Ru surface density effect on ammonia synthesis activity and hydrogen poisoning of ceria-supported Ru catalysts

doi:10.1016/S1872-2067(20)63787-1

Abstract

Abstract:

Evaluating the effect of metal surface density on catalytic performance is critical for designing high-activity metal-based catalysts. In this study, a series of ceria (CeO₂)-supported Ru catalysts (Ru/CeO₂) were prepared to analyze the effect of Ru surface density on the catalytic performance of Ru/CeO₂ for ammonia synthesis. For the Ru/CeO₂ catalysts with Ru surface densities lower than 0.68 Ru nm^-2, the Ru layers were in close contact with CeO₂, and electrons were transferred directly from the CeO₂ defect sites to the Ru species. In such cases, the adsorption of hydrogen species on the Ru sites in the vicinity of O atoms was high, leading to a high ammonia synthesis activity and strong hydrogen poisoning. In contrast, the preferential aggregation of Ru species into large particles on top of the Ru overlayer resulted in the coexistence of Ru clusters and particles, for catalysts with a Ru surface density higher than 1.4 Ru nm^-2, for which Ru particles were isolated from the direct electronic influence of CeO₂. Consequently, the Ru-CeO₂ interactions were weak, and hydrogen poisoning can be significantly alleviated. Overall, electron transfer and hydrogen adsorption synergistically affected the synthesis of ammonia over Ru/CeO₂ catalysts, and catalyst samples with a Ru surface density lower than 0.31 Ru nm^-2 or exactly 2.1 Ru nm^-2 exhibited high catalytic activity for ammonia synthesis.

Key words: Ammonia synthesis, Ceria-supported Ru catalyst, Ru surface density, Hydrogen adsorption, Hydrogen poisoning

Bingyu Lin, Yuyuan Wu, Biyun Fang, Chunyan Li, Jun Ni, Xiuyun Wang, Jianxin Lin, Lilong Jiang. Ru surface density effect on ammonia synthesis activity and hydrogen poisoning of ceria-supported Ru catalysts[J]. Chinese Journal of Catalysis, 2021, 42(10): 1712-1723.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(20)63787-1

https://www.cjcatal.com/EN/Y2021/V42/I10/1712

Figures/Tables 10

Fig. 1. Initial NH3 synthesis rate (a) and reaction order (b) as a function of Ru surface density for the Ru/CeO2 catalysts. Reaction conditions: 400 °C, 1 MPa.

Fig. 2. XRD patterns of CeO2 and Ru/CeO2 catalysts.

Fig. 3. Aberration-corrected high-angle annular dark-field scanning transmission electron microscopy images of the fresh 0.15Ru/CeO2 (a) and 0.68Ru/CeO2 (b) catalysts. HRTEM images of the fresh 0.31Ru/CeO2 (c) and 3.4Ru/CeO2 (d) catalysts.

Fig. 4. H2-TPR profiles of CeO2 and Ru/CeO2 catalysts.

Fig. 5. Raman spectra of CeO2 and Ru/CeO2 catalysts with different Ru surface densities at a laser excitation wavelength of 532 nm; here, 2TA, F2g, D, and 2LO denote the second-order transverse acoustic, fluorite, defect-induced, and second-order longitudinal optical modes of CeO2.

Fig. 6. (a) In situ Ru 3d XPS profiles of Ru/CeO2 catalysts with different Ru surface densities; (b) Intensity ratio of Oβ/Oα dependence on the Ru surface density; (c) XPS IRu 3d/ICe 3d ratio dependence on Ru surface density of Ru/CeO2 catalysts. Here, Oα and Oβ denote lattice O and O vacancies, respectively.

Fig. 7. Time-resolved D/H exchange reaction at 50 °C and TPSR; signals at m/z = 3 (HD), m/z = 4 (D2), m/z = 16 (NH2 or ND), m/z = 18 (H2O or DO), m/z = 19 (HDO) and m/z = 20 (D2O).

Fig. 8. H2 evolution during CO-TPR studies.

Fig. 9. In situ DRIFTS profiles of CeO2 (a), 0.15Ru/CeO2 (b), and Ru/CeO2 (c) catalysts with different Ru surface densities after exposure to H2 at 200 °C for 10 min.

Fig. 10. DRIFTS profiles for the adsorption of D2 on 2.1Ru/CeO2 after H2 pre-exposure.

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