Density functional theory study on the microscopic mechanism of NO₂ adsorption and reduction by potassium-doped biochar: the key role of the active sites

Abstract

Biochar is a porous carbon material that can effectively remove NO_x from flue gas. The influence of K element and active sites on the microscopic mechanism of NO₂ gas adsorption and reduction reaction remains elusive. Through density functional theory (DFT), two NO₂ molecules are selected on reasonable biochar models to calculate the reaction pathway. The reaction pathways involve the sequential adsorption of two NO₂ molecules at different active sites for reduction reaction, and desorption of two NO molecules and one CO₂ molecule. Through the energy barrier difference of the reaction path and interaction region indicator (IRI) analysis of important molecular structures, it was found that K atom promotes the adsorption reduction reaction in three reaction processes: the breakage of N–O bond, the desorption of NO molecule, and the dissociation of CO₂ molecule. Based on the different numbers of active sites in the four reactant models, it can be concluded that the promotion range of the K atom for the adsorption and reduction process of NO₂ molecules is 0.6157 nm. Thermodynamic and kinetic analyses indicate that the addition of K enhances the upper limit and the maximum reaction rate of the reaction pathways. This study provides certain theoretical guidance for preparing biochar to regulate NO₂ emissions.

Graphical Abstract

Keywords

Density functional theory / Nitrogen dioxide / Potassium / Biochar / Active sites / Chemical Sciences / Physical Chemistry (incl. Structural)

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Funding

Joint Research program for ecological conservation and high-quality development of the Yellow River Basin(NO.2022-YRUC-01-0203)

Research on Water Ecological Environment Protection of the Yangtze River in Guangyuan City(NO.2022-LHYJ-02-0509-06)

RIGHTS & PERMISSIONS

The Author(s)