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:
-
- Xiamen Univ. of Technology (China)
- Yuan Ze Univ., Taoyuan (Taiwan); Univ. of Tennessee, Knoxville, TN (United States)
- Yuan Ze Univ., Taoyuan (Taiwan)
- Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
- National Chiao Tung Univ., Hsinchu (Taiwan)
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- 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. doi: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 = {Tue Nov 26 00:00:00 EST 2019},
month = {Tue Nov 26 00:00:00 EST 2019}
}
Web of Science
Works referenced in this record:
Electrochemical Capacitors Based on Graphene Oxide Sheets Using Different Aqueous Electrolytes
journal, June 2011
- Hsieh, Chien-Te; Hsu, Shu-Min; Lin, Jia-Yi
- The Journal of Physical Chemistry C, Vol. 115, Issue 25
Facile Synthetic Method for Pristine Graphene Quantum Dots and Graphene Oxide Quantum Dots: Origin of Blue and Green Luminescence
journal, May 2013
- Liu, Fei; Jang, Min-Ho; Ha, Hyun Dong
- Advanced Materials, Vol. 25, Issue 27
A green heterogeneous synthesis of N-doped carbon dots and their photoluminescence applications in solid and aqueous states
journal, January 2014
- Xu, Minghan; He, Guili; Li, Zhaohui
- Nanoscale, Vol. 6, Issue 17
Thermal conductivity from hierarchical heat sinks using carbon nanotubes and graphene nanosheets
journal, January 2015
- Hsieh, Chien-Te; Lee, Cheng-En; Chen, Yu-Fu
- Nanoscale, Vol. 7, Issue 44
Blue Photoluminescence from Chemically Derived Graphene Oxide
journal, January 2010
- Eda, Goki; Lin, Yun-Yue; Mattevi, Cecilia
- Advanced Materials, Vol. 22, Issue 4, p. 505-509
Exploring Adsorption and Reactivity of NH 3 on Reduced Graphene Oxide
journal, May 2013
- Mattson, Eric C.; Pande, Kanupriya; Unger, Miriam
- The Journal of Physical Chemistry C, Vol. 117, Issue 20
Formation Mechanism of Carbogenic Nanoparticles with Dual Photoluminescence Emission
journal, December 2011
- Krysmann, Marta J.; Kelarakis, Antonios; Dallas, Panagiotis
- Journal of the American Chemical Society, Vol. 134, Issue 2
Chemical reactivity of graphene oxide towards amines elucidated by solid-state NMR
journal, January 2016
- Vacchi, Isabella A.; Spinato, Cinzia; Raya, Jésus
- Nanoscale, Vol. 8, Issue 28
Atomic layer deposition for nanomaterial synthesis and functionalization in energy technology
journal, January 2017
- Meng, Xiangbo; Wang, Xinwei; Geng, Dongsheng
- Materials Horizons, Vol. 4, Issue 2
Visualizing Individual Nitrogen Dopants in Monolayer Graphene
journal, August 2011
- Zhao, L.; He, R.; Rim, K. T.
- Science, Vol. 333, Issue 6045
Thermal properties of graphene and nanostructured carbon materials
journal, August 2011
- Balandin, Alexander A.
- Nature Materials, Vol. 10, Issue 8, p. 569-581
Graphene: Status and Prospects
journal, June 2009
- Geim, A. K.
- Science, Vol. 324, Issue 5934, p. 1530-1534
Electrochemical Properties of Graphene Paper Electrodes Used in Lithium Batteries
journal, July 2009
- Wang, Caiyun; Li, Dan; Too, Chee O.
