Unraveling the Role of Intrinsic Carbon Defects for the Heterogeneous Reduction of NO with NH3

Abstract

ABSTRACT This study investigates the impact of intrinsic carbon defects on the reduction of nitrogen oxides (NOx) during coal combustion, with a focus on the synergistic effect of ammonia (NH3) and pulverized coal. Two representative computational models containing intrinsic carbon defects are described, and their influence on NH3 reduction of NO is studied. Stable species and transition states present in the pathways are calculated using B3LYP/6-31 G(d). Results indicate that exposed edge carbon atoms exhibit higher charge density distribution, affecting NH3 adsorption and NO reduction. The maximum energy barriers for both pathways do not exceed 45 kcal/mol, achievable in practical coal combustion systems. This paper also calculates the heterogeneous reduction process of a model without intrinsic carbon defects (Char model), with the aim of observing the specific effects of intrinsic carbon defects on the processes of migration of H/O atoms, migration and recombination of N atoms, and formation and desorption of N2 molecules. Furthermore, the analyses demonstrated an increase in the rate of heterogeneous reduction of NH3 and NO on defective carbon surfaces in comparison to the Char/NH/NO system, indicating that the intrinsic defects of the carbon have a contributory effect on the catalytic activity. With regard to the magnitude of the increase in reaction rate with increasing temperature, the presence of intrinsic defects in the carbon base serves to reinforce the role of temperature in the rate-determining step. Overall, this study provides insights into the role of intrinsic defects in carbon-based catalysis and offers implications for nitrogen oxide emission control strategies.