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Title: One-Pot Pyrolysis Method to Fabricate Carbon Nanotube Supported Ni Single-Atom Catalysts with Ultrahigh Loading

Abstract

The practical application of single atom catalysts (SACs) is constrained by the low achievable loading of single metal atoms. In this work, nickel SACs stabilized on a nitrogen-doped carbon nanotube structure (NiSA-N-CNT) with ultrahigh Ni atomic loading up to 20.3 wt % have been successfully synthesized using a new one-pot pyrolysis method employing Ni acetylacetonate (Ni(acac)2) and dicyandiamide (DCD) as precursors. The yield and formation of NiSA-N-CNT depends strongly on the Ni(acac)2/DCD ratio and annealing temperature. Pyrolysis at 350 and 650 °C led to the formation of Ni single atom dispersed melem and graphitic carbon nitride (Ni-melem and Ni-g-C3N4). Transition from a stacked and layered Ni-g-C3N4 structure to a bamboo-shaped tubular NiSA-N-CNT structure most likely occurs via a solid-to-solid curling or rolling-up mechanism, thermally activated at temperatures of 700–900 °C. Extended X-ray absorption fine structure (EXAFS) experiments and simulations show that Ni single atoms are stabilized in the N-CNT structure through nitrogen coordination, forming a structure with four nearest N coordination shell surrounded by two carbon shells, Ni–N4. The NiSA-N-CNT catalysts show an excellent activity and selectivity for the electrochemical reduction of CO2, achieving a turnover frequency (TOF) of 11.7 s–1 at -0.55 V (vs RHE), but a low activitymore » for the O2 reduction and O2 evolution reactions, as compared to Ni nanoparticles supported on N-CNTs.« less

Authors:
 [1];  [1];  [1];  [2];  [3];  [4];  [4];  [5]; ORCiD logo [6]; ORCiD logo [7]; ORCiD logo [5]; ORCiD logo [1]
  1. Curtin Univ., Perth, WA (Australia)
  2. Australian Synchrotron, Clayton, ViIC (Australia)
  3. Univ. of Western Australia, Perth, WA (Australia)
  4. Chinese Academy of Sciences, Shenyang, LN (China)
  5. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  6. Univ. of Sunshine Coast, Maroochydore DC, QLD (Australia); The Univ. of Queensland, Brisbane (Australia)
  7. Univ. of Surrey, Guildford (United Kingdom)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science (CNMS); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
Sponsoring Org.:
Australian Research Council (ARC); National Science Foundation (NSF); National Natural Science Foundation of China (NNSFC); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Scientific User Facilities Division
OSTI Identifier:
1607268
Grant/Contract Number:  
AC05-00OR22725; LE120100026; AC02-05CH11231; ACI-1053575
Resource Type:
Accepted Manuscript
Journal Name:
ACS Applied Energy Materials
Additional Journal Information:
Journal Volume: 1; Journal Issue: 10; Journal ID: ISSN 2574-0962
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Ni single-atom catalysts; bamboo-like carbon nanotubes; one-pot pyrolysis; synthesis rolling-up mechanism; carbon dioxide reduction

Citation Formats

Zhao, Shiyong, Cheng, Yi, Veder, Jean-Pierre, Johannessen, Bernt, Saunders, Martin, Zhang, Lianji, Liu, Chang, Chisholm, Matthew F., De Marco, Roland, Liu, Jian, Yang, Shi-Ze, and Jiang, San Ping. One-Pot Pyrolysis Method to Fabricate Carbon Nanotube Supported Ni Single-Atom Catalysts with Ultrahigh Loading. United States: N. p., 2018. Web. doi:10.1021/acsaem.8b00903.
Zhao, Shiyong, Cheng, Yi, Veder, Jean-Pierre, Johannessen, Bernt, Saunders, Martin, Zhang, Lianji, Liu, Chang, Chisholm, Matthew F., De Marco, Roland, Liu, Jian, Yang, Shi-Ze, & Jiang, San Ping. One-Pot Pyrolysis Method to Fabricate Carbon Nanotube Supported Ni Single-Atom Catalysts with Ultrahigh Loading. United States. doi:10.1021/acsaem.8b00903.
Zhao, Shiyong, Cheng, Yi, Veder, Jean-Pierre, Johannessen, Bernt, Saunders, Martin, Zhang, Lianji, Liu, Chang, Chisholm, Matthew F., De Marco, Roland, Liu, Jian, Yang, Shi-Ze, and Jiang, San Ping. Mon . "One-Pot Pyrolysis Method to Fabricate Carbon Nanotube Supported Ni Single-Atom Catalysts with Ultrahigh Loading". United States. doi:10.1021/acsaem.8b00903. https://www.osti.gov/servlets/purl/1607268.
@article{osti_1607268,
title = {One-Pot Pyrolysis Method to Fabricate Carbon Nanotube Supported Ni Single-Atom Catalysts with Ultrahigh Loading},
author = {Zhao, Shiyong and Cheng, Yi and Veder, Jean-Pierre and Johannessen, Bernt and Saunders, Martin and Zhang, Lianji and Liu, Chang and Chisholm, Matthew F. and De Marco, Roland and Liu, Jian and Yang, Shi-Ze and Jiang, San Ping},
abstractNote = {The practical application of single atom catalysts (SACs) is constrained by the low achievable loading of single metal atoms. In this work, nickel SACs stabilized on a nitrogen-doped carbon nanotube structure (NiSA-N-CNT) with ultrahigh Ni atomic loading up to 20.3 wt % have been successfully synthesized using a new one-pot pyrolysis method employing Ni acetylacetonate (Ni(acac)2) and dicyandiamide (DCD) as precursors. The yield and formation of NiSA-N-CNT depends strongly on the Ni(acac)2/DCD ratio and annealing temperature. Pyrolysis at 350 and 650 °C led to the formation of Ni single atom dispersed melem and graphitic carbon nitride (Ni-melem and Ni-g-C3N4). Transition from a stacked and layered Ni-g-C3N4 structure to a bamboo-shaped tubular NiSA-N-CNT structure most likely occurs via a solid-to-solid curling or rolling-up mechanism, thermally activated at temperatures of 700–900 °C. Extended X-ray absorption fine structure (EXAFS) experiments and simulations show that Ni single atoms are stabilized in the N-CNT structure through nitrogen coordination, forming a structure with four nearest N coordination shell surrounded by two carbon shells, Ni–N4. The NiSA-N-CNT catalysts show an excellent activity and selectivity for the electrochemical reduction of CO2, achieving a turnover frequency (TOF) of 11.7 s–1 at -0.55 V (vs RHE), but a low activity for the O2 reduction and O2 evolution reactions, as compared to Ni nanoparticles supported on N-CNTs.},
doi = {10.1021/acsaem.8b00903},
journal = {ACS Applied Energy Materials},
number = 10,
volume = 1,
place = {United States},
year = {2018},
month = {9}
}

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