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Title: Quantum Chemical Simulations Reveal Acetylene-Based Growth Mechanisms in the Chemical Vapor Deposition Synthesis of Carbon Nanotubes

Nonequilibrium quantum chemical molecular dynamics (QM/MD) simulation of early stages in the nucleation process of carbon nanotubes from acetylene feedstock on an Fe38 cluster was performed based on the density-functional tight-binding (DFTB) potential. Representative chemical reactions were studied by complimentary static DFTB and density functional theory (DFT) calculations. Oligomerization and cross-linking reactions between carbon chains were found as the main reaction pathways similar to that suggested in previous experimental work. The calculations highlight the inhibiting effect of hydrogen for the condensation of carbon ring networks, and a propensity for hydrogen disproportionation, thus enriching the hydrogen content in already hydrogen-rich species and abstracting hydrogen content in already hydrogen-deficient clusters. The ethynyl radical C2H was found as a reactive, yet continually regenerated species, facilitating hydrogen transfer reactions across the hydrocarbon clusters. The nonequilibrium QM/MD simulations show the prevalence of a pentagon-first nucleation mechanism where hydrogen may take the role of one arm of an sp2 carbon Y-junction. The results challenge the importance of the metal carbide formation for SWCNT cap nucleation in the VLS model and suggest possible alternative routes following hydrogen-abstraction acetylene addition (HACA)-like mechanisms commonly discussed in combustion synthesis.
 [1] ;  [2] ;  [3] ;  [4] ;  [5] ;  [2] ;  [5] ;  [6]
  1. ORNL
  2. Nagoya University, Japan
  3. Institute of High Energy Physics, Chinese Academy of Sciences, China
  4. Jilin University, Changchun
  5. Fukui Institute of Fundamental Chemistry, Kyoto University, Kyoto 606-8103, Japan
  6. WPI-Institute of Transformative Bio-Molecules and Department of Chemistry, Nagoya University, Japan
Publication Date:
OSTI Identifier:
DOE Contract Number:
Resource Type:
Journal Article
Resource Relation:
Journal Name: Carbon; Journal Volume: 72
Research Org:
Oak Ridge National Laboratory (ORNL)
Sponsoring Org:
SC USDOE - Office of Science (SC)
Country of Publication:
United States
carbon nanotube; acetylene; quantum chemical simulation