Carbon-assisted catalyst pretreatment enables straightforward synthesis of high-density carbon nanotube forests

Nicholas T. Dee; Jinjing Li; Alvin Orbaek White; Christine Jacob; Wenbo Shi; Piran R. Kidambi; Kehang Cui; Dmitri N. Zakharov; Nina Z. Janković; Mostafa Bedewy; Cécile A.C. Chazot; Jennifer Carpena-Núñez; Benji Maruyama; Eric A. Stach; Desiree L. Plata; A. John Hart

doi:10.1016/j.carbon.2019.06.083

Carbon-assisted catalyst pretreatment enables straightforward synthesis of high-density carbon nanotube forests

Nicholas T. Dee, Jinjing Li, Alvin Orbaek White, Christine Jacob, Wenbo Shi, Piran R. Kidambi, Kehang Cui, Dmitri N. Zakharov, Nina Z. Janković, Mostafa Bedewy, Cécile A.C. Chazot, Jennifer Carpena-Núñez, Benji Maruyama, Eric A. Stach, Desiree L. Plata, A. John Hart^*

^*Corresponding author for this work

Materials Science and Engineering

Research output: Contribution to journal › Article › peer-review

34 Scopus citations

Abstract

Despite extensive academic and commercial development, a comprehensive understanding of the principles necessary for high-yield production of carbon nanotubes (CNTs) is lacking, whether in oriented films, bulk powders, or other forms. In chemical vapor deposition growth of CNT films on substrates, trace contaminants of carbon, such as deposits on the reactor tube walls, are known to cause inconsistency in key production metrics, including CNT density and alignment. In this study, we show that trace exposure of the catalyst to carbon during initial heating of the catalyst film is a critical determinant of CNT yield, and this carbon exposure accelerates catalyst nanoparticle formation via film dewetting and increases the probability of CNT nucleation and the resultant density of the CNT population. By controlled exposure of the catalyst to a trace amount of carbon, we show up to a 4-fold increase in bulk mass density for a given forest height, an 8-fold increase in local CNT number density, and a 2-fold increase in the growth lifetime, relative to a reference condition. We discuss potential mechanisms to explain the role of carbon exposure on the probability of CNT nucleation from nanoparticle catalysts, supported by microscopy and gas analysis.

Original language	English (US)
Pages (from-to)	196-205
Number of pages	10
Journal	Carbon
Volume	153
DOIs	https://doi.org/10.1016/j.carbon.2019.06.083
State	Published - Nov 2019

Funding

We thank Rahul Rao for insightful discussions, and Byeongdu Lee for assistance in the SAXS analysis. Financial support was provided by the MIT-Skoltech Next Generation Program (for N.T.D.); the Office of Naval Research Young Investigator Program , grant number N000141210815 (for J.L., A.O.W.); the Department of Energy, Office of Science under Grant No. DE-SC0010795 (for P.R.K.); the NSF Graduate Research Fellowship Program (for N.Z.J.); the Air Force Office of Scientific Research, AFOSR under LRIR# 16RXCOR322 ; and by the National Aeronautics and Space Administration (NASA) Space Technology Research Institute (STRI) for Ultra-Strong Composites by Computational Design (US-COMP) , grant number NNX17AJ32GNASA-USCOMP (for N.T.D and A.J.H). SEM and TEM imaging were performed at Harvard University's Center for Nanoscale Systems (CNS), a member of the National Nanotechnology Infrastructure Network (NNIN), which is supported by the National Science Foundation under NSF award no. ECS-0335765 . XPS and AFM measurements were performed in the Michigan Center for Materials Characterization at the University of Michigan. Raman characterization and thermogravimetric analysis were performed at the Institute for Soldier Nanotechnologies (ISN) at MIT. Catalyst deposition and substrate dicing was performed at the Microsystems Technology Laboratories (MTL) at MIT. SAXS characterization was performed at the 12-ID-B beamline at the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357 . ETEM studies were performed at the Center for Functional Nanomaterials, Brookhaven National Laboratory, which is supported by the U.S. Department of Energy, Office of Basic Energy Sciences , under Contract No. DE-SC0012704 . We thank Rahul Rao for insightful discussions, and Byeongdu Lee for assistance in the SAXS analysis. Financial support was provided by the MIT-Skoltech Next Generation Program (for N.T.D.); the Office of Naval Research Young Investigator Program, grant number N000141210815 (for J.L. A.O.W.); the Department of Energy, Office of Science under Grant No. DE-SC0010795 (for P.R.K.); the NSF Graduate Research Fellowship Program (for N.Z.J.); the Air Force Office of Scientific Research, AFOSR under LRIR#16RXCOR322; and by the National Aeronautics and Space Administration (NASA) Space Technology Research Institute (STRI) for Ultra-Strong Composites by Computational Design (US-COMP), grant number NNX17AJ32GNASA-USCOMP (for N.T.D and A.J.H). SEM and TEM imaging were performed at Harvard University's Center for Nanoscale Systems (CNS), a member of the National Nanotechnology Infrastructure Network (NNIN), which is supported by the National Science Foundation under NSF award no. ECS-0335765. XPS and AFM measurements were performed in the Michigan Center for Materials Characterization at the University of Michigan. Raman characterization and thermogravimetric analysis were performed at the Institute for Soldier Nanotechnologies (ISN) at MIT. Catalyst deposition and substrate dicing was performed at the Microsystems Technology Laboratories (MTL) at MIT. SAXS characterization was performed at the 12-ID-B beamline at the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. ETEM studies were performed at the Center for Functional Nanomaterials, Brookhaven National Laboratory, which is supported by the U.S. Department of Energy, Office of Basic Energy Sciences, under Contract No. DE-SC0012704.

