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Title: Amino-functionalization on graphene oxide sheets using an atomic layer amidation technique

Abstract

Nitrogen functionalization on graphene sheets has solely been demonstrated with a stepwise amidation implementation within the literature. The present work proposes an atomic layer amidation (ALN) technique to linearly adjust the surface amidation level on the carbon nanostructures. The ALN cycling protocol proposed in this work consists of an ammonia pulse, nitrogen pulse, and pumping at 100 and 150 °C. Both surface amidation and oxidation levels were linearly controlled by the ALN cycle number. The ALN technique was demonstrated as a self-limiting process capable of step-by-step N-functionalizing graphene oxide (GO) sheets on the atomic scale. The amidation reaction rates were ca. 0.023 (100 °C) and 0.028 atomic percent (at%) cycle–1 (150 °C), and the apparent activation energy was determined to be 14.3 kJ mol–1 (= 0.148 eV atom–1) from the Arrhenius equation. The amidation mechanism for forming the “chemical N” and “lattice N” at an atomic level was also proposed. Linearly controlling the optical band-gap with the ALN cycle number was suggested as a robust method for tuning the oxidation as well as the amidation level on the GO sheets. Here, nitrogen functionalization can be utilized for engineering any desirable properties within the graphene sheets.

Authors:
ORCiD logo [1]; ORCiD logo [2];  [3];  [4]; ORCiD logo [5]; ORCiD logo [6];  [7]
  1. Xiamen Univ. of Technology (China)
  2. Yuan Ze Univ., Taoyuan (Taiwan); Univ. of Tennessee, Knoxville, TN (United States)
  3. Yuan Ze Univ., Taoyuan (Taiwan)
  4. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
  5. National Chiao Tung Univ., Hsinchu (Taiwan)
  6. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  7. Univ. of Tennessee, Knoxville, TN (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE)
OSTI Identifier:
1606699
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Materials Chemistry C
Additional Journal Information:
Journal Volume: 8; Journal Issue: 2; Journal ID: ISSN 2050-7526
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Gu, Siyong, Hsieh, Chien-Te, Mallick, Bikash Chandra, Ashraf Gandomi, Yasser, Chang, Jeng-Kuei, Li, Jianlin, and Liaw, Peter K. Amino-functionalization on graphene oxide sheets using an atomic layer amidation technique. United States: N. p., 2019. Web. https://doi.org/10.1039/c9tc05748j.
Gu, Siyong, Hsieh, Chien-Te, Mallick, Bikash Chandra, Ashraf Gandomi, Yasser, Chang, Jeng-Kuei, Li, Jianlin, & Liaw, Peter K. Amino-functionalization on graphene oxide sheets using an atomic layer amidation technique. United States. https://doi.org/10.1039/c9tc05748j
Gu, Siyong, Hsieh, Chien-Te, Mallick, Bikash Chandra, Ashraf Gandomi, Yasser, Chang, Jeng-Kuei, Li, Jianlin, and Liaw, Peter K. Tue . "Amino-functionalization on graphene oxide sheets using an atomic layer amidation technique". United States. https://doi.org/10.1039/c9tc05748j. https://www.osti.gov/servlets/purl/1606699.
@article{osti_1606699,
title = {Amino-functionalization on graphene oxide sheets using an atomic layer amidation technique},
author = {Gu, Siyong and Hsieh, Chien-Te and Mallick, Bikash Chandra and Ashraf Gandomi, Yasser and Chang, Jeng-Kuei and Li, Jianlin and Liaw, Peter K.},
abstractNote = {Nitrogen functionalization on graphene sheets has solely been demonstrated with a stepwise amidation implementation within the literature. The present work proposes an atomic layer amidation (ALN) technique to linearly adjust the surface amidation level on the carbon nanostructures. The ALN cycling protocol proposed in this work consists of an ammonia pulse, nitrogen pulse, and pumping at 100 and 150 °C. Both surface amidation and oxidation levels were linearly controlled by the ALN cycle number. The ALN technique was demonstrated as a self-limiting process capable of step-by-step N-functionalizing graphene oxide (GO) sheets on the atomic scale. The amidation reaction rates were ca. 0.023 (100 °C) and 0.028 atomic percent (at%) cycle–1 (150 °C), and the apparent activation energy was determined to be 14.3 kJ mol–1 (= 0.148 eV atom–1) from the Arrhenius equation. The amidation mechanism for forming the “chemical N” and “lattice N” at an atomic level was also proposed. Linearly controlling the optical band-gap with the ALN cycle number was suggested as a robust method for tuning the oxidation as well as the amidation level on the GO sheets. Here, nitrogen functionalization can be utilized for engineering any desirable properties within the graphene sheets.},
doi = {10.1039/c9tc05748j},
journal = {Journal of Materials Chemistry C},
number = 2,
volume = 8,
place = {United States},
year = {2019},
month = {11}
}

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