Tuning clusters-metal oxide promoters electronic interaction of Ru-based catalyst for ammonia synthesis under mild conditions

doi:10.1016/S1872-2067(23)64644-3

Abstract

Abstract:

Ammonia (NH₃) is an excellent candidate for hydrogen storage and transport. However, producing NH₃ under mild conditions is a long-term, arduous task. Atomic cluster catalysts (ACCs) have been shown to be effective for catalytic N₂-to-NH₃ conversion, opening the door to the development of efficient catalysts under mild conditions. Still, ACC formation with thermally stable catalytic sites remains a challenge because of their high surface free energy. Herein, we report anchoring Ba and/or Ce onto Ru ACCs (2 wt% Ru atomic clusters supported on N-doped carbon) to form so-called clusters-metal oxide promoters electronic interaction (CMEI) to stabilize the Ru atomic clusters. The resulting Ba/Ce/Ru ACCs significantly boost the NH₃ synthesis rate to 56.2 mmol_NH3 g_cat^-1 h^-1 at 400 °C and 1 MPa, which is 7.5-fold higher than that of Ru ACC. The strengthened CMEI between the Ba/Ce and Ru atomic clusters across the Ba/Ce/Ru ACC enables electron transfer from Ba and/or Ce to Ru atomic clusters. As such, the electron-enriched Ru atom could facilitate electron transfer to N≡N bond π* orbitals, which would weaken the N≡N bond and drive the eventual conversion of N₂ to NH₃. This study offers insight into the role of CMEI in Ru ACCs and provides an effective approach for designing stable atomic cluster catalysts for NH₃ synthesis.

Key words: Atomic cluster, Promoter, N₂ activation, Ammonia synthesis, Electronic interaction

Tianhua Zhang, Haihui Hu, Jiaxin Li, Yinglong Gao, Lingling Li, Mingyuan Zhang, Xuanbei Peng, Yanliang Zhou, Jun Ni, Bingyu Lin, Jianxin Lin, Bing Zhu, Dongshuang Wu, Linjie Zhang, Lili Han, Lirong Zheng, Xiuyun Wang, Lilong Jiang. Tuning clusters-metal oxide promoters electronic interaction of Ru-based catalyst for ammonia synthesis under mild conditions[J]. Chinese Journal of Catalysis, 2024, 60: 209-218.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(23)64644-3

https://www.cjcatal.com/EN/Y2024/V60/I5/209

Figures/Tables 5

Scheme 1. Schematic illustration of clusters-metal oxide promoters electronic interaction over the Ru atomic clusters catalysts.

Fig. 1. NH3 synthesis rate (a) and TOFRu surface and TOFRu total (b) over the as-synthesized catalysts at 400 °C and 1 MPa. Arrhenius plot under 1 MPa (c), NH3 reaction order (d), N2 reaction order (e), and H2 reaction order (f) over the as-synthesized catalysts at 400 °C and 1 MPa.

Fig. 2. AC-STEM images of 2 wt% Ru ACC (Ru ACC) (a) and Ba/Ce/Ru ACC (b) showing the presence of dimers (yellow circles) and trimers (blue circles). Ru K-edge EXAFS (c) and normalized Ru K-edge XANES (d) spectra of the as-prepared catalysts.

Fig. 3. XPS spectra of Ru 3p (a), Ba 3d (b), Ce 3d (c) over Ru ACCs, Ba/Ru ACCs, Ce/Ru ACCs, and Ba/Ce/Ru ACCs.

Fig. 4. Quasi-in situ XPS spectra of Ru 3p (a), Ba 3d (b), and Ce 3d (c) acquired over Ba/Ce/Ru ACC upon H2 and 25% N2-75% H2 treatment at 400 °C for 2 h; (d) in situ DRIFTS acquired over the as-prepared catalysts under 25% N2-75% D2 at different temperatures.

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