- Chemistry of Materials, Vol. 21, Issue 13
Efficient Process for Direct Atomic Layer Deposition of Metallic Cu Thin Films Based on an Organic Reductant
journal, January 2017
- Tripathi, Tripurari S.; Karppinen, Maarit
- Chemistry of Materials, Vol. 29, Issue 3
Chemistry and physics of a single atomic layer: strategies and challenges for functionalization of graphene and graphene-based materials
journal, January 2012
- Yan, Liang; Zheng, Yue Bing; Zhao, Feng
- Chem. Soc. Rev., Vol. 41, Issue 1
Functionalization of carbon nanotubes with amines and enzymes
journal, January 2005
- Wang, Yubing; Iqbal, Zafar; Malhotra, Sanjay V.
- Chemical Physics Letters, Vol. 402, Issue 1-3
Bandgap opening in graphene induced by patterned hydrogen adsorption
journal, March 2010
- Balog, Richard; Jørgensen, Bjarke; Nilsson, Louis
- Nature Materials, Vol. 9, Issue 4
3D graphene preparation via covalent amide functionalization for efficient metal-free electrocatalysis in oxygen reduction
journal, February 2017
- Ahmed, Mohammad Shamsuddin; Kim, Young-Bae
- Scientific Reports, Vol. 7, Issue 1
Atomic layer oxidation on graphene sheets for tuning their oxidation levels, electrical conductivities, and band gaps
journal, January 2018
- Gu, Siyong; Hsieh, Chien-Te; Lin, Tzu-Wei
- Nanoscale, Vol. 10, Issue 33
Atomic layer deposition for perovskite solar cells: research status, opportunities and challenges
journal, January 2017
- Zardetto, V.; Williams, B. L.; Perrotta, A.
- Sustainable Energy & Fuels, Vol. 1, Issue 1
Facile synthesis of high-quality graphene nanoribbons
journal, April 2010
- Jiao, Liying; Wang, Xinran; Diankov, Georgi
- Nature Nanotechnology, Vol. 5, Issue 5
Graphene oxide as a promising photocatalyst for CO 2 to methanol conversion
journal, January 2013
- Hsu, Hsin-Cheng; Shown, Indrajit; Wei, Hsieh-Yu
- Nanoscale, Vol. 5, Issue 1
High dispersion of 1-nm SnO2 particles between graphene nanosheets constructed using supercritical CO2 fluid for sodium-ion battery anodes
journal, October 2016
- Patra, Jagabandhu; Chen, Hung-Ching; Yang, Cheng-Hsien
- Nano Energy, Vol. 28
Synthesis, characterization and cytotoxicity of surface amino-functionalized water-dispersible multi-walled carbon nanotubes
journal, June 2009
- Vuković, Goran; Marinković, Aleksandar; Obradović, Maja
- Applied Surface Science, Vol. 255, Issue 18
Large-Scale Growth and Characterizations of Nitrogen-Doped Monolayer Graphene Sheets
journal, April 2011
- Jin, Zhong; Yao, Jun; Kittrell, Carter
- ACS Nano, Vol. 5, Issue 5
Amide Functionalization of Graphene and Carbon Nanotubes: Coverage- and Pattern-Dependent Electronic and Magnetic Properties
journal, June 2012
- Lu, Peng; Zhou, Rulong; Guo, Wanlin
- The Journal of Physical Chemistry C, Vol. 116, Issue 25
Adsorption and Dissociation of Ammonia on Graphene Oxides: A First-Principles Study
journal, April 2012
- Tang, Shaobin; Cao, Zexing
- The Journal of Physical Chemistry C, Vol. 116, Issue 15
Selective Nitrogen Functionalization of Graphene by Bucherer-Type Reaction
journal, March 2015
- Chua, Chun Kiang; Sofer, Zdeněk; Luxa, Jan
- Chemistry - A European Journal, Vol. 21, Issue 22
Prediction of very large values of magnetoresistance in a graphene nanoribbon device
journal, June 2008
- Kim, Woo Youn; Kim, Kwang S.
