Data availability
All data generated or analysed during this study are included in this published Article and its Supplementary Information files. Source data are provided with this paper.
Code availability
All codes necessary are available via GitHub (https://github.com/liushuhui84/CalculateStrain).
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Acknowledgements
We extend our sincere gratitude to A. Goldbach (Dalian Institute of Chemical Physics) for providing expert insight during manuscript preparation. Y. Cui and Y. Li are thanked for their contributions to the APXPS experiments facilitated by Vacuum Interconnected Nanotech Workstation (Nano-X) at Suzhou Institute of Nano-Tech and Nano-Bio-nics, Chinese Academy of Sciences (CAS). This work was supported by the Strategic Priority Research Programme of CAS (grant no. XDB1530000), the NSFC Centre for Single-Atom-Catalysis (grant no. 22388102), the CAS Project for Young Scientists in Basic Research (grant no. YSBR-022), the National Natural Science Foundation of China (grant nos. 21925803, 22572012, 22202027 and 22427801), the Youth Innovation Promotion Association CAS (grant no. Y2022061 and Y2023053), National Key R&D Programme of China (grant no. 2022YFA1503102), the Young Top-notch Talents of Liaoning Province (grant no. XLYC2203108), New Cornerstone Science Foundation through the XPLORER PRIZE and Guangdong Provincial Key Laboratory of Catalysis (grant no. 2020B121201002). The computational resources were supported by Centre for Computational Science and Engineering at Southern University of Science and Technology (SUSTech) and the CHEM high-performance supercomputer cluster (CHEM-HPC) located in the Department of Chemistry, SUSTech.
Author information
Author notes
These authors contributed equally: Weijue Wang, Hongbin Xu
Authors and Affiliations
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, China
Weijue Wang (王玮珏), Xiaofeng Yang (杨小峰), Wei Liu (刘伟), Yanqiang Huang (黄延强) & Tao Zhang (张涛)
University of Chinese Academy of Sciences, Beijing, China
Weijue Wang (王玮珏), Xiaofeng Yang (杨小峰), Wei Liu (刘伟), Yanqiang Huang (黄延强) & Tao Zhang (张涛)
Department of Chemistry and Guangdong Provincial Key Laboratory of Catalytic Chemistry, Southern University of Science and Technology, Shenzhen, China
Hongbin Xu (许泓斌) & Yang-Gang Wang (王阳刚)
School of Railway Intelligent Engineering, Dalian Jiaotong University, Dalian, China
Shuhui Liu (刘淑慧)
Authors
- Weijue Wang (王玮珏)
- Hongbin Xu (许泓斌)
- Shuhui Liu (刘淑慧)
- Xiaofeng Yang (杨小峰)
- Wei Liu (刘伟)
- Yang-Gang Wang (王阳刚)
- Yanqiang Huang (黄延强)
- Tao Zhang (张涛)
Contributions
W.L., Y.H. and T.Z. conceived this project and supervised the study. W.W. performed the material synthesis, microscopy, spectroscopy and other experiments. W.W., X.Y. and W.L. performed the data analysis. H.X. and Y.-G.W. conducted DFT calculations. S.L. and W.L. developed the method for atom displacement analysis. W.W., X.Y., W.L., Y.-G.W. and Y.H. wrote the manuscript, with the help of the other authors.
Corresponding authors
Correspondence to Wei Liu (刘伟), Yang-Gang Wang (王阳刚), Yanqiang Huang (黄延强) or Tao Zhang (张涛).
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Extended data figures and tables
Extended Data Fig. 1 Microstructure of fresh Ru/TiO2 catalysts and schematic diagrams of the metal-support synergy configuration.
a,b, The diffraction patterns and morphologies of anatase-TiO2 (a-TiO2) and rutile-TiO2 (r-TiO2), respectively (scale bars in the insets are 20 nm). c, Synthesized Ru NPs and corresponding particle size distribution (4.05 ± 0.47 nm). d, Interior interfacial synergy configuration of Ru/r-TiO2, establishing bulk oxygen spillover characteristics. e, Switching off bulk spillover by manipulating Ru/TiO2 interface. f, Conventional metal-support interaction forming active sites ensemble at peripheral interface. g, Side view of d.
Extended Data Fig. 2 Identification of the site of Ru initial oxidation.
In situ HRTEM images of Ru/r-TiO2 before oxidation (a) and at the beginning of oxidation (b). c–f, The intensity profiles derived from areas 1–4 in a and b, respectively, where red dashed lines highlighted the position of 1st layer of Ti atom columns at outmost surface of r-TiO2(110). It demonstrates precisely the first occurrence of Ru epitaxial oxidation at the interior interface (area 3). g, Initial Ru NP after pre-annealing at 700 °C in vacuum. h, The status of Ru initial oxidation, and inset enlarges the oxidation region where spillover occurs first at the interior interface rather than exposed surface. i, Ru further oxidized in a “bottom-up” manner (10 Pa). j,k, Classical cation and anion transport models. l, Anion transport model of Ru/r-TiO2 in this work.
Extended Data Fig. 3 Isotopic labelling experiments.
a, Oxidation-reduction isotope labelling experiments of Ru/r-TiO2. b, Isotopic labelling experiments in CO oxidation reaction catalysed by RuO2/r-TiO2. c,d, HRTEM images of RuO2/r-TiO2 after isotope experiment of CO oxidation.
