The Activation of Methane on Ru, Rh, and Pd Decorated Carbon Nanotube and Boron Nitride Nanotube: A DFT Study

Abstract

Methane decomposition catalyzed by an Ru, Rh, or Pd atom supported on a carbon or boron nitride nanotubes was analyzed by means of the density functional theory with the M06-L hybrid functional. The results suggested that the dissociative reaction of methane was a single-step mechanism. Based on the calculated activation energy, the Ru-decorated carbon nanotube showed superior catalytic activity with an activation barrier of 14.5 kcal mol −1 , followed by the Rh-decorated carbon nanotube (18.1 kcal mol −1) and the Pd-decorated carbon nanotube (25.6 kcal mol −1). The catalytic performances of metals supported on a boron nitride nanotube were better than those on a carbon nanotube. The total activation barrier for the Ru, Rh, and Pd atoms on boron nitride nanotube was 10.2, 14.0, and 20.5 kcal mol −1 , respectively. Dissociative adsorption complexes on the Ru-boron nitride nanotube were the most stable. The anionic state of the supported metal atom was responsible for decreasing the activation energy of methane decomposition. Our finding provides a crucial point for further investigation.

Pt-, Rh-, Ru-, and Cu-Single-Wall Carbon Nanotubes Are Exceptional Candidates for Design of Anti-Viral Surfaces: A Theoretical Study

“…The adsorption energy for Pt, Pd, Ni, Cu, Rh, and Ru on SWCNT were calculated to be −2.57, −1.53, −2.02, −0.75, −2.63, and −2.96 eV, respectively, in good agreement with literature data [ 64 , 68 , 74 , 79 , 80 , 81 , 82 , 83 , 84 ]. The interactions between the Pt, Pd, Ni, Cu, Rh, and Ru atoms and SWCNT produced a charge transfer of 0.159, 0.125, 0.502, 0.426, 0.312, and 0.376 e from the metals to the nanotube, respectively.…”

Partial Oxidation of Methane to Methanol on the M–O–Ag/Graphene (M = Ag, Cu) Composite Catalyst: A DFT Study

“…Interestingly, regardless of the spin state of the complex, methane shows only one stable adsorption configuration, with one of the hydrogen atoms on CH 4 pointing to the μ-O atom. For the Ag−O−Ag/ graphene catalyst, the C−H length in the reactant complex RC is 1.10 Å, which is the same as that of gas methane (1.10 Å) and close to that of the experimental value (1.09 Å), 57 58 and on the FeO/ graphene catalyst reported by Impeng et al 29 3, compared with one-dimensional material catalysts, for example, Pd-boron nitride nanotubes (0.89 eV), 60 Pd-carbon nanotubes (1.11 eV), 60 NCNT(4,4)-O 2 (1.12 eV), 61 and NCNT(4,4)-O (1.08 eV), 61 Ag−O−Ag/ graphene and Cu−O−Ag/graphene catalysts both show lower activation energies of the C−H bond in CH 4 , which is mainly attributed to the strong composite interaction inducing high reactivity. In addition, it is the same in comparison with diverse two-dimensional composite catalysts, such as Co/G(0.80 eV), 62 Mn/G (0.99 eV), 62 CoN 3 /G (0.83 eV), 63 Fe@GY (0.98 eV), 64 and OFe/N x G (1.34−1.91 eV), 47 31 and Pt 2 /GO sheet (0.33 eV), 66 which also means that the presence of these noble metal catalysts can easily realize CH 4 activation.…”

“…Table summarizes the reaction energies of C–H bond activation, C–O bond formation, and the desorption energy of CH 3 OH. As listed in Table , compared with one-dimensional material catalysts, for example, Pd-boron nitride nanotubes (0.89 eV), Pd-carbon nanotubes (1.11 eV), NCNT­(4,4)-O 2 (1.12 eV), and NCNT­(4,4)-O (1.08 eV), Ag–O–Ag/graphene and Cu–O–Ag/graphene catalysts both show lower activation energies of the C–H bond in CH 4 , which is mainly attributed to the strong composite interaction inducing high reactivity. In addition, it is the same in comparison with diverse two-dimensional composite catalysts, such as Co/G­(0.80 eV), Mn/G (0.99 eV), CoN 3 /G (0.83 eV), Fe@GY (0.98 eV), and OFe/N x G (1.34–1.91 eV), that is due to the introduction of noble metal Ag in Ag–O–Ag/graphene and Cu–O–Ag/graphene catalysts.…”

Catalytic Oxidation of NO on [Au–M]− (M = Pd and Pt) Bimetallic Dimers: An Insight from Density Functional Theory Approach

“…For geometry relaxation and frequency calculations, a local density M06L functional is chosen which has a good result on both the main group and transition metals by establishing the dependency of the exchange-correlation energy on local spin density, spin density gradient, and spin kinetic energy density. Previous studies − also show the reliability of the M06L functional that it works quite well in producing the accurate structure and exploring the properties of precious metals. To locate the atomic orbitals of the atoms, a density-fitting triple-ζ valence with single-polarization (def2TZVP) , is employed in the calculation.…”