Skip to content
DraconiticResearch
Search Sources API
203,234 studies31 sourcesUpdated 57 min ago
PreprintCC BY-NCChemRxiv

Vacancy-Controlled Stabilization and Reactivity of Single Metal Atoms on Titanium Nitride and Titanium Oxynitride

  • Lazar Bijelic1,2
  • Ana S. Dobrota3
  • Natalia V. Skorodumova4,5
  • Igor A. Pašti3,6
6 affiliations
  1. 1National Institute of Chemistry, Hajdrihova 19, Ljubljana, Slovenia, 1000
  2. 2University of Nova Gorica, Vipavska 13, Nova Gorica, Slovenia, 5000
  3. 3Faculty of Physical Chemistry, University of Belgrade, Studentski trg 12-16, Belgrade, Serbia, 11000
  4. 4Applied Physics, Division of Materials Science, Department of Engineering Sciences and Mathematics
  5. 5Luleå University of Technology
  6. 6Serbian Academy of Sciences and Arts, Kneza Mihaila 35, Belgrade, Serbia, 11000
Open at sourcePDFDOICite

Abstract

Titanium nitride (TiN) and titanium oxynitride (TiON) are attractive conductive supports for single-atom electrocatalysts, but the role of surface vacancies in balancing metal stabilization and catalytic reactivity remains unclear. Here, we used density functional theory to screen the formation of Ag, Au, Co, Cu, Ir, Ni, Pd, Pt, Rh, and Ru single atoms on pristine and vacancy-containing TiN and TiON surfaces, and their reactivity toward the hydrogen evolution reaction (HER). Vacancy formation generally strengthens single-atom anchoring, but the corresponding changes in hydrogen adsorption are strongly metal- and defect-dependent, showing that a stronger metal–support interaction does not necessarily imply improved HER activity. Combining hydrogen adsorption thermodynamics with electrochemical dissolution stability identifies Pd atoms trapped in Ti vacancies (VTi) as the most promising candidates. Importantly, Pd@VTi shows nearly identical hydrogen adsorption energetics and dissolution potentials above 0 V vs. SHE for TiN and both investigated TiON configurations, indicating remarkable insensitivity to the local O/N arrangement. Electronic-structure analysis, ab initio molecular dynamics, and surface Pourbaix calculations further support the viability of these configurations. These results highlight cation-vacancy-confined Pd as a robust HER motif on compositionally variable Ti(O)N supports.

Related

  1. Diffusion-controlled reactions with time-dependent surface reactivity
    Denis S. Grebenkov, Yilin Ye
    arXivPreprintCC BY 4.0Full textPhysical chemistryStatistical & nonlinear physicsarXiv
  2. Condition-Controlled Divergent Reactivity of Nitroaldol Isatin Adducts with Phenols: Friedel–Crafts Alkylation, Skeletal Rearrangement, and Spirocyclic Oxime Formation
    Nikolai A. Arutiunov, Daria A. Shtal, Kirill V. Tolstov +6
    International Journal of Molecular SciencesPeer-reviewedCC BY 4.0Organic chemistryCrossref
  3. Zirconium Oxynitride for the Oxygen Evolution Reaction
    Mathias Stokkebye Nissen, Christodoulos Chatzichristodoulou, Yang Hu +1
    ChemRxivPreprintCC BYFull textElectrochemistry & energyChemRxiv
  4. Bidirectional interconversion of microwave and light with diamond nitrogen vacancy center
    Javad Yektaaval, Mohammad Mahmoudi
    Scientific ReportsPeer-reviewedCC BY-NC-ND 4.0Full textMaterials & polymersCrossref
  5. Energy-level alignment of vacancy-ordered halide double perovskites
    Ibrahim Buba Garba, George Volonakis
    Applied Physics LettersPeer-reviewedLicence not statedFull textGeneral chemistryHAL

Cite

BibTeXRIS
BibTeX
@misc{bijelic2026vacancycontrolled,
  title = {{Vacancy-Controlled Stabilization and Reactivity of Single Metal Atoms on Titanium Nitride and Titanium Oxynitride}},
  author = {Lazar Bijelic and Ana S. Dobrota and Natalia V. Skorodumova and Igor A. Pašti},
  howpublished = {ChemRxiv},
  year = {2026},
  month = sep,
  doi = {10.26434/chemrxiv.15008701/v1},
  url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008701/v1},
  note = {CC BY-NC},
}
RIS
TY  - UNPB
TI  - Vacancy-Controlled Stabilization and Reactivity of Single Metal Atoms on Titanium Nitride and Titanium Oxynitride
AU  - Lazar Bijelic
AU  - Ana S. Dobrota
AU  - Natalia V. Skorodumova
AU  - Igor A. Pašti
PY  - 2026
DA  - 2026/09/11
PB  - ChemRxiv
DO  - 10.26434/chemrxiv.15008701/v1
UR  - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008701/v1
AB  - Titanium nitride (TiN) and titanium oxynitride (TiON) are attractive conductive supports for single-atom electrocatalysts, but the role of surface vacancies in balancing metal stabilization and catalytic reactivity remains unclear. Here, we used density functional theory to screen the formation of Ag, Au, Co, Cu, Ir, Ni, Pd, Pt, Rh, and Ru single atoms on pristine and vacancy-containing TiN and TiON surfaces, and their reactivity toward the hydrogen evolution reaction (HER). Vacancy formation generally strengthens single-atom anchoring, but the corresponding changes in hydrogen adsorption are strongly metal- and defect-dependent, showing that a stronger metal–support interaction does not necessarily imply improved HER activity. Combining hydrogen adsorption thermodynamics with electrochemical dissolution stability identifies Pd atoms trapped in Ti vacancies (VTi) as the most promising candidates. Importantly, Pd@VTi shows nearly identical hydrogen adsorption energetics and dissolution potentials above 0 V vs. SHE for TiN and both investigated TiON configurations, indicating remarkable insensitivity to the local O/N arrangement. Electronic-structure analysis, ab initio molecular dynamics, and surface Pourbaix calculations further support the viability of these configurations. These results highlight cation-vacancy-confined Pd as a robust HER motif on compositionally variable Ti(O)N supports.
ER  -