Effect of the Ni size on CH4/CO2 reforming over Ni/MgO catalyst:A DFT study

doi:10.1016/j.cjche.2017.03.024

Abstract

Abstract: Carbon deposition is sensitive to the metal particle sizes of supported Ni catalysts in CH₄/CO₂ reforming. To explore the reason of this phenomenon, Ni4, Ni8, and Ni12 which reflect the different cluster thicknesses supported on the MgO(100) slabs, have been employed to simulate Ni/MgO catalysts, and the reaction pathways of CH₄/CO₂ reforming on Nix/MgO(100) models are investigated by density functional theory. The reforming mechanisms of CH₄/CO₂ on different Nix/MgO(100) indicate the energy barriers of CH₄ dissociated adsorption, CH dissociation, and C oxidation three factors are all declining with the decrease of the Ni cluster sizes. The Hirshfeld charges analyses of three steps as described above show only Ni atoms in bottom two layers can obtain electrons from the MgO supporters, and the main electron transfer occurs between adsorbed species and their directly contacted Ni atoms. Due to more electron-rich Ni atoms in contact with the MgO supporters, the Ni/MgO catalysts with small Ni particles have a strong metal particle size effect and lead to its better catalytic activity.

Key words: Particle size effect, Ni/MgO catalyst, CH₄/CO₂ reforming, Density functional theory

摘要： Carbon deposition is sensitive to the metal particle sizes of supported Ni catalysts in CH₄/CO₂ reforming. To explore the reason of this phenomenon, Ni4, Ni8, and Ni12 which reflect the different cluster thicknesses supported on the MgO(100) slabs, have been employed to simulate Ni/MgO catalysts, and the reaction pathways of CH₄/CO₂ reforming on Nix/MgO(100) models are investigated by density functional theory. The reforming mechanisms of CH₄/CO₂ on different Nix/MgO(100) indicate the energy barriers of CH₄ dissociated adsorption, CH dissociation, and C oxidation three factors are all declining with the decrease of the Ni cluster sizes. The Hirshfeld charges analyses of three steps as described above show only Ni atoms in bottom two layers can obtain electrons from the MgO supporters, and the main electron transfer occurs between adsorbed species and their directly contacted Ni atoms. Due to more electron-rich Ni atoms in contact with the MgO supporters, the Ni/MgO catalysts with small Ni particles have a strong metal particle size effect and lead to its better catalytic activity.

关键词: Particle size effect, Ni/MgO catalyst, CH₄/CO₂ reforming, Density functional theory

Yunpeng Guo, Jie Feng, Wenying Li. Effect of the Ni size on CH₄/CO₂ reforming over Ni/MgO catalyst:A DFT study[J]. , 2017, 25(10): 1442-1448.

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Effect of the Ni size on CH₄/CO₂ reforming over Ni/MgO catalyst:A DFT study

Effect of the Ni size on CH₄/CO₂ reforming over Ni/MgO catalyst:A DFT study

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