Construction of high-performance catalysts for CO2 hydrogenation to aromatics with the assisted of DFT calculations

The adsorption properties of CH3O* and CHOO* adsorbed on the three crystal planes (001, 010, 101) of HZSM-5 were simulated by the generalized gradient approximation (GGA) of density functional theory (DFT), it was found that the (010) plane corresponding to the b-axis of the sheet HZSM-5 had the strongest adsorption energy for CH3O* and CHOO*. Therefore, we successfully synthesized sheet HZSM-5 with different thicknesses by adding the inhibitor (urea) and mineralizer (F-) to the synthesis system based on the theoretical calculations. The physicochemical properties of HZSM-5 were investigated by the characterization methods of SEM, TEM, Py-IR, OH-IR, CO2-TPD and so on. The results showed the thickness of HZSM-5 can be precisely adjusted by adding urea and NH4F and changing the ratio of urea/NH4F or TPAOH/NH4F. Then, the sheet HZSM-5 and ZnZr7O were connected in tandem to investigate the reaction conditions and catalytic performance for the direct conversion of CO2 hydrogenation to aromatics. It was found that the HZ-1.5NH4F had a large specific surface area, suitable B acid content and more defect sites. These advantages resulted in a high aromatic selectivity of 77.5% and CO2 conversion of 17.6% over ZnZr7O/HZ-1.5NH4F. Meanwhile, it exhibits stable performance and no significant deactivation after 80 h of operation.