ASJC Scopus subject areas

General Chemistry
General Materials Science

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10.1016/j.carbon.2019.06.083

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Dee, N. T., Li, J., Orbaek White, A., Jacob, C., Shi, W., Kidambi, P. R., Cui, K., Zakharov, D. N., Janković, N. Z., Bedewy, M., Chazot, C. A. C., Carpena-Núñez, J., Maruyama, B., Stach, E. A., Plata, D. L., & Hart, A. J. (2019). Carbon-assisted catalyst pretreatment enables straightforward synthesis of high-density carbon nanotube forests. Carbon, 153, 196-205. https://doi.org/10.1016/j.carbon.2019.06.083

@article{37c19ec7c181463c9236722408f3d0ec,

title = "Carbon-assisted catalyst pretreatment enables straightforward synthesis of high-density carbon nanotube forests",

abstract = "Despite extensive academic and commercial development, a comprehensive understanding of the principles necessary for high-yield production of carbon nanotubes (CNTs) is lacking, whether in oriented films, bulk powders, or other forms. In chemical vapor deposition growth of CNT films on substrates, trace contaminants of carbon, such as deposits on the reactor tube walls, are known to cause inconsistency in key production metrics, including CNT density and alignment. In this study, we show that trace exposure of the catalyst to carbon during initial heating of the catalyst film is a critical determinant of CNT yield, and this carbon exposure accelerates catalyst nanoparticle formation via film dewetting and increases the probability of CNT nucleation and the resultant density of the CNT population. By controlled exposure of the catalyst to a trace amount of carbon, we show up to a 4-fold increase in bulk mass density for a given forest height, an 8-fold increase in local CNT number density, and a 2-fold increase in the growth lifetime, relative to a reference condition. We discuss potential mechanisms to explain the role of carbon exposure on the probability of CNT nucleation from nanoparticle catalysts, supported by microscopy and gas analysis.",

author = "Dee, {Nicholas T.} and Jinjing Li and {Orbaek White}, Alvin and Christine Jacob and Wenbo Shi and Kidambi, {Piran R.} and Kehang Cui and Zakharov, {Dmitri N.} and Jankovi{\'c}, {Nina Z.} and Mostafa Bedewy and Chazot, {C{\'e}cile A.C.} and Jennifer Carpena-N{\'u}{\~n}ez and Benji Maruyama and Stach, {Eric A.} and Plata, {Desiree L.} and Hart, {A. John}",

