Crystallographic and Morphological Sensitivity of N<sub>2</sub> Activation over Ruthenium

Hao Lin; Jin-xun Liu; Hong-jun Fan; Wei-xue Li

doi:10.1063/1674-0068/cjcp2009171

Volume 34 Issue 3

Jun. 2021

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Hao Lin, Jin-xun Liu, Hong-jun Fan, Wei-xue Li. Crystallographic and Morphological Sensitivity of N2 Activation over Ruthenium[J]. Chinese Journal of Chemical Physics , 2021, 34(3): 263-272. doi: 10.1063/1674-0068/cjcp2009171

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Hao Lin, Jin-xun Liu, Hong-jun Fan, Wei-xue Li. Crystallographic and Morphological Sensitivity of N₂ Activation over Ruthenium[J]. Chinese Journal of Chemical Physics , 2021, 34(3): 263-272. doi: 10.1063/1674-0068/cjcp2009171

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Crystallographic and Morphological Sensitivity of N₂ Activation over Ruthenium

doi: 10.1063/1674-0068/cjcp2009171

Hao Lin^{a, d, †},
Jin-xun Liu^{b, †},
Hong-jun Fan^{a
,
,},
Wei-xue Li^{b, c
,
,}

a.
State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Science, Dalian 116023, China
b.
Department of Chemical Physics, School of Chemistry and Materials Science, University of Science and Technology of China, Hefei 230026, China
c.
Hefei National Laboratory for Physical Science at the Microscale, iCHEM, University of Science and Technology of China, Hefei 230026, China
d.
University of Chinese Academy of Sciences, Beijing 100049, China

More Information

Corresponding author: Hong-jun Fan, E-mail: fanhj@dicp.ac.cn; Wei-xue Li, E-mail: wxli70@ustc.edu.cn
Received Date: 2020-09-25
Accepted Date: 2020-11-17
Publish Date: 2021-06-27

Abstract

Abstract

Ruthenium (Ru) serves as a promising catalyst for ammonia synthesis via the Haber-Bosch process, identification of the structure sensitivity to improve the activity of Ru is important but not fully explored yet. We present here density functional theory calculations combined with micro-kinetic simulations on nitrogen molecule activation, a crucial step in ammonia synthesis, over a variety of hexagonal close-packed (hcp) and face-center cubic (fcc) Ru facets. Hcp $\left\{ {21\overline 3 0} \right\}$ facet exhibits the highest activity toward N$_2$ dissociation in hcp Ru, followed by the (0001) monatomic step sites. The other hcp Ru facets have N$_2$ dissociation rates at least three orders lower. Fcc $\{211\}$ facet shows the best performance for N$_2$ activation in fcc Ru, followed by $\{311\}$, which indicates stepped surfaces make great contributions to the overall reactivity. Although hcp Ru $\left\{ {21\overline 3 0} \right\}$ facet and (0001) monatomic step sites have lower or comparable activation barriers compared with fcc Ru $\{211\}$ facet, fcc Ru is proposed to be more active than hcp Ru for N$_2$ conversion due to the exposure of the more favorable active sites over step surfaces in fcc Ru. This work provides new insights into the crystal structure sensitivity of N$_2$ activation for mechanistic understanding and rational design of ammonia synthesis over Ru catalysts.
- Ammonia synthesis,
- N$_2$ activation,
- Density functional theory,
- Ru,
- Crystallographic and morphological sensitivity

^†These authors contributed equally to this work.

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References(74)

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