DFT studies of hydrocarbon combustion on metal surfaces

• Published in: Journal of molecular modeling 2018, Vol.24 (2), p.47-10, Article 47
• Main Authors: Arya, Mina, Mirzaei, Ali Akbar, Davarpanah, Abdol Mahmood, Barakati, Seyed Masoud, Atashi, Hossein, Mohsenzadeh, Abas, Bolton, Kim
• Format: Article
• Language: English
• Subjects: Activation energy; Aluminum; Brønsted-Evans-Polanyi relationship; Catalysis; Catalyst; Characterization and Evaluation of Materials; Chemistry; Chemistry and Materials Science; Cobalt; Computer Appl. in Life Sciences; Computer Applications in Chemistry; Copper; Density functional theory; Gold; Hydrocarbon combustion; Hydrocarbons; Iron; Mathematical analysis; Metal surfaces; Molecular Medicine; Nickel; Original Paper; Palladium; Platinum; Resource Recovery; Resursåtervinning; Silver; Studies; Theoretical and Computational Chemistry
• ISSN: 1610-2940; 0948-5023; 0948-5023
• DOI: 10.1007/s00894-018-3585-z

Catalytic combustion of hydrocarbons is an important technology to produce energy. Compared to conventional flame combustion, the catalyst enables this process to operate at lower temperatures; hence, reducing the energy required for efficient combustion. The reaction and activation energies of direct combustion of hydrocarbons (CH → C + H) on a series of metal surfaces were investigated using density functional theory (DFT). The data obtained for the Ag, Au, Al, Cu, Rh, Pt, and Pd surfaces were used to investigate the validity of the Brønsted-Evans-Polanyi (BEP) and transition state scaling (TSS) relations for this reaction on these surfaces. These relations were found to be valid (R 2  = 0.94 for the BEP correlation and R 2  = 1.0 for the TSS correlation) and were therefore used to estimate the energetics of the combustion reaction on Ni, Co, and Fe surfaces. It was found that the estimated transition state and activation energies (E TS  = −69.70 eV and E a  = 1.20 eV for Ni, E TS  = −87.93 eV and E a  = 1.08 eV for Co and E TS  = −92.45 eV and E a  = 0.83 eV for Fe) are in agreement with those obtained by DFT calculations (E TS  = −69.98 eV and E a  = 1.23 eV for Ni, E TS  = −87.88 eV and E a  = 1.08 eV for Co and E TS  = −92.57 eV and E a  = 0.79 eV for Fe). Therefore, these relations can be used to predict energetics of this reaction on these surfaces without doing the time consuming transition state calculations. Also, the calculations show that the activation barrier for CH dissociation decreases in the order Ag ˃ Au ˃ Al ˃ Cu ˃ Pt ˃ Pd ˃ Ni > Co > Rh > Fe.