- Nature Nanotechnology, Vol. 3, Issue 7
Graphitic carbon nitride materials: variation of structure and morphology and their use as metal-free catalysts
journal, January 2008
- Thomas, Arne; Fischer, Anna; Goettmann, Frederic
- Journal of Materials Chemistry, Vol. 18, Issue 41
Electrically Conductive “Alkylated” Graphene Paper via Chemical Reduction of Amine-Functionalized Graphene Oxide Paper
journal, February 2010
- Compton, Owen C.; Dikin, Dmitriy A.; Putz, Karl W.
- Advanced Materials, Vol. 22, Issue 8
Regioselectivity control of graphene functionalization by ripples
journal, January 2011
- Gao, Xingfa; Wang, Ying; Liu, Xin
- Physical Chemistry Chemical Physics, Vol. 13, Issue 43
Enabling high rate charge and discharge capability, low internal resistance, and excellent cycleability for Li-ion batteries utilizing graphene additives
journal, May 2018
- Tsai, Hsiu-Ling; Hsieh, Chien-Te; Li, Jianlin
- Electrochimica Acta, Vol. 273
Electric Field Effect in Atomically Thin Carbon Films
journal, October 2004
- Novoselov, K. S.
- Science, Vol. 306, Issue 5696, p. 666-669
Covalent bulk functionalization of graphene
journal, March 2011
- Englert, Jan M.; Dotzer, Christoph; Yang, Guang
- Nature Chemistry, Vol. 3, Issue 4
Graphene-supported Pt and PtPd nanorods with enhanced electrocatalytic performance for the oxygen reduction reaction
journal, January 2014
- Chen, Hong-Shuo; Liang, Yu-Ting; Chen, Tsan-Yao
- Chem. Commun., Vol. 50, Issue 76
In situnitrogen-doped graphene grown from polydimethylsiloxane by plasma enhanced chemical vapor deposition
journal, January 2013
- Wang, Chundong; Zhou, Yungang; He, Lifang
- Nanoscale, Vol. 5, Issue 2
Synthesis of N-Doped Graphene by Chemical Vapor Deposition and Its Electrical Properties
journal, May 2009
- Wei, Dacheng; Liu, Yunqi; Wang, Yu
- Nano Letters, Vol. 9, Issue 5
Mechanisms of Oxygen Reduction Reaction on Nitrogen-Doped Graphene for Fuel Cells
journal, May 2011
- Zhang, Lipeng; Xia, Zhenhai
- The Journal of Physical Chemistry C, Vol. 115, Issue 22
The role of surface chemistry in catalysis with carbons
journal, February 2010
- Figueiredo, José Luís; Pereira, Manuel Fernando R.
- Catalysis Today, Vol. 150, Issue 1-2
Hierarchically aminated graphene honeycombs for electrochemical capacitive energy storage
journal, January 2012
- Chen, Cheng-Meng; Zhang, Qiang; Zhao, Xiao-Chen
- Journal of Materials Chemistry, Vol. 22, Issue 28
Catalytic Reduction of NO with NH 3 over Carbons Impregnated with Cu and Fe
journal, June 2001
- Teng, Hsisheng; Hsu, Li-Yeh; Lai, Yu-Chung
- Environmental Science & Technology, Vol. 35, Issue 11
Workfunction-Tunable, N-Doped Reduced Graphene Transparent Electrodes for High-Performance Polymer Light-Emitting Diodes
journal, December 2011
- Hwang, Jin Ok; Park, Ji Sun; Choi, Dong Sung
- ACS Nano, Vol. 6, Issue 1
Etching and narrowing of graphene from the edges
journal, June 2010
- Wang, Xinran; Dai, Hongjie
- Nature Chemistry, Vol. 2, Issue 8, p. 661-665
Tuning oxidation level, electrical conductance and band gap structure on graphene sheets by a cyclic atomic layer reduction technique
journal, October 2018
- Gu, Si-Yong; Hsieh, Chien-Te; Lin, Tzu-Wei
- Carbon, Vol. 137
Π-Bond maximization of graphene in hydrogen addition reactions
journal, January 2012
- Gao, Xingfa; Zhao, Yuliang; Liu, Bo
- Nanoscale, Vol. 4, Issue 4
Graphene: The New Two-Dimensional Nanomaterial
journal, October 2009
- Rao, C. N. R.; Sood, A. K.; Subrahmanyam, K. S.
