Size-dependent interfacial interactions in CeO2/Co3O4 catalysts: From single atoms to nanoparticles

doi:10.1016/S1872-2067(26)65120-0

Abstract

Abstract:

Although CeO₂/Co₃O₄ composites exhibit excellent catalytic performance in oxidation reactions, the atomic-scale origin of their interfacial interactions remains unclear. In this work, we compare two contrasting catalysts: Co₃O₄-supported Ce single atoms and Co₃O₄-supported CeO₂ nanoparticles. We reveal that these two forms of Ce promote catalytic performance through different mechanisms. Ce single atoms occupy the octahedral Co³⁺ sites within the Co₃O₄ structure, forming Ce³⁺-Vo-Co active sites and thereby induce local compressive strain and facilitate the formation of point-defective oxygen vacancies. More importantly, Ce³⁺ acts as an electron donor, elevating the d-band center of Co and facilitating O₂ activation via enhanced electron transfer to O₂ antibonding orbitals. In contrast, the extensive interfacial contact between CeO₂ nanoparticles and Co₃O₄ triggers ion migration, which subsequently generates defects or amorphous interfacial domains with high oxygen mobility. The configuration of interfacial defects is highly dependent on the size of CeO₂ nanoparticles. Catalytic tests for the liquid-phase aerobic oxidation of benzyl alcohol confirm the superior performance of the single-atom catalyst, which exhibits 1.5 times higher activity and a 27.7 kJ/mol lower activation energy than its CeO₂ nanoparticle counterpart. Our findings demonstrate that the interaction between Ce species and Co₃O₄ is dominated by electronic effects when Ce is atomically dispersed, whereas interfacial reconstruction becomes predominant with increasing CeO₂ nanoparticles size.

Key words: Co₃O₄ catalyst, CeO₂, Catalytic oxidation, Interface reconstruction, Single atoms, Nanoparticles

Yue Zeng, Hongsheng Wang, Jing Xuan, Ping Xiao, Yaoyao Feng, Shuai Lyu, Junjiang Zhu. Size-dependent interfacial interactions in CeO₂/Co₃O₄ catalysts: From single atoms to nanoparticles[J]. Chinese Journal of Catalysis, 2026, 88: 478-491.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65120-0

https://www.cjcatal.com/EN/Y2026/V88/I9/478

Figures/Tables 9

Fig. 1. TEM characterization of Ce supported Co3O4 catalysts. Atomic-resolution STEM image of SA-Ce-Co3O4 (A) and 5.7NP-CeO2/Co3O4 (C). HAADF-STEM image and corresponding EDX elemental mappings of SA-Ce-Co3O4 (B) and 5.7NP-CeO2/Co3O4 (D).

Fig. 2. Surface chemical states and coordination information of as-prepared catalysts. (A) Ce k-edge XANES profiles for as-prepared catalysts. (B) Ce k-edge EXAFS spectra in R space for as-prepared catalysts. WT analysis of SA-Ce-Co3O4 (C), 5.7NP-CeO2/Co3O4 (D), and CeO2 (E). (F) Ce 3d XPS data of as-prepared catalysts. (G) The percentage of Ce3+ in the catalysts.

Fig. 3. Catalytic performance of as-prepared catalysts. (A) The BzOH conversion as the function time for different catalysts. (B) The BzOH conversion and BzH selectivity at 180 min for different catalyst. (C) The Arrhenius plots for calculating activation energies for SA-Ce-Co3O4, 5.7NP-CeO2/Co3O4 and Co3O4 catalyst. Reaction conditions: 80 °C, 20 μL substrates, O2: 50 mL/min, Toluene 20 mL.

Fig. 4. Microstructural analysis of the catalyst series. (A) Raman spectra of Co3O4, SA-Ce-Co3O4 and 5.7NP-CeO2/Co3O4 catalyst. Peak center (B) and FWHM (C) of A1g for different catalyst. HRTEM image of Co3O4 (D), SA-Ce-Co3O4 (E), and 5.7NP-CeO2/Co3O4 (F) catalysts. Schematic diagram of single atom Ce modified Co3O4 (G) and CeO2 nanoparticle supported on Co3O4 (H).

Fig. 5. DFT calculation. (A) Surface structure of Co3O4 (111) facet. (B) Surface structure of Ce1/Co3O4 (111) facet. (C) Oxygen vacancy formation energy on Co3O4 (111) and Ce1/Co3O4 (111) facets. (D) The density of states of Co3O4. (E) The density of states of Ce1/Co3O4. (F) Oxygen adsorption structure on the oxygen vacancy site of Ce1/Co3O4-Vo with charge density difference and Bader charge analysis. (G) Oxygen adsorption structure on the oxygen vacancy site of Co3O4-Vo with charge density difference and Bader charge analysis. (H) Oxygen dissociation pathways and corresponding energy barriers on different structures. The balls in blue, red, and yellow colors represent Co, O, and Ce atoms, respectively.

Fig. 6. Interfacial microstructure of Co3O4 with different-sized CeO2. STEM image (A) and HRTEM image (B) of 2.4NP-CeO2/Co3O4. STEM image (C) and HRTEM image (D) of 7.3NP-CeO2/Co3O4. (E) Schematic diagram of the interfacial microstructure of Co3O4 tuned by CeO2 size. (F) Raman spectra of synthesized Co3O4-Supported CeO2 Catalysts. (G) Position of the A1g peak of the catalyst as a function of CeO2 size. (H) FWHM of the A1g peak of the catalyst as a function of CeO2 size.

Fig. 7. XRD patterns (A) and Raman spectra (B) of 5.7CeO2/Co3O4 catalyst calcined at 400 °C for different time. (C) STEM and the corresponding EDX line scan image of 5.7CeO2/Co3O4. (D) Schematic illustration of the octahedral to tetrahedral structural transformation driven by electron transfer. (E) The formation mechanism schematic diagram of the amorphous region at the interface.

Fig. 8. (A) The BzOH conversion as the function time for different catalysts. (B) The BzOH conversion and BzH selectivity at 180 min for different catalysts. (C) The Arrhenius plots for calculating activation energies for different catalyst. (D) Activation energies of the catalyst as a function of CeO2 size. Ov percentage (E) and Co3+ percentage (F) in the catalyst as a function of CeO2 size. H2-TPR profiles (G) and O2-TPD profiles (H) of different catalysts. (I) Ce3+ percentage in the catalyst as a function of CeO2 size.

Fig. 9. Schematic illustrating the enhanced catalytic oxidation activity of Co3O4 promoted by single atom Ce and CeO2 nanoparticles with different size.

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Size-dependent interfacial interactions in CeO₂/Co₃O₄ catalysts: From single atoms to nanoparticles

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