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Title: FeMo sub-nanoclusters/single atoms for neutral ammonia electrosynthesis

Abstract

Electrochemical N2 reduction reaction (NRR) has long been regarded as a promising process to generate NH3 under ambient conditions. Therefore, developing cost-effective and high-performance non-noble-metal catalysts for NRR is highly desirable. Inspired by the biological nitrogenase structure, we here designed and synthesized a catalyst with iron-molybdenum sub-nanoclusters and single atoms on porous nitrogen-doped carbon (FeMo/NC). The catalyst features porous structure beneficial to active site exposure and accessibility to electrolyte as well as FeMo sub-nanoclusters and single atoms enabling to activate N2 molecular. In situ near-ambient pressure X-ray photoelectron spectroscopy tests reveal that during the process from vacuum to nitrogen saturation, N2 was close to, adsorbed on and interacted with Fe and Mo in FeMo/NC. The Fe and Mo through electron transfer play a key role in activating the N2 molecules. Therefore, when tested for NRR, FeMo/NC achieves the maximum Faradaic efficiency (FE) of 11.8 ± 0.8% at -0.25 V and NH3 yield rate of 26.5 ± 0.8 μg h-1 mgcat.-1 at -0.3 V in neutral electrolyte. Moreover, the catalyst exhibits ignorable variations in the FE and a slight decrease in current density for 100,000 s. This work develops a non-precious bimetallic electrocatalyst with synergetic effect capability for efficient NH3 productionmore » and provides a guideline for the design of efficient and robust catalysts with coexistence of sub-nanoclusters and single atoms.« less

Authors:
 [1];  [2];  [3];  [4]; ORCiD logo [5];  [1];  [6];  [7];  [8];  [1];  [9];  [3];  [10]
  1. Tianjin Univ. of Technology (China)
  2. Tianjin Univ. of Technology (China); Univ. of California, Irvine, CA (United States)
  3. Tamkang Univ. (China)
  4. Tianjin Univ. (China)
  5. Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
  6. National Synchrotron Radiation Research Center (Taiwan)
  7. Chinese Academy of Sciences (CAS), Shanxi (China)
  8. Xi'an Univ. of Technology (China)
  9. Lanzhou Univ. of Technology (China)
  10. Univ. of California, Irvine, CA (United States)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1756175
Alternate Identifier(s):
OSTI ID: 1809800
Report Number(s):
BNL-220762-2020-JAAM
Journal ID: ISSN 2211-2855
Grant/Contract Number:  
SC0012704
Resource Type:
Accepted Manuscript
Journal Name:
Nano Energy
Additional Journal Information:
Journal Volume: 77; Journal ID: ISSN 2211-2855
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
77 NANOSCIENCE AND NANOTECHNOLOGY; Nitrogen fixation; Ammonia electrosynthesis; Neutral electrolyte; Sub-nanocluster; Single atom; FeMo electrocatalyst

Citation Formats

Liu, Wei, Han, L., Wang, H.-T., Zhao, X., Boscoboinik, Jorge A., Liu, X., Pao, C.-W., Sun, Jiaqiang, Zhuo, L., Luo, J., Ren, J., Pong, W.-F., and Xin, H.L.. FeMo sub-nanoclusters/single atoms for neutral ammonia electrosynthesis. United States: N. p., 2020. Web. https://doi.org/10.1016/j.nanoen.2020.105078.
Liu, Wei, Han, L., Wang, H.-T., Zhao, X., Boscoboinik, Jorge A., Liu, X., Pao, C.-W., Sun, Jiaqiang, Zhuo, L., Luo, J., Ren, J., Pong, W.-F., & Xin, H.L.. FeMo sub-nanoclusters/single atoms for neutral ammonia electrosynthesis. United States. https://doi.org/10.1016/j.nanoen.2020.105078
Liu, Wei, Han, L., Wang, H.-T., Zhao, X., Boscoboinik, Jorge A., Liu, X., Pao, C.-W., Sun, Jiaqiang, Zhuo, L., Luo, J., Ren, J., Pong, W.-F., and Xin, H.L.. Thu . "FeMo sub-nanoclusters/single atoms for neutral ammonia electrosynthesis". United States. https://doi.org/10.1016/j.nanoen.2020.105078. https://www.osti.gov/servlets/purl/1756175.
@article{osti_1756175,
title = {FeMo sub-nanoclusters/single atoms for neutral ammonia electrosynthesis},
author = {Liu, Wei and Han, L. and Wang, H.-T. and Zhao, X. and Boscoboinik, Jorge A. and Liu, X. and Pao, C.-W. and Sun, Jiaqiang and Zhuo, L. and Luo, J. and Ren, J. and Pong, W.-F. and Xin, H.L.},
abstractNote = {Electrochemical N2 reduction reaction (NRR) has long been regarded as a promising process to generate NH3 under ambient conditions. Therefore, developing cost-effective and high-performance non-noble-metal catalysts for NRR is highly desirable. Inspired by the biological nitrogenase structure, we here designed and synthesized a catalyst with iron-molybdenum sub-nanoclusters and single atoms on porous nitrogen-doped carbon (FeMo/NC). The catalyst features porous structure beneficial to active site exposure and accessibility to electrolyte as well as FeMo sub-nanoclusters and single atoms enabling to activate N2 molecular. In situ near-ambient pressure X-ray photoelectron spectroscopy tests reveal that during the process from vacuum to nitrogen saturation, N2 was close to, adsorbed on and interacted with Fe and Mo in FeMo/NC. The Fe and Mo through electron transfer play a key role in activating the N2 molecules. Therefore, when tested for NRR, FeMo/NC achieves the maximum Faradaic efficiency (FE) of 11.8 ± 0.8% at -0.25 V and NH3 yield rate of 26.5 ± 0.8 μg h-1 mgcat.-1 at -0.3 V in neutral electrolyte. Moreover, the catalyst exhibits ignorable variations in the FE and a slight decrease in current density for 100,000 s. This work develops a non-precious bimetallic electrocatalyst with synergetic effect capability for efficient NH3 production and provides a guideline for the design of efficient and robust catalysts with coexistence of sub-nanoclusters and single atoms.},
doi = {10.1016/j.nanoen.2020.105078},
journal = {Nano Energy},
number = ,
volume = 77,
place = {United States},
year = {2020},
month = {7}
}

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