- Angewandte Chemie International Edition, Vol. 48, Issue 42, p. 7752-7777
Versatile Graphene Quantum Dots with Tunable Nitrogen Doping
journal, December 2013
- Dai, Yunqian; Long, Huan; Wang, Xiaotian
- Particle & Particle Systems Characterization, Vol. 31, Issue 5
The rise of graphene
journal, March 2007
- Geim, A. K.; Novoselov, K. S.
- Nature Materials, Vol. 6, Issue 3, p. 183-191
Thermal transport in stereo carbon framework using graphite nanospheres and graphene nanosheets
journal, September 2016
- Hsieh, Chien-Te; Chen, Yu-Fu; Lee, Cheng-En
- Carbon, Vol. 106
Atomic Layer Deposition of Platinum Nanocatalysts onto Three-Dimensional Carbon Nanotube/Graphene Hybrid
journal, December 2012
- Hsieh, Chien-Te; Liu, Yung-Ying; Tzou, Dong-Ying
- The Journal of Physical Chemistry C, Vol. 116, Issue 51
Electronic spin transport and spin precession in single graphene layers at room temperature
journal, July 2007
- Tombros, Nikolaos; Jozsa, Csaba; Popinciuc, Mihaita
- Nature, Vol. 448, Issue 7153, p. 571-574
Controlled, Stepwise Reduction and Band Gap Manipulation of Graphene Oxide
journal, March 2012
- Mathkar, Akshay; Tozier, Dylan; Cox, Paris
- The Journal of Physical Chemistry Letters, Vol. 3, Issue 8
Synthesis, characterization, and electrochemical capacitance of amino-functionalized carbon nanotube/carbon paper electrodes
journal, December 2010
- Hsieh, Chien-Te; Teng, Hsisheng; Chen, Wei-Yu
- Carbon, Vol. 48, Issue 15
Structural evolution during the reduction of chemically derived graphene oxide
journal, June 2010
- Bagri, Akbar; Mattevi, Cecilia; Acik, Muge
- Nature Chemistry, Vol. 2, Issue 7, p. 581-587
The rise of graphene
book, August 2009
- Rodgers, Peter; Geim, A. K.; Novoselov, K. S.
- Nanoscience and Technology: A Collection of Reviews from Nature Journals, p. 11-19
Selective Nitrogen Functionalization of Graphene by Bucherer-Type Reaction
journal, March 2015
- Chua, Chun Kiang; Sofer, Zdeněk; Luxa, Jan
- Chemistry - A European Journal, Vol. 21, Issue 22
Electronic spin transport and spin precession in single graphene layers at room temperature
text, January 2007
- Tombros, Nikolaos; Jozsa, Csaba; Popinciuc, Mihaita
- arXiv
Blue photoluminescence from chemically derived graphene oxide
preprint, January 2009
- Eda, Goki; Lin, Yun-Yue; Mattevi, Cecilia
- arXiv
Facile Synthesis of High Quality Graphene Nanoribbons
text, January 2010
- Jiao, Liying; Wang, Xinran; Diankov, Georgi
- arXiv
Etching and Narrowing of Graphene from the Edges
text, January 2010
- Wang, Xinran; Dai, Hongjie
- arXiv
Visualizing Individual Nitrogen Dopants in Monolayer Graphene
text, January 2011
- Zhao, Liuyan; He, Rui; Rim, Kwang Taeg
- arXiv
Electric Field Effect in Atomically Thin Carbon Films
text, January 2004
- Novoselov, K. S.; Geim, A. K.; Morozov, S. V.
- arXiv