Reaction kinetics of NH3-SCR over Cu-CHA from first principles
Licentiate thesis, 2021
In this thesis, density functional theory (DFT) calculations and first principles microkinetic simulations are used to investigate the reaction path and the reaction kinetics for low temperature-NH3-SCR. Based on a previously proposed catalytic cycle for NH3-SCR over Cu-CHA, an N2O formation path is put forward. It is proposed that N2O can form over linear [Cu(NH3)2]+ complexes, which are present during low temperature operation. N2O is formed from H2NNO, which is generated via NH2-NO coupling over a Cu-OOH-Cu site. The reaction proceeds with a low barrier and rationalizes the low-temperature
N2O emission peak observed experimentally at high Cu-loadings. N2O formation at high temperatures is instead proposed to occur through the decomposition of NH4NO3.
With a catalytic cycle including N2O formation, a first principles microkinetic model is developed to investigate the reaction kinetic of NH3-SCR over Cu-CHA. When developing the model, special attention is paid assessing the change in entropy for each reaction step. The results from the kinetic model show good agreement with the experimental data of apparent activation energies, reaction orders and N2O selectivity. The model links the catalytic performance with structure and forms the basis for further developments of the NH3-SCR technology.
density functional theory
ammonia assisted selective catalytic reduction
Cu-CHA
microkinetic modeling
Catalysis
Author
Yingxin Feng
Chalmers, Physics, Chemical Physics
The Role of H+- and Cu+-Sites for N2O Formation during NH3-SCR over Cu-CHA
Journal of Physical Chemistry C,;Vol. 125(2021)p. 4595-4601
Journal article
A First-Principles Microkinetic Model for Low-Temperature NH3 Assisted Selective Catalytic Reduction of NO over Cu-CHA
ACS Catalysis,;Vol. 11(2021)p. 14395-14407
Journal article
Subject Categories
Inorganic Chemistry
Theoretical Chemistry
Publisher
Chalmers
Kollektorn, Kemivägen 9 (online disputation password: 574747)
Opponent: Docent Peter Broqvist, Uppsala University, Sweden