Extended Data Fig. 4 Crystallographic universality of the iBOT spillover mechanism in Ru/r-TiO2.
State of Ru NPs supported on r-TiO2(110) and (100) facets before oxidation (a), after oxidation (b). c, In situ oxidation experiments of Ru/r-TiO2 and Ru/a-TiO2 using APXPS. (yellow: Ru0 ~280.3 eV, green: Ru4+ ~281.4 eV). d,e, Oxidation of Ru/r-TiO2 and Ru/a-TiO2 in practical reaction conditions: 1 bar air, 250 °C in muffle furnace. Ru/r-TiO2 initiates oxygen spillover while Ru/a-TiO2 is incompletely oxidised.
Extended Data Fig. 5 HRTEM images of the oxidation process of Ru/a-TiO2 and pristine Ru NPs.
a–c, One Ru NP supported on a-TiO2(101) undergoes surface oxidation. d,e, Another Ru NP pre-annealed in vacuum evolves into Ru@RuO2 core-shell after oxidation. f, HRTEM image of the other two Ru@RuO2 from a beam irradiation-free area. g–i, In situ oxidation of one free-standing Ru particle into Ru@RuO2 core-shell. j,k, HRTEM images of another Ru NP after oxidation at 500 °C, showing clear Ru@RuO2 core-shell architecture. l, The low-magnification TEM image of multiple Ru NPs confirming their uniformity of surface oxidation configuration. O2 pressure 10 Pa.
Extended Data Fig. 6 DFT calculations on oxygen transport pathway in Ru/TiO2.
a–d, Relative interfacial energies per unit area of RuO2 formation starting from Ru top surface or Ru/TiO2 interface in Ru/r-TiO2 (a,b) and Ru/a-TiO2 (c,d), respectively. e, Oxygen spillover energy barriers (Ea) in individual components of the Ru/RuO2/r-TiO2 system. Pathways correspond to oxygen vacancy (VO) diffusion in r-TiO2(110) (I-IV), r-TiO2 bulk (V-VII), and r-RuO2 bulk (VIII-X); Oxygen spillover at Ru/RuO2 interface (XI). The primary pathways of low energy barrier are underlined. Top panel of e shows oxygen atom incorporation on Ru(0001) (surface oxidation).
Extended Data Fig. 7 DFT calculations on oxygen activation and transport in Ru/TiO2.
a–c, Phase diagram of O2 adsorption on r-TiO2 surface loading with different number of Ru atoms. The green area represents different O2 coverage states in function of pressure and temperature (pentagram: 723 K, 10 Pa). The second row of panels shows for Ru/r-TiO2 calculated charge spin density (d), energy barrier associated with oxygen vacancy diffusion from VO1 → VO2 (e), the depth distribution of rutile oxygen vacancies (f) and their formation energies (g). h–k, The third row of panels presents analogous calculation study for Ru/a-TiO2. It shows for Ru/r-TiO2 promoted charge transfer, lower diffusion barrier and preferred surface formation of oxygen vacancy in contrast to Ru/a-TiO2. Work 1–4 correspond to the calculation results of refs. 26,53,54 and 55 respectively. l, Calculated adsorption energy (eV) of CO, CO2 and O2 at different sites of RuO2/r-TiO2. Graph in g adapted with permission from refs. 26,53, American Physical Society. Graph in k adapted with permission from refs. 54,55, American Physical Society.
Extended Data Fig. 8 The reversible transformation of Ru/r-TiO2 in reduction and reoxidation, and the iBOT spillover in different catalyst systems.
a, 1st complete oxidation of the Ru NP. b, RuO2 restores into Ru after in situ reduction in H2. c,d, 2nd complete oxidation process of Ru NP. e,f, 1st complete oxidation of the Ru NP. g, RuO2 restores into Ru after CO reduction. h, 2nd complete oxidation of Ru NP. Reaction condition: 10 Pa O2, H2 or CO. These results show that the RuO2 formed through oxygen spillover in Ru/r-TiO2 serves as facile oxygen storage and reactive supply. Similar oxidation behaviour was observed in both Ru/SnO2 (i,j) and Ir/r-TiO2 (k,l).
Extended Data Fig. 9 In situ observation of oxygen spillover in Ru/r-TiO2 and Ru/a-TiO2 during catalysing N2O decomposition.
Low-magnified TEM images of Ru/r-TiO2 before (a) and during (b) reaction. HRTEM images of one Ru NP on r-TiO2 before (c) and during (d) the reaction. During N2O decomposition, Ru achieved interfacial oxidation on r-TiO2 (b,d). In situ TEM images of Ru/a-TiO2 before (e) and during (f) the reaction. g,h, HRTEM images of Ru NPs from two locations during the reaction. In sharp contrary, the absence of interfacial synergy in Ru/a-TiO2 cannot facilitate absolutely the formation of RuO2.
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Wang, W., Xu, H., Liu, S. et al. Imaging interface-controlled bulk oxygen spillover. Nature 652, 655–659 (2026). https://doi.org/10.1038/s41586-026-10324-x
Received: 30 October 2024
Accepted: 24 February 2026
Published: 15 April 2026
Version of record: 15 April 2026
Issue date: 16 April 2026
DOI: https://doi.org/10.1038/s41586-026-10324-x
