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DFT studies of hydrocarbon combustion on metal surfaces.

ABSTRACT: 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 (R2?=?0.94 for the BEP correlation and R2?=?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 (ETS?=?-69.70 eV and Ea?=?1.20 eV for Ni, ETS?=?-87.93 eV and Ea?=?1.08 eV for Co and ETS?=?-92.45 eV and Ea?=?0.83 eV for Fe) are in agreement with those obtained by DFT calculations (ETS?=?-69.98 eV and Ea?=?1.23 eV for Ni, ETS?=?-87.88 eV and Ea?=?1.08 eV for Co and ETS?=?-92.57 eV and Ea?=?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.

SUBMITTER: Arya M

PROVIDER: S-EPMC5797216 | biostudies-literature | 2018 Feb

REPOSITORIES: biostudies-literature

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DFT studies of hydrocarbon combustion on metal surfaces.

Arya Mina M Mirzaei Ali Akbar AA Davarpanah Abdol Mahmood AM Barakati Seyed Masoud SM Atashi Hossein H Mohsenzadeh Abas A Bolton Kim K

Journal of molecular modeling 20180202 2

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 ...[more]

PMID: 29396776

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Project description:Cooperite (PtS) is one of the main sources of platinum in the world and has not been given much attention, in particular from the computational aspect. Besides, the surface stability of cooperite is not fully understood, in particular the preferred surface cleavage. In the current study, we employed computer modeling methods within the plane-wave framework of density functional theory with dispersion correction and the U parameter to correctly predict the bulk and surface properties. We reconstructed and calculated the geometries and surface energies of (001), (100), (101), (112), (110), (111), and (211) cooperite surfaces of stoichiometric planes. The Pt d-orbitals with U = 4.5 eV and S p-orbitals with U = 5.5 eV were found optimum to correctly predict a band gap of 1.408 eV for the bulk cooperite model, which agreed with an experimental value of 1.41 eV. The PtS-, Pt-, and S-terminated surfaces were investigated. The structural and electronic properties of the reconstructed surfaces were discussed in detail. We observed one major mechanism of relaxation of cooperite surface reconstructions that emerged from this study, which was the formation of Pt-Pt bonds. It emanated that the (110) and (111) cooperite surfaces underwent significant reconstruction in which the Pt2+ cation relaxed into the surface, forming new Pt-Pt (Pt2 2+) bonds. Similar behavior was perceived for (101) and (211) surfaces, where the Pt2+ cation relaxed inward and sideways on the surface, forming new Pt-Pt (Pt2 2+) bonds. The surface stability decreased in the order (101) > (100) ≈ (112) > (211) > (111) > (110) > (001), indicating that the (101) surface was the most stable, leading to an octahedron cooperite crystal morphology with truncated corners under equilibrium conditions. However, the electronic structures indicated that the chemical reactivity stability of the surfaces would be determined by band gaps. It was found that the (112) surface had a larger band gap than the other surfaces and thus was a chemical stability competitor to the (101) surface. In addition, it was established that the surfaces had different reactivities, which largely depended on the atomic coordination and charge state based on population atomic charges. This study has shown that cooperite has many planes/surface cleavages as determined by the computed crystal morphology, which is in agreement with experimental X-ray diffraction (XRD) pattern findings and the formation of irregular morphology shapes.

Project description:BackgroundPollutant particles containing environmentally persistent free radicals (EPFRs) are formed during many combustion processes (e.g. thermal remediation of hazardous wastes, diesel/gasoline combustion, wood smoke, cigarette smoke, etc.). Our previous studies demonstrated that acute exposure to EPFRs results in dendritic cell maturation and Th17-biased pulmonary immune responses. Further, in a mouse model of asthma, these responses were enhanced suggesting exposure to EPFRs as a risk factor for the development and/or exacerbation of asthma. The aryl hydrocarbon receptor (AHR) has been shown to play a role in the differentiation of Th17 cells. In the current study, we determined whether exposure to EPFRs results in Th17 polarization in an AHR dependent manner.ResultsExposure to EPFRs resulted in Th17 and IL17A dependent pulmonary immune responses including airway neutrophilia. EPFR exposure caused a significant increase in pulmonary Th17 cytokines such as IL6, IL17A, IL22, IL1β, KC, MCP-1, IL31 and IL33. To understand the role of AHR activation in EPFR-induced Th17 inflammation, A549 epithelial cells and mouse bone marrow-derived dendritic cells (BMDCs) were exposed to EPFRs and expression of Cyp1a1 and Cyp1b1, markers for AHR activation, was measured. A significant increase in Cyp1a1 and Cyp1b1 gene expression was observed in pulmonary epithelial cells and BMDCs in an oxidative stress and AHR dependent manner. Further, in vivo exposure of mice to EPFRs resulted in oxidative stress and increased Cyp1a1 and Cyp1b1 pulmonary gene expression. To further confirm the role of AHR activation in pulmonary Th17 immune responses, mice were exposed to EPFRs in the presence or absence of AHR antagonist. EPFR exposure resulted in a significant increase in pulmonary Th17 cells and neutrophilic inflammation, whereas a significant decrease in the percentage of Th17 cells and neutrophilic inflammation was observed in mice treated with AHR antagonist.ConclusionExposure to EPFRs results in AHR activation and induction of Cyp1a1 and in vitro this is dependent on oxidative stress. Further, our in vivo studies demonstrated a role for AHR in EPFR-induced pulmonary Th17 responses including neutrophilic inflammation.

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DFT studies of hydrocarbon combustion on metal surfaces.

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DFT studies of hydrocarbon combustion on metal surfaces.

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