note = "Funding Information: We thank Rahul Rao for insightful discussions, and Byeongdu Lee for assistance in the SAXS analysis. Financial support was provided by the MIT-Skoltech Next Generation Program (for N.T.D.); the Office of Naval Research Young Investigator Program , grant number N000141210815 (for J.L., A.O.W.); the Department of Energy, Office of Science under Grant No. DE-SC0010795 (for P.R.K.); the NSF Graduate Research Fellowship Program (for N.Z.J.); the Air Force Office of Scientific Research, AFOSR under LRIR# 16RXCOR322 ; and by the National Aeronautics and Space Administration (NASA) Space Technology Research Institute (STRI) for Ultra-Strong Composites by Computational Design (US-COMP) , grant number NNX17AJ32GNASA-USCOMP (for N.T.D and A.J.H). SEM and TEM imaging were performed at Harvard University's Center for Nanoscale Systems (CNS), a member of the National Nanotechnology Infrastructure Network (NNIN), which is supported by the National Science Foundation under NSF award no. ECS-0335765 . XPS and AFM measurements were performed in the Michigan Center for Materials Characterization at the University of Michigan. Raman characterization and thermogravimetric analysis were performed at the Institute for Soldier Nanotechnologies (ISN) at MIT. Catalyst deposition and substrate dicing was performed at the Microsystems Technology Laboratories (MTL) at MIT. SAXS characterization was performed at the 12-ID-B beamline at the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357 . ETEM studies were performed at the Center for Functional Nanomaterials, Brookhaven National Laboratory, which is supported by the U.S. Department of Energy, Office of Basic Energy Sciences , under Contract No. DE-SC0012704 . Funding Information: We thank Rahul Rao for insightful discussions, and Byeongdu Lee for assistance in the SAXS analysis. Financial support was provided by the MIT-Skoltech Next Generation Program (for N.T.D.); the Office of Naval Research Young Investigator Program, grant number N000141210815 (for J.L. A.O.W.); the Department of Energy, Office of Science under Grant No. DE-SC0010795 (for P.R.K.); the NSF Graduate Research Fellowship Program (for N.Z.J.); the Air Force Office of Scientific Research, AFOSR under LRIR#16RXCOR322; and by the National Aeronautics and Space Administration (NASA) Space Technology Research Institute (STRI) for Ultra-Strong Composites by Computational Design (US-COMP), grant number NNX17AJ32GNASA-USCOMP (for N.T.D and A.J.H). SEM and TEM imaging were performed at Harvard University's Center for Nanoscale Systems (CNS), a member of the National Nanotechnology Infrastructure Network (NNIN), which is supported by the National Science Foundation under NSF award no. ECS-0335765. XPS and AFM measurements were performed in the Michigan Center for Materials Characterization at the University of Michigan. Raman characterization and thermogravimetric analysis were performed at the Institute for Soldier Nanotechnologies (ISN) at MIT. Catalyst deposition and substrate dicing was performed at the Microsystems Technology Laboratories (MTL) at MIT. SAXS characterization was performed at the 12-ID-B beamline at the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. ETEM studies were performed at the Center for Functional Nanomaterials, Brookhaven National Laboratory, which is supported by the U.S. Department of Energy, Office of Basic Energy Sciences, under Contract No. DE-SC0012704. Publisher Copyright: {\textcopyright} 2019",

year = "2019",

month = nov,

doi = "10.1016/j.carbon.2019.06.083",

language = "English (US)",

volume = "153",

pages = "196--205",

journal = "Carbon",

issn = "0008-6223",

publisher = "Elsevier Ltd",

}

Dee, NT, Li, J, Orbaek White, A, Jacob, C, Shi, W, Kidambi, PR, Cui, K, Zakharov, DN, Janković, NZ, Bedewy, M, Chazot, CAC, Carpena-Núñez, J, Maruyama, B, Stach, EA, Plata, DL & Hart, AJ 2019, 'Carbon-assisted catalyst pretreatment enables straightforward synthesis of high-density carbon nanotube forests', Carbon, vol. 153, pp. 196-205. https://doi.org/10.1016/j.carbon.2019.06.083

TY - JOUR

T1 - Carbon-assisted catalyst pretreatment enables straightforward synthesis of high-density carbon nanotube forests

AU - Dee, Nicholas T.

AU - Li, Jinjing

AU - Orbaek White, Alvin

AU - Jacob, Christine

AU - Shi, Wenbo

AU - Kidambi, Piran R.

AU - Cui, Kehang

AU - Zakharov, Dmitri N.

AU - Janković, Nina Z.

AU - Bedewy, Mostafa

AU - Chazot, Cécile A.C.

AU - Carpena-Núñez, Jennifer

AU - Maruyama, Benji

AU - Stach, Eric A.

AU - Plata, Desiree L.

