A DFT study on catalytic cracking mechanism of tar by Ni or Fe doped CaO during biomass steam gasification

The presence of byproduct tar seriously reduces the efficiency and syngas quality in the biomass gasification process. The current understanding of CaO-catalyzed tar cracking mainly depends on experimental findings and conjecture about CaO properties. However, there is a significant lack of simulation studies that explore the conversion mechanism at the molecular level. In this work, the reaction mechanism of tar catalytic cracking on Ni or Fe doped CaO was studied using density functional theory simulation. The benzene, phenol and toluene were chosen as the tar model compounds to determine the influences of Ni and Fe on the adsorption characteristics of CaO surface. CaO doped with Ni and Fe increases its electron affinity and electron conductivity from 4.99 to 9.21/5.58 eV-1. It also enhances the interactions between the d-orbitals of Ni/Fe atoms and the p-orbitals of O atoms. The C-H activation of center dot CH3 is the most kinetically and energetically feasible first step. The Ni-doped CaO and Fe-doped CaO decrease the energy barriers by 15.7 % and 21.7 %, respectively, compared with undoped CaO. Ni enhances the surface adsorption capacity for center dot H radicals to form OH* at the O top site, whereas Fe promotes the stabilization of center dot H radicals at the Ca-O vacancy. Through the enhancement of chemical adsorption capacity, improvement of electronic properties, introduction of electron reorganization and orbital hybridization, low-energy shift of energy levels, and generation of new energy states (from -0.85 to -1.64/-3.05 eV), the surfaces of Ni-doped CaO and Fe-doped CaO provide a favorable electronic environment for the tar catalytic cracking, which improves the reaction efficiency and selectivity.