Non-thermal plasma to boost lattice oxygen activation in Ce1-xCoxO2-δ catalysts for efficient soot combustion at low temperatures

doi:10.1016/S1872-2067(25)64775-9

Abstract

Abstract:

Effective lattice oxygen (O_latt) activation at low temperatures has long been a challenge in catalytic oxidation reactions. Traditional thermal catalytic soot combustion, even with Pt/Pd catalysts, is inefficient at exhaust temperatures below 200 °C, particularly under conditions of frequent idling. Herein, we report an effective strategy utilizing non-thermal plasma (NTP) to activate O_latt in Ce_1-_xCo_xO_2-_δ catalysts, achieving dramatic enhancement of the soot combustion rate at low temperatures. At 200 °C and 4.3 W (discharge power, P_dis), NTP-Ce_0.8Co_0.2O_2-_δ achieved 96.9% soot conversion (X_C), 99.0% CO₂ selectivity (S(CO₂)) and a maximum energy conversion efficiency (E_max) of 14.7 g kWh^-1. Compared with previously reported results, NTP-Ce_0.8Co_0.2O_2-_δ exhibits the highest S(CO₂) and E_max values. Remarkably, even without heating, X_C, E_max, and S(CO₂) reached 92.1%, 6.1 g kWh^-1, and 97.5%, respectively, at 6.3 W (P_dis). The results of characterization and theoretical calculation demonstrated that Co dopes into the CeO₂ crystal lattice and forms an asymmetric Ce-O-Co structure, making oxygen “easy come, easy go”, thereby enabling the rapid combustion of soot over NTP-Ce_0.8Co_0.2O_2-_δ. This study highlights the great potential of NTP for activating O_latt and provides valuable insights into the design of efficient NTP-adapted catalysts for oxidation reactions.

Key words: Reactive oxygen species, Lattice oxygen, Asymmetric Ce-O-Co structure, Non-thermal plasma, Soot combustion

Feiyang Zhang, Yanjun Chen, Mengyao Sun, Peng Wang, Yuxin Miao, Zhongyang Zheng, Shixin Liu, Xuehua Yu, Zhen Zhao. Non-thermal plasma to boost lattice oxygen activation in Ce_1-_xCo_xO_2-_δ catalysts for efficient soot combustion at low temperatures[J]. Chinese Journal of Catalysis, 2025, 77: 99-109.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64775-9

https://www.cjcatal.com/EN/Y2025/V77/I10/99

Figures/Tables 4

Fig. 1. (a) XRD patterns of Ce1-xCoxO2-δ catalysts. (b) Magnified XRD patterns of Ce1-xCoxO2-δ catalysts in the range from 27° to 30°. (c) Raman spectra of Ce1-xCoxO2-δ catalysts. (d) HRTEM images of Ce0.8Co0.2O2-δ catalyst. (e) HRTEM images of Ce0.6Co0.4O2-δ catalyst. (f) O2-TPD profiles of Ce1-xCoxO2-δ catalysts.

Fig. 2. (a) Time-dependent curves of COx concentrations of NTP-Ce1-xCoxO2-δ (x = 0, 0.2, and 1). (b) XC of NTP-Blank and NTP-Ce1-xCoxO2-δ (x = 0, 0.2, 0.4, and 1) as a function of reaction time. (c) XC and S(CO2) of NTP-Blank and NTP-Ce1-xCoxO2-δ/-HCl. (d) The stability of Ce0.8Co0.2O2-δ catalyst. (e) Emax of the NTP-Ce1-xCoxO2-δ (200 °C, Pin = 13 W and 10% O2/N2). (f) Water resistance of Ce1-xCoxO2-δ (x = 0.1-0.4) catalysts (200 °C, Pin = 13 W and 10% O2/10% H2O/N2). (g) Effect of NO concentration (Pin = 13 W and 150 °C) on the catalytic activity of Ce0.8Co0.2O2-δ catalyst. (h) Effect of Pdis (without heating and 10% O2/N2) and reaction temperature (Pin = 13 W and 10% O2/N2) on the catalytic activity of Ce0.8Co0.2O2-δ catalyst. (i) XRD patterns of Ce1-xCoxO2-δ/-HCl (x = 0.2, 0.4).

Fig. 3. (a-c) Isothermal plasma isotope exchange reactions on Ce1-xCoxO2-δ (x = 0, 0.2 and 1) catalysts without soot (a) and with soot (b,c) (Pin = 13 W). (d) XRD patterns of Ce1-xCoxO2-δ, Ce1-xCoxO2-δ-R and Ce1-xCoxO2-δ-S catalysts (x = 0 and 0.2). (e) Raman spectra of Ce1-xCoxO2-δ, Ce1-xCoxO2-δ-R and Ce1-xCoxO2-δ-S catalysts (x = 0 and 0.2). (f) Ce 3d XPS spectra of Ce0.8Co0.2O2-δ, Ce0.8Co0.2O2-δ-R and Ce0.8Co0.2O2-δ-S catalysts (Ce3+: Ce3+/(Ce3+ + Ce4+) × 100). (Ce1-xCoxO2-δ-R and Ce1-xCoxO2-δ-S are the used catalysts in soot combustion by NTP-catalyst without gas-phase oxygen and regenerated by NTP in 10% O2/N2 flow, respectively.)

Fig. 4. Structural configurations of CeO2 (a), Co-CeO2 (b), CeO2-Vo (c), and Co-CeO2-Vo (d). Energy of formation of the second Vo by the direct (e) and migration (f) removal processes. (g) Energy profiles of the O2 supplement for CeO2 and Co-CeO2. Electron localization function (ELF) maps of CeO2 (h) and Co-CeO2 (i). Projected crystal orbital Hamilton populations (pCOHP) for CeO2 (j) and Co-CeO2 (k) (red, yellow, and blue balls represent O, Ce, and Co atoms, respectively). (l) Synergistic catalytic mechanism of the NTP-Ce1-xCoxO2-δ hybrid for soot oxidation.

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