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Nano Research 2019, 12(9): 2341-2347 https://doi.org/10.1007/s12274-019-2349-0
Research Article | Issue | Published: 23 March 2019

Highly efficient K-Fe/C catalysts derived from metal-organic frameworks towards ammonia synthesis

Show Author's Information Pengqi Yan1,§,  Wenhan Guo2,§,  Zibin Liang2,  Wei Meng2,  Zhen Yin3,  Siwei Li1,  Mengzhu Li1,  Mengtao Zhang1,  Jie Yan1,  Dequan Xiao4,  Ruqiang Zou2( ),  Ding Ma1( )
Beijing National Laboratory for Molecular SciencesCollege of Chemistry and Molecular Engineering and College of Engineering, and BIC-ESATPeking UniversityBeijing100871China
Beijing Key Laboratory for Theory and Technology of Advanced Battery MaterialsDepartment of Materials Science and EngineeringCollege of EngineeringPeking UniversityBeijing10087China
State Key Laboratory of Separation Membranes and Membrane ProcessesSchool of Chemistry and Chemical EngineeringTianjin Polytechnic UniversityTianjin300387China
Department of Chemistry and Chemical EngineeringUniversity of New Haven, West HavenCT06516USA

§ Pengqi Yan and Wenhan Guo contributed equally to this work.

Keywords:
metal-organic frameworks, pyrolysis, ammonia synthesis, iron nanoparticles, K promotion
Topics:
Catalyst activityCrystalline materials IronKinetic theoryMetal nanoparticlesOrganic polymersOrganometallicsSynthesis (chemical)
Cite this article:
Yan P, Guo W, Liang Z, et al. Highly efficient K-Fe/C catalysts derived from metal-organic frameworks towards ammonia synthesis. Nano Research, 2019, 12(9): 2341-2347. https://doi.org/10.1007/s12274-019-2349-0
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Abstract Full text Electronic supplementary material About this article

Fe-based catalysts have been discovered as the best elementary metal-based heterogeneous catalysts for the ammonia synthesis in industrial application during the last century. Herein, a novel and scalable strategy is developed to prepare the K-promoted Fe/C catalyst with extremely high Fe loading (> 50 wt.%) through pyrolysis of the Fe-based metal-organic framework (MOF) xerogel. The obtained K-Fe/C catalysts exhibited superior activity and stability towards ammonia synthesis. The weight-specific reaction rate of Fe/C with K2O as promoter can achieve 12.4 mmol·g-1·h-1 at 350 ℃ and 30.4 mmol·g-1·h-1 at 400 ℃, approximately four and two times higher than that of the commercial fused-iron catalyst (3.4 mmol·g-1·h-1 at 350 ℃ and 16.7 mmol·g-1·h-1 at 400 ℃) under the same condition, respectively. The excellent performance of K-Fe/C can be ascribed to the inherited structure derived from the metal-organic frame precursors and the promotion of potassium, which can modify the binding energy of reactant molecules on the Fe surface, transfer electrons to iron for effective activation of nitrogen, prevent agglomeration of Fe nanoparticle (NPs) and restrain side reaction of carbon matrix to methane.


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About this article

Highly efficient K-Fe/C catalysts derived from metal-organic frameworks towards ammonia synthesis

Show Author's information Pengqi Yan1,§, Wenhan Guo2,§, Zibin Liang2, Wei Meng2, Zhen Yin3, Siwei Li1, Mengzhu Li1, Mengtao Zhang1, Jie Yan1, Dequan Xiao4, Ruqiang Zou2( ), Ding Ma1( )
Beijing National Laboratory for Molecular SciencesCollege of Chemistry and Molecular Engineering and College of Engineering, and BIC-ESATPeking UniversityBeijing100871China
Beijing Key Laboratory for Theory and Technology of Advanced Battery MaterialsDepartment of Materials Science and EngineeringCollege of EngineeringPeking UniversityBeijing10087China
State Key Laboratory of Separation Membranes and Membrane ProcessesSchool of Chemistry and Chemical EngineeringTianjin Polytechnic UniversityTianjin300387China
Department of Chemistry and Chemical EngineeringUniversity of New Haven, West HavenCT06516USA

§ Pengqi Yan and Wenhan Guo contributed equally to this work.

Abstract

Fe-based catalysts have been discovered as the best elementary metal-based heterogeneous catalysts for the ammonia synthesis in industrial application during the last century. Herein, a novel and scalable strategy is developed to prepare the K-promoted Fe/C catalyst with extremely high Fe loading (> 50 wt.%) through pyrolysis of the Fe-based metal-organic framework (MOF) xerogel. The obtained K-Fe/C catalysts exhibited superior activity and stability towards ammonia synthesis. The weight-specific reaction rate of Fe/C with K2O as promoter can achieve 12.4 mmol·g-1·h-1 at 350 ℃ and 30.4 mmol·g-1·h-1 at 400 ℃, approximately four and two times higher than that of the commercial fused-iron catalyst (3.4 mmol·g-1·h-1 at 350 ℃ and 16.7 mmol·g-1·h-1 at 400 ℃) under the same condition, respectively. The excellent performance of K-Fe/C can be ascribed to the inherited structure derived from the metal-organic frame precursors and the promotion of potassium, which can modify the binding energy of reactant molecules on the Fe surface, transfer electrons to iron for effective activation of nitrogen, prevent agglomeration of Fe nanoparticle (NPs) and restrain side reaction of carbon matrix to methane.

Keywords: metal-organic frameworks, pyrolysis, ammonia synthesis, iron nanoparticles, K promotion

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Publication history
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Acknowledgements

Publication history

Received: 20 December 2018
Revised: 16 February 2019
Accepted: 18 February 2019
Published: 23 March 2019
Issue date: September 2019

Copyright

© Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature 2019

Acknowledgements

Acknowledgements

This work was financially supported by the National Key Research and Development Program of China (Nos. 2017YFB0602200 and 2017YFA0206701), National Program for Support of Top-notch Young Professionals, Changjiang Scholar Program and the National Natural Science Foundation of China (Nos. 21725301, 91645115, 21673273, 21473003, 21872104, and 21821004). The XPS experiments were conducted at Lab of Multitechniques Electron & Ion Spectrometer for Surface Analysis of Peking University. We thank Jinglin Xie for XPS data discussion.

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