Simulating Crystal Structure, Acidity, Proton Distribution, and IR Spectra of Acid Zeolite HSAPO-34: A High Accuracy Study.

It is a challenge to characterize the acid properties of microporous materials in either experiments or theory. This study presents the crystal structure, acid site, acid strength, proton siting, and IR spectra of HSAPO-34 from the SCAN + rVV10 method. The results indicate: the crystal structures of various acid sites of HSAPO-34 deviate from the space group of R3¯; the acid strength inferred from the DPE value likely decreases with the proton binding sites at O(2), O(4), O(1),and O(3), contrary to the stability order in view of the internal energy; the calculated ensemble-averaged DPE is about 1525 kJ/mol at 673.15 K; and the proton siting and the proton distribution are distinctly influenced by the temperature: at low temperatures, the proton is predominantly located at O(3), while it prefers O(2) at high temperatures, and the proton at O(4) assumedly has the least distribution at 273.15-773.15 K. In line with the neutron diffraction experiment, a correction factor of 0.979 is needed to correct for the calculated hydroxyl stretching vibration (ν(O-H)) of HSAPO-34. It seems that the SCAN meta-GGA method, compensating for some drawbacks of the GGA method, could provide satisfying results regarding the acid properties of HSAPO-34.