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Title: Efficient Nitrogen Fixation via a Redox-Flexible Single-Iron Site with Reverse-Dative Iron -> Boron s Bonding

Abstract

Model systems of the FeMo cofactor of nitrogenase have been explored extensively in catalysis to gain insights into their ability for nitrogen fixation that is of vital importance to the human society. Here we investigate the trigonal pyramidal borane-ligand Fe complex by first-principles calculations, and find that the variation of oxidation state of Fe along the reaction path correlates with that of the reverse-dative Fe?B bonding. The redox-flexibility of the reverse-dative Fe?B bonding helps to provide an electron reservoir that buffers and stabilizes the evolution of Fe oxidation state, which is essential for forming the key intermediates of N2 activation. Our work provides insights for understanding and optimizing homogeneous and surface single-atom catalysts with reverse-dative donating ligands for efficient dinitrogen fixation. The extension of this kind of molecular catalytic active center to heterogeneous catalysts is also discussed.

Authors:
 [1];  [1];  [1];  [1];  [1]; ORCiD logo [2]
  1. Tsinghua University
  2. BATTELLE (PACIFIC NW LAB)
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1545031
Report Number(s):
PNNL-SA-133169
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Journal of Physical Chemistry A
Additional Journal Information:
Journal Volume: 122; Journal Issue: 18
Country of Publication:
United States
Language:
English
Subject:
Single-Fe-atom catalyst, nitrogen fixation, redox-flexible, reverse-dative Fe?B bond, Oxidation state, CASSCF

Citation Formats

Lu, Jun-Bo, Ma, Xue-Lu, Wang, Jia-Qi, Liu, Jin-Cheng, Xiao, Hai, and Li, Jun. Efficient Nitrogen Fixation via a Redox-Flexible Single-Iron Site with Reverse-Dative Iron -> Boron s Bonding. United States: N. p., 2018. Web. doi:10.1021/acs.jpca.8b02089.
Lu, Jun-Bo, Ma, Xue-Lu, Wang, Jia-Qi, Liu, Jin-Cheng, Xiao, Hai, & Li, Jun. Efficient Nitrogen Fixation via a Redox-Flexible Single-Iron Site with Reverse-Dative Iron -> Boron s Bonding. United States. doi:10.1021/acs.jpca.8b02089.
Lu, Jun-Bo, Ma, Xue-Lu, Wang, Jia-Qi, Liu, Jin-Cheng, Xiao, Hai, and Li, Jun. Thu . "Efficient Nitrogen Fixation via a Redox-Flexible Single-Iron Site with Reverse-Dative Iron -> Boron s Bonding". United States. doi:10.1021/acs.jpca.8b02089.
@article{osti_1545031,
title = {Efficient Nitrogen Fixation via a Redox-Flexible Single-Iron Site with Reverse-Dative Iron -> Boron s Bonding},
author = {Lu, Jun-Bo and Ma, Xue-Lu and Wang, Jia-Qi and Liu, Jin-Cheng and Xiao, Hai and Li, Jun},
abstractNote = {Model systems of the FeMo cofactor of nitrogenase have been explored extensively in catalysis to gain insights into their ability for nitrogen fixation that is of vital importance to the human society. Here we investigate the trigonal pyramidal borane-ligand Fe complex by first-principles calculations, and find that the variation of oxidation state of Fe along the reaction path correlates with that of the reverse-dative Fe?B bonding. The redox-flexibility of the reverse-dative Fe?B bonding helps to provide an electron reservoir that buffers and stabilizes the evolution of Fe oxidation state, which is essential for forming the key intermediates of N2 activation. Our work provides insights for understanding and optimizing homogeneous and surface single-atom catalysts with reverse-dative donating ligands for efficient dinitrogen fixation. The extension of this kind of molecular catalytic active center to heterogeneous catalysts is also discussed.},
doi = {10.1021/acs.jpca.8b02089},
journal = {Journal of Physical Chemistry A},
number = 18,
volume = 122,
place = {United States},
year = {2018},
month = {5}
}