The dehydrogenation of CH4 on Rh(111), Rh(110) and Rh(100) surfaces: A density functional theory study

Wang, Baojun; Song, Li; Zhang, Riguang

doi:10.1016/j.apsusc.2011.12.012

Cited by 68 publications

(37 citation statements)

References 58 publications

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“…In the most stable co-adsorption configuration of HS/H and H/S, the distance of H\S bond is much longer than that in H 2 S (HS) adsorption and the free H 2 S (HS) molecule. This phenomenon has also been confirmed by our previous research [41,42] and other researchers' reports [45][46][47][48]. Fig.…”

Section: The Co-adsorption Of Hs/h and H/s On The Pd (1 0 0) Surfacesupporting

confidence: 91%

“…In addition, for validating the transition states involved in the reaction, Dmol3 program was employed to calculate the frequency of transition state since the CASTEP program cannot generate the frequency information. Additionally, it was confirmed that every transition state could lead to the desired reactants and products [47,48]. The double-numeric quality (DNP) basis set was used, which corresponds to Gauss-type 6-31G level.…”

Section: Computational Detailsmentioning

confidence: 99%

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Investigation on adsorption and decomposition of H2S on Pd (1 0 0) surface: A DFT study

2015

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Section: The Co-adsorption Of Hs/h and H/s On The Pd (1 0 0) Surfacesupporting

confidence: 91%

Section: Computational Detailsmentioning

confidence: 99%

Investigation on adsorption and decomposition of H2S on Pd (1 0 0) surface: A DFT study

2015

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“…Whereas we did not discuss this, it is the reason that the activation of σ chemical bonds, as for example in methane, occurs preferentially over an atop site [5,[69][70][71] When the adsorption energies of atop adsorbed species are compared with the bond energies of corresponding molecules, the adsorbate chemical bonds are always smaller. A common denominator of the different bonding aspects that we discussed is the increased Pauli repulsion of the adsorbate chemical bonds to the late transition metals compared to that for adsorbates on the early transition metal surface.…”

Section: Conclusion and Discussionmentioning

confidence: 91%

How molecular is the chemisorptive bond?

Santen

Tranca

2016

Phys. Chem. Chem. Phys.

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Trends in adsorption energies as a function of transition metal differ for adsorbates that are attached atop a surface atom or are adsorbed onto a high coordination site. When adsorption onto early and late transition metals is compared variation in relative bond energies of adsorbates attached to different sites is large. A theoretical understanding is provided based on the analysis of the electronic structure of the respective chemical bonds. The electronic structure analysis is based on partial density of states (PDOS) and bond order overlap population densities from crystal orbital Hamiltonian population (COHP) calculations available from DFT electronic structure computations. This is complemented by calculations of Bader charge densities and electron density topology properties. Variation of the respective bond energies depends on the symmetry of the molecular orbitals that form the chemical bond. The key electronic structure parameters are the position of the Fermi level in the bonding or antibonding molecular orbital partial density of states region of the chemical bond and chemical bond polarity. These are very different for adsorbates adsorbed onto the same transition metal surface, but which have different coordination with surface metal atoms. The adsorption energies and the respective electronic structures of adatoms H, C and O and molecular fragments CHx (x = 1-3) are compared with those of the analogous molecules that contain a single transition metal atom. When adsorbed atop, trends in bond energies are remarkably similar to those of the corresponding molecules. The difference in bond energies of adsorbates and transition metal molecules, i.e. the embedding energy, is shown to consist of three contributions: quenching of the sometimes high molecular spin states, weakening of the adsorbate-surface interaction energy and weakening of the metal-metal atom bond energies next to the adsorbate. Conventional scaling rules of the interaction energies of adsorbed CHx (0 < x ≤ 3) fragments are satisfied only for adsorbates in high coordination sites. For the early transition metals a breaking of this rule is found for C and CH or N and NH when adsorbed atop a transition metal surface or when they are part of a transition metal molecule. The M-C bond energy is found to be only stronger than that of the M-CH bond as long as the Fermi level or the HOMO is located in the antibonding molecular orbital partial density of states of the chemical bond.

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“…The DFT calculations were conducted using the program package Cambridge Sequential Total Energy Package (CASTEP) with a plane wave basis set in the Materials Studio software (Accelrys, Inc) [27,[35][36]. In this research, the Perdew-Wang-91 (PW91) functional with the generalized gradient approximation (GGA) was applied to calculate the exchange-correlation energy [37].…”

Section: Computational Detailsmentioning

confidence: 99%

Mechanism of ammonia decomposition on clean and oxygen-covered Cu (1 1 1) surface: A DFT study

2014

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The dehydrogenation of CH4 on Rh(111), Rh(110) and Rh(100) surfaces: A density functional theory study

Cited by 68 publications

References 58 publications

Investigation on adsorption and decomposition of H2S on Pd (1 0 0) surface: A DFT study

Investigation on adsorption and decomposition of H2S on Pd (1 0 0) surface: A DFT study

How molecular is the chemisorptive bond?

Mechanism of ammonia decomposition on clean and oxygen-covered Cu (1 1 1) surface: A DFT study

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