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Structures, Energetics and Reactions of Hydrocarbons on Nickel


Mueller, Jonathan Edward (2010) Structures, Energetics and Reactions of Hydrocarbons on Nickel. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/RVXX-Z341.


To better understand and improve reactive processes on nickel surfaces such as the catalytic steam reforming of hydrocarbons, the decomposition of hydrocarbons at fuel cell anodes, and the growth of carbon nanotubes, we have performed atomistic studies of hydrocarbon adsorption and decomposition on low index nickel surfaces and nickel catalyst nanoparticles. Quantum mechanics (QM) calculations utilizing the PBE flavor of density functional theory (DFT) were performed on all CHx and C2Hy species to determine their structures and energies on Ni(111). In good agreement with experiments, we find that CH is the most stable form of CHx on Ni(111). It is a stable intermediate in both methane dehydrogenation and CO methanation, while CH(2,ad) is only stable during methanation. We also find that nickel surface atoms play an important catalytic role in C-H bond formation and cleavage. For the C2Hy species we find a low surface coverage decomposition pathway proceeding through CHCHad, the most stable intermediate, and a high surface coverage pathway which proceeds through CCH3,ad, the next most stable intermediate. Our enthalpies along these pathways are consistent with experimental observations.

To extend our study to larger systems and longer time scales, we have developed the ReaxFF reactive force field to describe hydrocarbon decomposition and reformation on nickel catalyst surfaces. The ReaxFF parameters were fit to geometries and energy surfaces from DFT calculations involving a large number of reaction pathways and equations of state for nickel, nickel carbides, and various hydrocarbon species chemisorbed on Ni(111), Ni(110) and Ni(100). The resulting ReaxFF description was validated against additional DFT data to demonstrate its accuracy, and used to perform reaction dynamics (RD) simulations on methyl decomposition for comparison with experiment. Finally ReaxFF RD simulations were applied to the chemisorption and decomposition of six different hydrocarbons (methane, acetylene, ethylene, benzene, cyclohexane and propylene) on a 468 atom nickel nanoparticle. These simulations realistically model hydrocarbon feedstock decomposition and provide reaction pathways relevant to this part of the carbon nanotube growth process. They show that C-C π bonds provide a low barrier pathway for chemisorption, and that the low energy of subsurface C is an important driving force in breaking C-C bonds.

Item Type:Thesis (Dissertation (Ph.D.))
Subject Keywords:hydrocarbons; nickel; heterogeneous catalysis; chemisorption; surface chemistry; ReaxFF reactive force field; density functional theory; carbon nanotubes; methanation; Fischer-Tropsch; fuel cells; steam reformation
Degree Grantor:California Institute of Technology
Division:Chemistry and Chemical Engineering
Major Option:Chemistry
Thesis Availability:Public (worldwide access)
Research Advisor(s):
  • Goddard, William A., III
Thesis Committee:
  • Heath, James R. (chair)
  • Bercaw, John E.
  • Wang, Zhen-Gang
  • Goddard, William A., III
Defense Date:4 May 2010
Record Number:CaltechTHESIS:05262010-132424180
Persistent URL:
Mueller, Jonathan Edward0000-0001-8811-8799
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:5844
Deposited By: Jonathan Mueller
Deposited On:27 May 2010 22:40
Last Modified:08 Nov 2019 18:10

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