result, the 4% composite delivers ~682 µmol g-1 h -1 (AQY ~0.57% at 410 nm), outperforming all other samples at both wavelengths. With a surface area similar to C3N4, the gain is electronic and defect-driven, not textural.
ER  -