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Title: Isolating the Roles of Hydrogen Exposure and Trace Carbon Contamination on the Formation of Active Catalyst Populations for Carbon Nanotube Growth

Abstract

Limited understanding of the factors influencing the yield of carbon nanotubes (CNTs) relative to the number of catalyst particles remains an important barrier to their large-scale production with high quality, and to tailoring CNT properties for applications. This lack of understanding is evident in the frequent use of Edisonian approaches to give high-yield CNT growth, and in the sometimes-confusing influence of trace residues on the reactor walls. In order to create conditions wherein CNT yield is reproducible and to enable large-scale and reliable CNT synthesis, it is imperative to understand—fundamentally—how these common practices impact catalytic activity and thus CNT number density. In this paper, we use ambient pressure-X-ray photoelectron spectroscopy (AP-XPS) to reveal the influence of carbon and hydrogen on the coupling between catalyst reduction and CNT nucleation, from an iron catalyst film. We observe a positive correlation between the degree of catalyst reduction and the density of vertically aligned CNTs (forests), verifying that effective catalyst reduction is critical to CNT nucleation and to the resulting CNT growth yield. We demonstrate that the extent of catalyst reduction is the reason for low CNT number density and for lack of self-organization, lift-off, and growth of CNT forests. We also show thatmore » hydrocarbon byproducts from consecutive growths can facilitate catalyst reduction and increase CNT number density significantly. These findings suggest that common practices used in the field—such as reactor preconditioning—aid in the reduction of the catalyst population, thus improving CNT number density and enabling the growth of dense forests. Finally, our results also motivate future work using AP-XPS and complementary metrology tools to optimize CNT growth conditions according to the catalyst chemical state.« less

Authors:
ORCiD logo [1]; ORCiD logo [2];  [3]; ORCiD logo [4]; ORCiD logo [2]; ORCiD logo [5]; ORCiD logo [6]; ORCiD logo [7];  [2]; ORCiD logo [7]; ORCiD logo [8];  [3]
+ Show Author Affiliations
  1. Air Force Research Laboratory, Wright-Patterson Air Force Base, Dayton, OH (United States); Brookhaven National Lab. (BNL), Upton, NY (United States)
  2. Brookhaven National Lab. (BNL), Upton, NY (United States)
  3. Air Force Research Laboratory, Wright-Patterson Air Force Base, Dayton, OH (United States)
  4. Air Force Research Laboratory, Wright-Patterson Air Force Base, Dayton, OH (United States); UES, Inc., Dayton, OH (United States)
  5. Columbia Univ., New York, NY (United States)
  6. Vanderbilt Univ., Nashville, TN (United States)
  7. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
  8. Brookhaven National Lab. (BNL), Upton, NY (United States); Univ. of Pennsylvania, Philadelphia, PA (United States)
Publication Date:
Research Org.:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1571415
Report Number(s):
BNL-212227-2019-JAAM
Journal ID: ISSN 1936-0851; TRN: US2001057
Grant/Contract Number:  
SC0012704; SC0010795
Resource Type:
Accepted Manuscript
Journal Name:
ACS Nano
Additional Journal Information:
Journal Volume: 13; Journal Issue: 8; Journal ID: ISSN 1936-0851
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
77 NANOSCIENCE AND NANOTECHNOLOGY; 36 MATERIALS SCIENCE; carbon nanotubes; nucleation success rate; CNT number density; iron oxide; ambient pressure XPS

