Mechanism of selective reduction of N2O by CO over Fe-β catalysts studied by in-situ/operando spectroscopy

doi:10.1016/S1872-2067(24)60161-0

Abstract

Abstract:

Selective reduction of N₂O by CO under excess O₂ was effectively catalyzed by Fe(0.9 wt%)-exchanged β zeolite (Fe0.9β) in the temperature range of 250-500 °C. Kinetic experiments showed that the apparent activation energy for N₂O reduction with CO was lower than that for the direct N₂O decomposition, and the rate of N₂O reduction with CO at 300 °C was 16 times higher than that for direct N₂O decomposition. Reaction order analyses showed that CO and N₂O were involved in the kinetically important step, while O₂ was not involved in the important step. At 300 °C, the rate of CO oxidation with 0.1% N₂O was two times higher than that of CO oxidation with 10% O₂. This quantitatively demonstrates the preferential oxidation of CO by N₂O under excess O₂ over Fe0.9β. Operando/in-situ diffuse reflectance ultraviolet-visible spectroscopy showed a redox-based catalytic cycle; α-Fe-O species are reduced by CO to give CO₂ and reduced Fe species, which are then re-oxidized by N₂O to regenerate the α-Fe-O species. The initial rate for the regeneration of α-Fe-O species under 0.1% N₂O was four times higher than that under 10% O₂. This result shows quantitative evidence on the higher reactivity of N₂O than O₂ for the regeneration of α-Fe-O intermediates, providing a fundamental reason why the Fe0.9β catalyst selectively promotes the CO + N₂O reaction under excess O₂ rather than the undesired side reaction of CO + O₂. The mechanistic model was verified by the results of in-situ Fe K-edge X-ray absorption spectroscopy.

Key words: Fe-exchanged zeolites, N₂O, Selective catalytic reduction, In-situ ultraviolet-visible

Yucheng Qian, Shunsaku Yasumura, Ningqiang Zhang, Akihiko Anzai, Takashi Toyao, Ken-ichi Shimizu. Mechanism of selective reduction of N₂O by CO over Fe-β catalysts studied by in-situ/operando spectroscopy[J]. Chinese Journal of Catalysis, 2025, 69: 185-192.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60161-0

https://www.cjcatal.com/EN/Y2025/V69/I2/185

Figures/Tables 8

Fig. 1. N2O and CO conversion over 30 mg Fe0.9β under 0.1% N2O/0.1% CO/(10% O2) versus temperature.

Fig. 2. N2O conversion for 0.1% N2O + 0.1% CO + 10% O2 over Fe0.9β (30 mg) and 0.1% N2O + 10% O2 over Fe0.9β (150 mg), and CO conversion of 0.1% CO + 10%O2 over Fe0.9β (30 mg) versus temperature.

Fig. 3. Arrhenius plots for CO + N2O (150-300 °C; 5-30 mg Fe0.9β), CO + O2 (200-300 °C; 10-30 mg Fe0.9β) and N2O decomposition (300-450 °C; 75-150 mg Fe0.9β). Ea based on Arrhenius equation are shown.

Fig. 4. Reaction rates versus concentration of (A) O2, (B) N2O, (C) CO for CO-SCR of N2O over Fe0.9β at 350 °C. The apparent reaction order are shown in the table.

Fig. 5. Selected UV-vis original spectrum of Fe0.9β (a,d), difference spectra (b,e), and mass spectrum (MS) intensity of CO2 or N2 and the α-Fe-O peak area (360 nm) versus time (c,f) under 1% CO (a?c), followed by a He purge (for 900 s), and a flow of 1% N2O (d?f) at 350 °C.

Fig. 6. Selected UV-vis spectra of Fe0.9β (a,d), difference spectra (b,e), and α-Fe-O peak area versus time (c,f) under 10% O2 (c) or 0.1% N2O (f) at 350 °C. The sample was pre-reduced by 1% CO for 1500 s, followed by a He purge for 900 s.

Fig. 7. Evolution of the Fe K-edge XANES spectrum of Fe0.9? during successive feeds of 1% CO (a) and 1% N2O (b): selected spectra (left) and energy at normalized adsorption of 0.8 and MS intensity versus time (right). Before the experiment, the pre-oxidized sample was reduced with 1% CO (950 s), followed by a He purge (300 s).

Fig. 8. XANES spectra (a) of the CO-reduced Fe0.9β, followed by re-oxidation by N2O or O2. Energy changes (b) at normalized absorption during re-oxidation in 1% N2O or 10% O2 at 350 °C.

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Mechanism of selective reduction of N₂O by CO over Fe-β catalysts studied by in-situ/operando spectroscopy

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