NH3 synthesis via visible-light-assisted thermocatalytic NO reduction by CO in the presence of H2O over Cu/CeO2

doi:10.1016/S1872-2067(23)64439-0

Abstract

Abstract:

A photothermal catalytic system comprising Cu/CeO₂ was applied to the reaction between NO, CO and H₂O for the production of NH₃ under visible-light irradiation. High NO conversion (94.4%) and NH₃ selectivity (66.5%) were achieved over Cu/CeO₂ in the presence of H₂O at 210 °C. Visible light further improved the conversion of NO (97.7%) and selectivity for NH₃ (69.1%). The quasi-situ EPR and in-situ DRIFTS results indicated that CO initially reacts with H₂O to form an HCO₃^* intermediate, which then decomposes into CO₂ and activated H*. Finally, NO reacts with activated H* to produce NH₃. The localized surface plasmon resonance effect of Cu nanoparticles induced by visible light promotes the decomposition of HCO₃^* to CO₂ and H*, while regenerating oxygen vacancies (OVs, H₂O activation sites) at the CeO₂sites, resulting in enhanced NH₃ production. This study offers a convenient approach for NH₃ production under mild conditions.

Key words: NO-CO-H₂O reaction, NH₃ production, Localized surface plasmon resonance, Oxygen vacancies, Cu/CeO₂

Xinjie Song, Shipeng Fan, Zehua Cai, Zhou Yang, Xun Chen, Xianzhi Fu, Wenxin Dai. NH₃ synthesis via visible-light-assisted thermocatalytic NO reduction by CO in the presence of H₂O over Cu/CeO₂[J]. Chinese Journal of Catalysis, 2023, 49: 168-179.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(23)64439-0

https://www.cjcatal.com/EN/Y2023/V49/I6/168

Figures/Tables 12

Fig. 1. (a) XRD patterns of CeO2 and Cu/CeO2. (b) H2-TPR profiles of CeO2, CuOx/CeO2, and CuO. (c) Dispersion of metal Cu over Cu/CeO2. (d) DRS spectra of CeO2 and Cu/CeO2.

Fig. 2. HRTEM images (a,b) and elemental mapping (c) of Cu/CeO2.

Fig. 3. CO conversion (a), NO conversion (b), yield of NH3 (c), and NH3 selectivity (d) at various reaction temperatures over Cu/CeO2 in the dark or under visible light irradiation.

Fig. 4. (a) CO conversion in the CO-H2O reaction. (b) Yield of NH3 in the NO-H2 reaction. (c) Yield of H2 in the NO-CO-H2O reaction. (d) Yield of H2 in the CO-H2O reaction over Cu/CeO2 in the dark or under visible light irradiation.

Fig. 5. Quasi-situ EPR spectra of the Cu/CeO2 sample obtained with each treatment condition in the experimental sequence.

Fig. 6. High-resolution XPS O 1s (a), Ce 3d (b), Cu 2p (c) spectra, and Cu LMM Auger electron spectra (d) of Cu/CeO2 samples obtained before and after the reaction in the presence or absence of light. (Fresh): after N2 pretreatment for 2 h at 300 °C, (In Dark): after reacting at 210 °C in the dark, (In Light) means after reacting at 210 °C under visible irradiation.

Table 1 Relative contents of O and Ce elements in Cu/CeO2 before and after the reaction in the presence or absence of light.

Sample	Treatment	O_ad/O_total (at%)	Ce³⁺/Ce_total (at%)
	Fresh	25.3	29.5
Cu/CeO₂	In dark	23.4	27.7
	In light	27.4	30.3

Fig. 7. In-situ DRIFTS of Cu/CeO2 confirming H2O+CO (a) and NO adsorption (b) during the visible light reaction process.

Fig. 8. Adsorption models: (a) CO-OVs; (b) OC-OVs; (c) H2O-OVs; (d) H2O-Cu. The pristine bond lengths of CO and H2O are 1.128 and 0.960 ?, respectively. H2O is more likely to be adsorbed onto the OVs.

Fig. 9. Adsorption models: (a) NO-Cu; (b) NO-OVs. The pristine bond length of NO is 1.151 ?. (c) Differences in the charge distribution of Cu/CeO2 with adsorbed NO; the blue and yellow represent charge loss and accumulation, respectively. Δq < 0 implies electron donation from Cu to NO.

Fig. 10. (a) Transient photocurrent responses. (b) Electrochemical impedance spectroscopy results. (c) PL spectra of CeO2 and Cu/CeO2.

Fig. 11. Proposed NO-CO-H2O reaction process over Cu/CeO2.

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NH₃ synthesis via visible-light-assisted thermocatalytic NO reduction by CO in the presence of H₂O over Cu/CeO₂

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