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Title: Single-atom catalysts templated by metal–organic frameworks for electrochemical nitrogen reduction

Abstract

The electrocatalytic nitrogen reduction reaction (NRR) offers much prospect for substituting the energy-consuming Haber–Bosch process. Nevertheless, its sluggish reaction kinetics and the competing hydrogen evolution reaction always result in limited ammonia yield and low faradaic efficiency (FE). Here, an Fe-decorated porphyrinic metal–organic framework (MOF) is employed as a precursor to construct single-atom Fe implanted nitrogen-doped carbon catalysts (Fe 1-N-C) through a mixed ligand strategy. Benefiting from the highly dispersed single-atom Fe sites, hierarchically porous structure and good conductivity, Fe 1-N-C shows a FE of 4.51% and an ammonia yield rate of 1.56 × 10 -11 mol cm -2 s -1 at -0.05 V versus the reversible hydrogen electrode, superior to those of Co 1-N-C and Ni 1-N-C. Theoretical calculations show that Fe 1-N-C shows the lowest energy barrier of the rate-determining step during the NRR process, consistent with its highest activity obtained in experiments. This work reveals the unique potential of single-atom catalysts for the electrochemical NRR and provides in-depth insights into the catalytic mechanism of the NRR.

Authors:
 [1];  [1]; ORCiD logo [2];  [3]; ORCiD logo [4]
  1. Univ. of Science and Technology of China, Hefei (China)
  2. Univ. of Science and Technology of China, Hefei (China); North China Electric Power Univ., Baoding (China)
  3. SLAC National Accelerator Lab., Menlo Park, CA (United States)
  4. Univ. of Science and Technology of China, Hefei (China); Chinese Academy of Sciences (CAS), Fuzhou (China)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1583128
Grant/Contract Number:  
AC02-76SF00515; 21725101, 21871244, 21521001; 2019TQ0298; WK2060030029
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Materials Chemistry. A
Additional Journal Information:
Journal Volume: 7; Journal Issue: 46; Journal ID: ISSN 2050-7488
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Zhang, Rui, Jiao, Long, Yang, Weijie, Wan, Gang, and Jiang, Hai-Long. Single-atom catalysts templated by metal–organic frameworks for electrochemical nitrogen reduction. United States: N. p., 2019. Web. doi:10.1039/C9TA10206J.
Zhang, Rui, Jiao, Long, Yang, Weijie, Wan, Gang, & Jiang, Hai-Long. Single-atom catalysts templated by metal–organic frameworks for electrochemical nitrogen reduction. United States. doi:10.1039/C9TA10206J.
Zhang, Rui, Jiao, Long, Yang, Weijie, Wan, Gang, and Jiang, Hai-Long. Thu . "Single-atom catalysts templated by metal–organic frameworks for electrochemical nitrogen reduction". United States. doi:10.1039/C9TA10206J.
@article{osti_1583128,
title = {Single-atom catalysts templated by metal–organic frameworks for electrochemical nitrogen reduction},
author = {Zhang, Rui and Jiao, Long and Yang, Weijie and Wan, Gang and Jiang, Hai-Long},
abstractNote = {The electrocatalytic nitrogen reduction reaction (NRR) offers much prospect for substituting the energy-consuming Haber–Bosch process. Nevertheless, its sluggish reaction kinetics and the competing hydrogen evolution reaction always result in limited ammonia yield and low faradaic efficiency (FE). Here, an Fe-decorated porphyrinic metal–organic framework (MOF) is employed as a precursor to construct single-atom Fe implanted nitrogen-doped carbon catalysts (Fe1-N-C) through a mixed ligand strategy. Benefiting from the highly dispersed single-atom Fe sites, hierarchically porous structure and good conductivity, Fe1-N-C shows a FE of 4.51% and an ammonia yield rate of 1.56 × 10-11 mol cm-2 s-1 at -0.05 V versus the reversible hydrogen electrode, superior to those of Co1-N-C and Ni1-N-C. Theoretical calculations show that Fe1-N-C shows the lowest energy barrier of the rate-determining step during the NRR process, consistent with its highest activity obtained in experiments. This work reveals the unique potential of single-atom catalysts for the electrochemical NRR and provides in-depth insights into the catalytic mechanism of the NRR.},
doi = {10.1039/C9TA10206J},
journal = {Journal of Materials Chemistry. A},
number = 46,
volume = 7,
place = {United States},
year = {2019},
month = {10}
}

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