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

Gong，Yutong1; Li，Hongchen1; Wu，Jiazhen2,3; Song，Xingyi1; Yang，Xueqing1; Bao，Xiaobing1; Han，Xiao1; Kitano，Masaaki2; Wang，Junjie1; Hosono，Hideo2

2022

10.1021/jacs.2c01899

Journal of the American Chemical Society   影响因子和分区

0002-7863

1520-5126

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 NHx 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.

EI

英语

NI论文

其他

20222012117683

Activation energy ; Ammonia ; Calculations ; Catalysis ; Catalyst activity ; Catalyst supports ; Crystal atomic structure ; Electronic structure ; Hydrogenation ; Intermetallics ; Silicon

Metallurgy:531.1 ; Precious Metals:547.1 ; Nonferrous Metals and Alloys excluding Alkali and Alkaline Earth Metals:549.3 ; Chemical Reactions:802.2 ; Chemical Agents and Basic Industrial Chemicals:803 ; Chemical Products Generally:804 ; Inorganic Compounds:804.2 ; Mathematics:921 ; Atomic and Molecular Physics:931.3 ; Crystal Lattice:933.1.1

2-s2.0-85130072860

Scopus

1.State Key Laboratory of Solidification Processing,School of Materials Science and Engineering,Northwestern Polytechnical University,Xi'an,Shaanxi,710072,China
2.Materials Research Center for Element Strategy,Tokyo Institute of Technology,Yokohama,4259 Nagatsuta-cho, Midori-ku, Kanagawa,226-8503,Japan
3.Department of Materials Science and Engineering,Southern University of Science and Technology,Shenzhen,Guangdong,518055,China

Gong，Yutong,Li，Hongchen,Wu，Jiazhen,et al. Unique Catalytic Mechanism for Ru-Loaded Ternary Intermetallic Electrides for Ammonia Synthesis[J]. Journal of the American Chemical Society,2022.

Gong，Yutong.,Li，Hongchen.,Wu，Jiazhen.,Song，Xingyi.,Yang，Xueqing.,...&Hosono，Hideo.(2022).Unique Catalytic Mechanism for Ru-Loaded Ternary Intermetallic Electrides for Ammonia Synthesis.Journal of the American Chemical Society.

Gong，Yutong,et al."Unique Catalytic Mechanism for Ru-Loaded Ternary Intermetallic Electrides for Ammonia Synthesis".Journal of the American Chemical Society (2022).