In Situ FTIR Spectroscopy for Scanning Accessible Active Sites in Defect-Engineered UiO-66

Three UiO-66 samples were prepared by solvothermal synthesis using the defect engineering approach with benzoic acid as a modulator. They were characterized by different techniques and their acidic properties were assessed by FTIR spectroscopy of adsorbed CO and CD₃CN. All samples evacuated at room temperature contained bridging μ₃-OH groups that interacted with both probe molecules. Evacuation at 250 °C leads to the dehydroxylation and disappearance of the μ₃-OH groups. Modulator-free synthesis resulted in a material with open Zr sites. They were detected by low-temperature CO adsorption on a sample evacuated at 200 °C and by CD₃CN even on a sample evacuated at RT. However, these sites were lacking in the two samples obtained with a modulator. IR and Raman spectra revealed that in these cases, the Zr⁴⁺ defect sites were saturated by benzoates, which prevented their interaction with probe molecules. Finally, the dehydroxylation of all samples produced another kind of bare Zr sites that did not interact with CO but formed complexes with acetonitrile, probably due to structural rearrangement. The results showed that FTIR spectroscopy is a powerful tool for investigating the presence and availability of acid sites in UiO-66, which is crucial for its application in adsorption and catalysis.