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Nano Research 2020, 13(9): 2393-2398 https://doi.org/10.1007/s12274-020-2863-0
Research Article | Issue | Published: 16 June 2020

Single-molecule imaging of dinitrogen molecule adsorption on individual iron phthalocyanine

Show Author's Information Chengding Gu1,  Jia Lin Zhang1,2( ),  Jian Qiang Zhong3,  Qian Shen4,  Xiong Zhou5,  Kaidi Yuan6,  Shuo Sun2,  Xu Lian1,  Zhirui Ma1,  Wei Chen1,2,7,8( )
Department of Chemistry, National University of Singapore, Singapore 117543, Singapore
Department of Physics, National University of Singapore, Singapore 117542, Singapore
Department of Interface Science, Fritz-Haber-Institut der Max-Planck-Gesellschaft, Berlin 14195, Germany
Institute of Advanced Materials, Nanjing Tech University, Nanjing 210009, China
BNLMS, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China
School of Physical Science and Technology, Shanghai Tech University, Shanghai 200031, China
Joint School of National University of Singapore and Tianjin University, International Campus of Tianjin University, Fuzhou 350207, China
National University of Singapore (Suzhou) Research Institute, Suzhou 215123, China
Keywords:
single-molecule, dinitrogen, iron phthalocyanine, axial coordination
Topics:
Electronic structureIronScanning tunneling microscopyTemperatureX-ray photoelectron spectroscopy
Cite this article:
Gu C, Zhang JL, Qiang Zhong J, et al. Single-molecule imaging of dinitrogen molecule adsorption on individual iron phthalocyanine. Nano Research, 2020, 13(9): 2393-2398. https://doi.org/10.1007/s12274-020-2863-0
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Abstract Full text Electronic supplementary material About this article

Nitrogen fixation is a vital process for both nature and industry. Whereas the nitrogenase can reduce nitrogen in ambient environment in nature, the industrialized Haber-Bosch process is a high temperature and high-pressure process. Since the discovery of the first dinitrogen complex in 1965, many dinitrogen complexes are prepared in a homogeneous solution to mimic the nitrogenase enzyme in nature. However, studies of the heterogeneous process on surface are rarely addressed. Moreover, molecular scale characterization for such dinitrogen complex is lacking. Here, we present a simple model system to investigate, at the single-molecule level, the binding of dinitrogen on a surface confined iron phthalocyanine (FePc) monolayer through the combination of in-situ low-temperature scanning tunneling microscopy (LT-STM) and x-ray photoelectron spectroscopy (XPS) measurements. The iron center in FePc molecule deposited on Au(111) and highly oriented pyrolytic graphite (HOPG) surface can adsorb dinitrogen molecule at room temperature and low pressure. A comparative study reveals that the adsorption behaviors of FePc on these two different substrates are identical. Chemical bond is formed between the dinitrogen and the Fe atom in the FePc molecule, which greatly modifies the electronic structure of FePc. The bonding is reversible and can be manipulated by applying bias using a STM tip or by thermal annealing.


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Electronic supplementary material
About this article

Single-molecule imaging of dinitrogen molecule adsorption on individual iron phthalocyanine

Show Author's information Chengding Gu1, Jia Lin Zhang1,2( ), Jian Qiang Zhong3, Qian Shen4, Xiong Zhou5, Kaidi Yuan6, Shuo Sun2, Xu Lian1, Zhirui Ma1, Wei Chen1,2,7,8( )
Department of Chemistry, National University of Singapore, Singapore 117543, Singapore
Department of Physics, National University of Singapore, Singapore 117542, Singapore
Department of Interface Science, Fritz-Haber-Institut der Max-Planck-Gesellschaft, Berlin 14195, Germany
Institute of Advanced Materials, Nanjing Tech University, Nanjing 210009, China
BNLMS, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China
School of Physical Science and Technology, Shanghai Tech University, Shanghai 200031, China
Joint School of National University of Singapore and Tianjin University, International Campus of Tianjin University, Fuzhou 350207, China
National University of Singapore (Suzhou) Research Institute, Suzhou 215123, China

Abstract

Nitrogen fixation is a vital process for both nature and industry. Whereas the nitrogenase can reduce nitrogen in ambient environment in nature, the industrialized Haber-Bosch process is a high temperature and high-pressure process. Since the discovery of the first dinitrogen complex in 1965, many dinitrogen complexes are prepared in a homogeneous solution to mimic the nitrogenase enzyme in nature. However, studies of the heterogeneous process on surface are rarely addressed. Moreover, molecular scale characterization for such dinitrogen complex is lacking. Here, we present a simple model system to investigate, at the single-molecule level, the binding of dinitrogen on a surface confined iron phthalocyanine (FePc) monolayer through the combination of in-situ low-temperature scanning tunneling microscopy (LT-STM) and x-ray photoelectron spectroscopy (XPS) measurements. The iron center in FePc molecule deposited on Au(111) and highly oriented pyrolytic graphite (HOPG) surface can adsorb dinitrogen molecule at room temperature and low pressure. A comparative study reveals that the adsorption behaviors of FePc on these two different substrates are identical. Chemical bond is formed between the dinitrogen and the Fe atom in the FePc molecule, which greatly modifies the electronic structure of FePc. The bonding is reversible and can be manipulated by applying bias using a STM tip or by thermal annealing.

Keywords: single-molecule, dinitrogen, iron phthalocyanine, axial coordination

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Publication history
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Acknowledgements

Publication history

Received: 18 March 2020
Revised: 17 April 2020
Accepted: 08 May 2020
Published: 16 June 2020
Issue date: September 2020

Copyright

© Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature 2020

Acknowledgements

Authors acknowledge the financial support from Singapore National Research Foundation under NRF2017NRF-NSFC001-007, Singapore MOE grant of MOE2019-T2-1-002 and NUS Flagship Green Energy Program.

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