Unique Catalytic Mechanism for Ru-Loaded Ternary Intermetallic Electrides for Ammonia Synthesis

Intermetallic electrides have recently shown their priority as catalyst components in ammonia synthesis and CO2 activation. However, their function mechanism has been elusive since its inception, which hinders the further development of such catalysts. In this work, ternary intermetallic electrides...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2022-05, Vol.144 (19), p.8683-8692
Main Authors: Gong, Yutong, Li, Hongchen, Wu, Jiazhen, Song, Xingyi, Yang, Xueqing, Bao, Xiaobing, Han, Xiao, Kitano, Masaaki, Wang, Junjie, Hosono, Hideo
Format: Article
Language:English
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Summary:Intermetallic electrides have recently shown their priority as catalyst components in ammonia synthesis and CO2 activation. However, their function mechanism has been elusive since its inception, which hinders the further development of such catalysts. In this work, ternary intermetallic electrides La–TM–Si (TM = Co, Fe, and Mn) were synthesized as hosts of ruthenium (Ru) particles for ammonia synthesis catalysis. Although they have the same crystal structure and possess low work functions commonly, the promotion effects on Ru particles rather differ from each other. The catalytic activity follows the sequence of Ru/LaCoSi > Ru/LaFeSi > Ru/LaMnSi. Furthermore, Ru/LaCoSi exhibits much better catalytic durability than the other two. A combination of experiments and first-principles calculations shows that apparent N2 activation energy on each catalyst is much lower than that over conventional Ru-based catalysts, which suggests that N2 dissociation can be conspicuously promoted by the concerted actions of the specific electronic structure and atomic configuration of intermetallic electride-supported catalysts. The NH x formations proceeded on La are energetically favored, which makes it possible to bypass the scaling relations based on only Ru as the active site. The rate-determining step of Ru/La–TM–Si was identified to be NH2 formation. The transition metal (TM) in La–TM–Si electrides has a significant influence on the metal–support interaction of Ru and La–TM–Si. These findings provide a guide for the development of new and effective catalyst hosts for ammonia synthesis and other hydrogenation reactions.
ISSN:0002-7863
1520-5126
DOI:10.1021/jacs.2c01899