Distribution of Al and adsorption of NH<sub>3</sub> in mordenite：A computational study

GUO Hai-yan; REN Jun; FENG Gang; LI Chang-sheng; PENG Xing; CAO Duan-lin

Volume 42 Issue 05

May 2014

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Article Navigation > Journal of Fuel Chemistry and Technology > 2014 > 42(05): 582-590

GUO Hai-yan, REN Jun, FENG Gang, LI Chang-sheng, PENG Xing, CAO Duan-lin. Distribution of Al and adsorption of NH3 in mordenite：A computational study[J]. Journal of Fuel Chemistry and Technology, 2014, 42(05): 582-590.

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GUO Hai-yan, REN Jun, FENG Gang, LI Chang-sheng, PENG Xing, CAO Duan-lin. Distribution of Al and adsorption of NH₃ in mordenite：A computational study[J]. Journal of Fuel Chemistry and Technology, 2014, 42(05): 582-590.

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Distribution of Al and adsorption of NH₃ in mordenite：A computational study

1.
College of Chemical Engineering and Environment, North University of China, Taiyuan 030051, China;
2.
Shanghai Research Institute of Petrochemical Technology SINOPEC, Shanghai 201208, China

Funds: Supported by the National Science Foundation of China (21371159), the Natural Science Foundation of Shanxi Province (2009011014) and Shenzhen Strategic Emerging Industries Special Fund Program of China (GGJS20120619101655715).

Received Date: 2013-10-31
Rev Recd Date: 2014-01-07
Publish Date: 2014-05-30

Abstract

Abstract

Dispersion corrected density functional theory (DFT-D2) were employed to investigate the distribution of Al in the framework of H-[Al]MOR and the strengths of Brönsted acid sites by NH₃ adsorption. Thermodynamically, the most favorable site for distribution of Al is T2O5, followed by T4O2, T1O7 and T3O1, which are a little higher in energy when Al is incorporated. It was found that the energy differences for Al in different T sites are 0.03~ 0.07 eV, indicating that the Al atoms might distribute in all kinds of four non-equivalent crystallographic tetrahedral sites of MOR. Moreover, it is also suggested that the location of protons plays an important role in the stability of the Al substitution site. In addition, we also computed the adsorption energies for NH₃ adsorbed at each crystallographic position of H-[Al]MOR by DFT and DFT-D2, respectively. By comparison, the DFT method always underestimates the substitution energy by 0.41 eV for the adsorption of NH₃, indicating that the dispersion correction is necessary to calculate the adsorption of NH₃ in H-[Al]MOR. The results show that the Brönsted acid site at T2O5 is stronger than the other acid sites, and the adsorption of NH₃ on the Lewis acid sites is clearly weaker than on the Brönsted acid sites.
- mordenite,
- Al distribution,
- NH₃ adsorption,
- DFT-D2

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