AU - Hart, A. John

N1 - Funding Information: We thank Rahul Rao for insightful discussions, and Byeongdu Lee for assistance in the SAXS analysis. Financial support was provided by the MIT-Skoltech Next Generation Program (for N.T.D.); the Office of Naval Research Young Investigator Program , grant number N000141210815 (for J.L., A.O.W.); the Department of Energy, Office of Science under Grant No. DE-SC0010795 (for P.R.K.); the NSF Graduate Research Fellowship Program (for N.Z.J.); the Air Force Office of Scientific Research, AFOSR under LRIR# 16RXCOR322 ; and by the National Aeronautics and Space Administration (NASA) Space Technology Research Institute (STRI) for Ultra-Strong Composites by Computational Design (US-COMP) , grant number NNX17AJ32GNASA-USCOMP (for N.T.D and A.J.H). SEM and TEM imaging were performed at Harvard University's Center for Nanoscale Systems (CNS), a member of the National Nanotechnology Infrastructure Network (NNIN), which is supported by the National Science Foundation under NSF award no. ECS-0335765 . XPS and AFM measurements were performed in the Michigan Center for Materials Characterization at the University of Michigan. Raman characterization and thermogravimetric analysis were performed at the Institute for Soldier Nanotechnologies (ISN) at MIT. Catalyst deposition and substrate dicing was performed at the Microsystems Technology Laboratories (MTL) at MIT. SAXS characterization was performed at the 12-ID-B beamline at the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357 . ETEM studies were performed at the Center for Functional Nanomaterials, Brookhaven National Laboratory, which is supported by the U.S. Department of Energy, Office of Basic Energy Sciences , under Contract No. DE-SC0012704 . Funding Information: We thank Rahul Rao for insightful discussions, and Byeongdu Lee for assistance in the SAXS analysis. Financial support was provided by the MIT-Skoltech Next Generation Program (for N.T.D.); the Office of Naval Research Young Investigator Program, grant number N000141210815 (for J.L. A.O.W.); the Department of Energy, Office of Science under Grant No. DE-SC0010795 (for P.R.K.); the NSF Graduate Research Fellowship Program (for N.Z.J.); the Air Force Office of Scientific Research, AFOSR under LRIR#16RXCOR322; and by the National Aeronautics and Space Administration (NASA) Space Technology Research Institute (STRI) for Ultra-Strong Composites by Computational Design (US-COMP), grant number NNX17AJ32GNASA-USCOMP (for N.T.D and A.J.H). SEM and TEM imaging were performed at Harvard University's Center for Nanoscale Systems (CNS), a member of the National Nanotechnology Infrastructure Network (NNIN), which is supported by the National Science Foundation under NSF award no. ECS-0335765. XPS and AFM measurements were performed in the Michigan Center for Materials Characterization at the University of Michigan. Raman characterization and thermogravimetric analysis were performed at the Institute for Soldier Nanotechnologies (ISN) at MIT. Catalyst deposition and substrate dicing was performed at the Microsystems Technology Laboratories (MTL) at MIT. SAXS characterization was performed at the 12-ID-B beamline at the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. ETEM studies were performed at the Center for Functional Nanomaterials, Brookhaven National Laboratory, which is supported by the U.S. Department of Energy, Office of Basic Energy Sciences, under Contract No. DE-SC0012704. Publisher Copyright: © 2019

PY - 2019/11

Y1 - 2019/11

N2 - Despite extensive academic and commercial development, a comprehensive understanding of the principles necessary for high-yield production of carbon nanotubes (CNTs) is lacking, whether in oriented films, bulk powders, or other forms. In chemical vapor deposition growth of CNT films on substrates, trace contaminants of carbon, such as deposits on the reactor tube walls, are known to cause inconsistency in key production metrics, including CNT density and alignment. In this study, we show that trace exposure of the catalyst to carbon during initial heating of the catalyst film is a critical determinant of CNT yield, and this carbon exposure accelerates catalyst nanoparticle formation via film dewetting and increases the probability of CNT nucleation and the resultant density of the CNT population. By controlled exposure of the catalyst to a trace amount of carbon, we show up to a 4-fold increase in bulk mass density for a given forest height, an 8-fold increase in local CNT number density, and a 2-fold increase in the growth lifetime, relative to a reference condition. We discuss potential mechanisms to explain the role of carbon exposure on the probability of CNT nucleation from nanoparticle catalysts, supported by microscopy and gas analysis.

AB - Despite extensive academic and commercial development, a comprehensive understanding of the principles necessary for high-yield production of carbon nanotubes (CNTs) is lacking, whether in oriented films, bulk powders, or other forms. In chemical vapor deposition growth of CNT films on substrates, trace contaminants of carbon, such as deposits on the reactor tube walls, are known to cause inconsistency in key production metrics, including CNT density and alignment. In this study, we show that trace exposure of the catalyst to carbon during initial heating of the catalyst film is a critical determinant of CNT yield, and this carbon exposure accelerates catalyst nanoparticle formation via film dewetting and increases the probability of CNT nucleation and the resultant density of the CNT population. By controlled exposure of the catalyst to a trace amount of carbon, we show up to a 4-fold increase in bulk mass density for a given forest height, an 8-fold increase in local CNT number density, and a 2-fold increase in the growth lifetime, relative to a reference condition. We discuss potential mechanisms to explain the role of carbon exposure on the probability of CNT nucleation from nanoparticle catalysts, supported by microscopy and gas analysis.

UR - http://www.scopus.com/inward/record.url?scp=85068545194&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85068545194&partnerID=8YFLogxK

U2 - 10.1016/j.carbon.2019.06.083

DO - 10.1016/j.carbon.2019.06.083

M3 - Article

AN - SCOPUS:85068545194

SN - 0008-6223

VL - 153

SP - 196

EP - 205

JO - Carbon

JF - Carbon

ER -

Carbon-assisted catalyst pretreatment enables straightforward synthesis of high-density carbon nanotube forests

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