Application of density functional theory on the NO-char heterogeneous reduction mechanism in the presence of CO<sub>2</sub>

ZHOU Sai; LIU Hu; YU Peng-fei; CHE De-fu

doi:10.1016/S1872-5813(21)60088-9

Volume 49 Issue 9

Sep. 2021

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ZHOU Sai, LIU Hu, YU Peng-fei, CHE De-fu. Application of density functional theory on the NO-char heterogeneous reduction mechanism in the presence of CO2[J]. Journal of Fuel Chemistry and Technology, 2021, 49(9): 1231-1238. doi: 10.1016/S1872-5813(21)60088-9

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ZHOU Sai, LIU Hu, YU Peng-fei, CHE De-fu. Application of density functional theory on the NO-char heterogeneous reduction mechanism in the presence of CO₂[J]. Journal of Fuel Chemistry and Technology, 2021, 49(9): 1231-1238. doi: 10.1016/S1872-5813(21)60088-9

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Application of density functional theory on the NO-char heterogeneous reduction mechanism in the presence of CO₂

doi: 10.1016/S1872-5813(21)60088-9

State Key Laboratory of Multiphase Flow in Power Engineering, School of Energy and Power Engineering, Xi’an Jiaotong University, Xi’an 710049, China

Funds: The project was supported by the Postdoctoral Research Foundation of China (2018M633507) and Natural Science Basic Research Plan in Shaanxi Province of China (2020JQ-063)

Received Date: 2021-02-05
Rev Recd Date: 2021-04-02

Available Online: 2021-04-22

Publish Date: 2021-09-30

Abstract

Abstract

In order to obtain the mechanism of the effect of CO₂ on the NO heterogeneous reduction, density functional theory (DFT) was adopted to investigate the interactions between char and NO with the participation of CO₂. The armchair configuration composed with several aromatic ring clusters was selected as the carbonaceous surfaces. Geometric optimizations were carried out at the B3LYP-D3/6-31G(d) level. Energies of optimized geometries were calculated at the B3LYP-D3/def2-TZVP level. The results show that, the surface carbonyl groups produced by the adsorption of CO₂ combine with the adsorbed NO to desorb CO₂, thereby providing adjacent carbon active sites for subsequent NO adsorption and N₂ desorption. Thermodynamic studies show that the exothermic heat of this reaction is 853.9 kJ/mol, and the highest energy barrier is 297.0 kJ/mol without the participation of CO₂, but the exothermic heat of this reaction is 593.7 kJ/mol, and the highest energy barrier is 214.1 kJ/mol with the participation of CO₂. Kinetic studies show that over the temperature range of 298.15–1800 K, the reaction rate constants of rate-limiting steps are calculated with conventional transition state theory. The rate constant with the participation of CO₂ is higher than that without the participation of CO₂. In summary, CO₂ plays a promoting role in interacting with NO and char and reducing energy barrier to form N₂ directly.
- CO₂,
- NO,
- heterogeneous reduction,
- density functional theory

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References(38)

References

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