Citation: ZHANG Xiu-xia, XIE Miao, WU Hui-xi, LÜ Xiao-xue, LIN Ri-yi, ZHOU Zhi-jun. Microscopic effect mechanism of Ca on NO heterogeneous reduction by char: A DFT study[J]. Journal of Fuel Chemistry and Technology, ;2020, 48(2): 163-171. shu

Microscopic effect mechanism of Ca on NO heterogeneous reduction by char: A DFT study

1.
College of New Energy, China University of Petroleum(East China), Qingdao 266580, China
2.
State Key Laboratory of Clean Energy Utilization, Zhejiang University, Hangzhou 310027, China

Corresponding author: ZHANG Xiu-xia, zhangxx@upc.edu.cn
Received Date: 22 November 2019
Revised Date: 14 January 2020

Fund Project: The project was supported by the Fundamental Research Funds for the Central Universities 18CX02073AThe project was supported by the Fundamental Research Funds for the Central Universities (18CX02073A) and National Natural Science Foundation of China (51874333)National Natural Science Foundation of China 51874333

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The effect mechanism of Ca on nitric oxide (NO) heterogeneous reduction by char was investigated using density functional theory (DFT). The electronic structure of char model was analyzed to predict reactive sites. Mayer bond orders were used to quantify formation and breaking of chemical bonds in the reactions. There is a region with high electron localization function values in the extended outer region of unsaturated carbon atoms at the edge. The minimum electrostatic potential of char model, -101.1 kJ/mol, also exists at the edge, indicating the presence of lone pair electrons on edge carbon atoms. The doping of Ca could promote adsorption of the first NO molecule, but has little effect on that of the second NO molecule. The activation energy of rate-determining step is 124.4 kJ/mol for heterogeneous reduction of NO at the edge of char, whereas it is 91.9 kJ/mol at the Ca-decorated char edge. The kinetic analysis shows that the anterior factor increases after doping of Ca, meaning more sites are activated. The promotion of Ca to NO heterogeneous reduction is attributed to combination of the above two aspects.
- calcium,
- char,
- nitric oxide,
- heterogeneous reaction,
- density functional theory
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