Heteropolyacids supported on boron nitride and carbon nitride for catalytic and catalytic photo-assisted alcohol dehydration

Keggin H3PM12O40 (PW12) and Wells-Dawson H6P2W18O60 (P2W18) hetempolyacids (HPAs) are photo(catalysts) for various acid-promoted and redox catalytic reactions. Their activity increases if they are deposited on certain supports as metal oxides or carbon materials. Although the surface area and acid-base interactions of the HPAs with supports are considered as key factors for the performance of the binary material, the role of the local structure changes in the HPAs upon their immobilization on solids must be also of primary importance, directly affecting both acidity and photoredox properties. Here, the (photo)catalytic performance of Keggin and Wells-Dawson heteropolytungstates supported on boron nitride (BN) and two types of carbon nitride (C3N4) in the gas-solid 2-pmpanol dehydration to propene has been studied. Apart from characterizing the materials by a set of conventional laboratory-scale structural and physical-chemical techniques, an insight into the variations of the local structure of supported HPAs is provided by means of X-ray absorption spectroscopy (XAS), and their influence on the supported HPAs (photo)catalytic activity is discussed. The irradiation with UV light increased the activity of both hetempolytungstates with respect to the catalytic experiments. The apparent activation energy calculated for the photo-assisted process resulted always lower with respect to that obtained for the catalytic one alone. Moreover, the materials that showed the highest apparent turnover frequency (TOF) were those in which the HPAs were impregnated on graphitic C3N4 or on BN and, in particular, the highest TOF values were observed at the highest temperature for the PW12/BN and P2W18/BN samples. Interestingly, the highest activity of HPAs supported on BN seems to be due to the stabilization of the W octahedral coordination, according to the XAS data.

Automated summary

The local structure changes of HPAs when immobilized on solids play a crucial role in influencing their acidity and photoredox properties. HPAs supported on carbon materials or metal oxides exhibit increased activity in photocatalytic experiments, with the highest activity observed in HPAs supported on BN. The XAS data suggests that the enhanced activity of HPAs supported on BN is due to the stabilization of W octahedral coordination.