Oxygen vacancy-mediated asymmetric Ni-Ov-Co sites for efficient low-temperature N2O decomposition

doi:10.1016/S1872-2067(26)65119-4

Abstract

Abstract:

The environmental persistence and potent greenhouse effect of N₂O call for efficient catalytic decomposition to address its environmental impact. However, achieving low-temperature N-O bond activation remains challenging due to the difficulty of constructing highly active sites. Herein, spinel cobalt oxides with controlled geometric configurations are successfully fabricated via the incorporation of heteroatoms. The Ni-substituted octahedral Co promotes the formation of oxygen vacancy, generating an asymmetric Ni-Ov-Co structure. Notably, NiCo₂O₄ catalyst with abundant asymmetric Ni-Ov-Co structure displays remarkable catalytic performance with a T₉₀ of 340 °C, which is 50 and 140 °C lower than that of comparative Co₃O₄ and CoAl₂O₄ catalysts, respectively. Structural characterizations and density functional theory calculation reveal that asymmetric Ni-Ov-Co sites possess high Co-O covalency and strong N₂O adsorption capacity, thus reducing the energy barriers in the key steps of N-O bond cleavage and O-O bond formation and boosting the catalytic activity. Moreover, the results of the mechanism research demonstrate that N₂O decomposition on asymmetric Ni-Ov-Co sites follows the Langmuir-Hinshelwood mechanism. This work underpins the design of asymmetric active sites in spinel oxides as efficient catalysts for greenhouse gas removal.

Key words: Spinel oxide, Asymmetric oxygen vacancy, N₂O decomposition, Reaction mechanism, Geometric engineering

Bingzhi Li, Ganggang Li, Zeyu Zhao, Fenglian Zhang, Zhongshen Zhang, Jie Cheng, Zhengping Hao. Oxygen vacancy-mediated asymmetric Ni-Ov-Co sites for efficient low-temperature N₂O decomposition[J]. Chinese Journal of Catalysis, 2026, 90: 276-286.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65119-4

https://www.cjcatal.com/EN/Y2026/V90/I11/276

Figures/Tables 6

Fig. 1. Structural and morphological characterization of spinel oxide catalysts. (a-c) Crystal structure models of NiCo2O4, Co3O4, and CoAl2O4. (d-f) Rietveld-refined XRD patterns of NiCo2O4, Co3O4, and CoAl2O4. (g-i) HAADF-STEM images of NiCo2O4, Co3O4, and CoAl2O4.

Fig. 2. Electronic structure and defect characterization of spinel oxide catalysts. Co K-edge XANES (a) and Fourier-transformed EXAFS spectra (b) of NiCo2O4, Co3O4, and CoAl2O4. (c) UV-vis spectra. (d) Raman spectra. (e) EPR spectra. O 1s (f) and Co 2p (g) XPS spectra.

Fig. 3. Catalytic performance and stability of spinel oxide catalysts toward N2O decomposition. (a) N2O decomposition profiles over NiCo2O4, Co3O4, and CoAl2O4. (b) Reaction rates of the catalysts at different temperatures. (c) Arrhenius plots used to calculate apparent activation energies. (d) Stability tests conducted at 340 °C. (e) Tolerance evaluation of NiCo2O4 in the presence of potential impurities (O2, NO, and H2O). (f) The comparison of T90 for different reported catalysts (the X-axis has no physical significance).

Fig. 4. Redox properties and electronic structure analysis of spinel oxide catalysts. H2-TPR profiles (a), O2-TPD profiles (b), PDOS (c) of Ni, Co, Al, and O orbitals, the blue dashed line implies the Fermi level energy (Ef). (d) Computed charge distributions of metal and oxygen atoms. (e) Calculated N2O adsorption energies on different surface sites of perfect surfaces of NiCo2O4, Co3O4, and CoAl2O4 spinel oxides.

Fig. 5. Model structures of N2O adsorbed on CoTh sites (a,b), CoOh sites (c,d), NiOh sites (e,f) in NiCo2O4 without and with an oxygen vacancy, respectively. The blue balls represent Co, red balls represent O, green balls represent Ni, and purple balls represent N.

Fig. 6. Mechanistic investigation of N2O decomposition over spinel oxide catalysts. (a,b) TPSR profiles of isotopically labeled Co318O4 and NiCo218O4. (c) Calculated free energy diagrams for N2O decomposition on Co3O4 (311) and NiCo2O4 (311) surfaces with oxygen vacancy.

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Oxygen vacancy-mediated asymmetric Ni-Ov-Co sites for efficient low-temperature N₂O decomposition

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