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Title: Single vs double atom catalyst for N 2 activation in nitrogen reduction reaction: A DFT perspective

Abstract

Abstract Ammonia synthesis through electrochemical reduction of nitrogen molecules is a promising strategy to significantly reduce the energy consumption in traditional industrial process. Detailed mechanism study of multistep complex nitrogen reduction reaction is prerequisite for the design of highly efficient catalyst. Stable atomically dispersed catalyst with unique geometric and electronic structure is suitable for the mechanism clarification of such a complex reaction. In this study, d ‐block transition‐metal (TM) anchored C 2 N single layer catalyst is investigated by the density functional theory (DFT) calculation. Both single TM‐anchored single atom catalyst (SAC) and double TM‐anchored double atom catalyst (DAC) exhibit good thermodynamic stability in atomically dispersed catalyst. In the case of SACs, IVB metals (Ti, Zr, Hf) exhibit the highest reactivity and lowest overpotential. While in the case of DACs, Cr─Cr system leads to the NH 3 formation, but V─V system leads to the N 2 H 4 formation. The SACs show much lower overpotential and stronger activation of N 2 molecule than the DACs due to the different activation mechanisms: traditional σ ‐donation/ π ‐backdonation N 2 activation mechanism is found in SACs, while a new π ‐donation/π‐backdonation N 2 activation mechanism is found in the DACs. The presentmore » work demonstrates that the different catalytic effect for NRR between SAC and DAC and their corresponding electronic structure origin, which gives more insight into the single atom catalyst. image« less

Authors:
 [1];  [2];  [3];  [3]; ORCiD logo [2]
+ Show Author Affiliations
  1. Institute of Functional Nano &, Soft Materials (FUNSOM) Jiangsu Key Laboratory for Carbon‐Based Functional Materials &, Devices, Soochow University Suzhou Jiangsu China, Materials Science and Engineering Program and Department of Mechanical Engineering The University of Texas at Austin Austin Texas
  2. Materials Science and Engineering Program and Department of Mechanical Engineering The University of Texas at Austin Austin Texas
  3. Institute of Functional Nano &, Soft Materials (FUNSOM) Jiangsu Key Laboratory for Carbon‐Based Functional Materials &, Devices, Soochow University Suzhou Jiangsu China
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1592491
Alternate Identifier(s):
OSTI ID: 1592492
Grant/Contract Number:  
DE‐SC0019019
Resource Type:
Published Article
Journal Name:
EcoMat
Additional Journal Information:
Journal Name: EcoMat Journal Volume: 2 Journal Issue: 1; Journal ID: ISSN 2567-3173
Publisher:
Wiley Blackwell (John Wiley & Sons)
Country of Publication:
China
Language:
English

Citation Formats

Qian, Yumin, Liu, Yuanyue, Zhao, Yu, Zhang, Xiaohong, and Yu, Guihua. Single vs double atom catalyst for N 2 activation in nitrogen reduction reaction: A DFT perspective. China: N. p., 2020. Web. doi:10.1002/eom2.12014.
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Qian, Yumin, Liu, Yuanyue, Zhao, Yu, Zhang, Xiaohong, & Yu, Guihua. Single vs double atom catalyst for N 2 activation in nitrogen reduction reaction: A DFT perspective. China. https://doi.org/10.1002/eom2.12014
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Qian, Yumin, Liu, Yuanyue, Zhao, Yu, Zhang, Xiaohong, and Yu, Guihua. Sun . "Single vs double atom catalyst for N 2 activation in nitrogen reduction reaction: A DFT perspective". China. https://doi.org/10.1002/eom2.12014.
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@article{osti_1592491,
title = {Single vs double atom catalyst for N 2 activation in nitrogen reduction reaction: A DFT perspective},
author = {Qian, Yumin and Liu, Yuanyue and Zhao, Yu and Zhang, Xiaohong and Yu, Guihua},
abstractNote = {Abstract Ammonia synthesis through electrochemical reduction of nitrogen molecules is a promising strategy to significantly reduce the energy consumption in traditional industrial process. Detailed mechanism study of multistep complex nitrogen reduction reaction is prerequisite for the design of highly efficient catalyst. Stable atomically dispersed catalyst with unique geometric and electronic structure is suitable for the mechanism clarification of such a complex reaction. In this study, d ‐block transition‐metal (TM) anchored C 2 N single layer catalyst is investigated by the density functional theory (DFT) calculation. Both single TM‐anchored single atom catalyst (SAC) and double TM‐anchored double atom catalyst (DAC) exhibit good thermodynamic stability in atomically dispersed catalyst. In the case of SACs, IVB metals (Ti, Zr, Hf) exhibit the highest reactivity and lowest overpotential. While in the case of DACs, Cr─Cr system leads to the NH 3 formation, but V─V system leads to the N 2 H 4 formation. The SACs show much lower overpotential and stronger activation of N 2 molecule than the DACs due to the different activation mechanisms: traditional σ ‐donation/ π ‐backdonation N 2 activation mechanism is found in SACs, while a new π ‐donation/π‐backdonation N 2 activation mechanism is found in the DACs. The present work demonstrates that the different catalytic effect for NRR between SAC and DAC and their corresponding electronic structure origin, which gives more insight into the single atom catalyst. image},
doi = {10.1002/eom2.12014},
journal = {EcoMat},
number = 1,
volume = 2,
place = {China},
year = {2020},
month = {1}
}
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