Citation Formats

Carpena-Núñez, Jennifer, Boscoboinik, Jorge Anibal, Saber, Sammy, Rao, Rahul, Zhong, Jian-Qiang, Maschmann, Matthew R., Kidambi, Piran R., Dee, Nicholas T., Zakharov, Dmitri N., Hart, A. John, Stach, Eric A., and Maruyama, Benji. Isolating the Roles of Hydrogen Exposure and Trace Carbon Contamination on the Formation of Active Catalyst Populations for Carbon Nanotube Growth. United States: N. p., 2019. Web. doi:10.1021/acsnano.9b01382.
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Carpena-Núñez, Jennifer, Boscoboinik, Jorge Anibal, Saber, Sammy, Rao, Rahul, Zhong, Jian-Qiang, Maschmann, Matthew R., Kidambi, Piran R., Dee, Nicholas T., Zakharov, Dmitri N., Hart, A. John, Stach, Eric A., & Maruyama, Benji. Isolating the Roles of Hydrogen Exposure and Trace Carbon Contamination on the Formation of Active Catalyst Populations for Carbon Nanotube Growth. United States. https://doi.org/10.1021/acsnano.9b01382
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Carpena-Núñez, Jennifer, Boscoboinik, Jorge Anibal, Saber, Sammy, Rao, Rahul, Zhong, Jian-Qiang, Maschmann, Matthew R., Kidambi, Piran R., Dee, Nicholas T., Zakharov, Dmitri N., Hart, A. John, Stach, Eric A., and Maruyama, Benji. Mon . "Isolating the Roles of Hydrogen Exposure and Trace Carbon Contamination on the Formation of Active Catalyst Populations for Carbon Nanotube Growth". United States. https://doi.org/10.1021/acsnano.9b01382. https://www.osti.gov/servlets/purl/1571415.
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@article{osti_1571415,
title = {Isolating the Roles of Hydrogen Exposure and Trace Carbon Contamination on the Formation of Active Catalyst Populations for Carbon Nanotube Growth},
author = {Carpena-Núñez, Jennifer and Boscoboinik, Jorge Anibal and Saber, Sammy and Rao, Rahul and Zhong, Jian-Qiang and Maschmann, Matthew R. and Kidambi, Piran R. and Dee, Nicholas T. and Zakharov, Dmitri N. and Hart, A. John and Stach, Eric A. and Maruyama, Benji},
abstractNote = {Limited understanding of the factors influencing the yield of carbon nanotubes (CNTs) relative to the number of catalyst particles remains an important barrier to their large-scale production with high quality, and to tailoring CNT properties for applications. This lack of understanding is evident in the frequent use of Edisonian approaches to give high-yield CNT growth, and in the sometimes-confusing influence of trace residues on the reactor walls. In order to create conditions wherein CNT yield is reproducible and to enable large-scale and reliable CNT synthesis, it is imperative to understand—fundamentally—how these common practices impact catalytic activity and thus CNT number density. In this paper, we use ambient pressure-X-ray photoelectron spectroscopy (AP-XPS) to reveal the influence of carbon and hydrogen on the coupling between catalyst reduction and CNT nucleation, from an iron catalyst film. We observe a positive correlation between the degree of catalyst reduction and the density of vertically aligned CNTs (forests), verifying that effective catalyst reduction is critical to CNT nucleation and to the resulting CNT growth yield. We demonstrate that the extent of catalyst reduction is the reason for low CNT number density and for lack of self-organization, lift-off, and growth of CNT forests. We also show that hydrocarbon byproducts from consecutive growths can facilitate catalyst reduction and increase CNT number density significantly. These findings suggest that common practices used in the field—such as reactor preconditioning—aid in the reduction of the catalyst population, thus improving CNT number density and enabling the growth of dense forests. Finally, our results also motivate future work using AP-XPS and complementary metrology tools to optimize CNT growth conditions according to the catalyst chemical state.},
doi = {10.1021/acsnano.9b01382},
journal = {ACS Nano},
number = 8,
volume = 13,
place = {United States},
year = {Mon Jul 22 00:00:00 EDT 2019},
month = {Mon Jul 22 00:00:00 EDT 2019}
}
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Journal Article:
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Publisher's Version of Record
https://doi.org/10.1021/acsnano.9b01382
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Cited by: 22 works
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Figures / Tables:

Figure 1 Figure 1: Experimental procedure and exemplary data collected along each stage of the experiment. (a-d) Schematic representation of the reduction of iron catalyst films and particle formation. (e-f) Schematic representation of CNT growth on the population of reduced catalyst particles. (g) AP-XPS spectra for the Fe 2p and C 1smore » core level spectra at multiple stages of the experiment described in the schematic. The reduction onsets 1 and 2 mark the conversion of the oxide film to a more reduced state, as indicated by the chemical states in the Fe 2p core level spectra (Fe3+, Fe2+, and Fe0).« less
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    HOT Graphene and HOT Graphene Nanotubes: New Low Dimensional Semimetals and Semiconductors
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