Photocatalytic Performance of Perovskite and Metal-Organic Framework Hybrid Material for the Reduction of N2 to Ammonia.

The orthorhombic phase of KNbO3 perovskite has been applied for nitrogen (N2) photoreduction to ammonia (NH3). However, this material suffers from a low surface area and low ammonia production efficiency under UV light irradiation. To eliminate these barriers, we used a metal-organic framework (MOF), named as TMU-5 ([Zn(OBA)(BPDH)0.5]n·1.5DMF, where H2OBA = 4,4'-oxybis(benzoic acid) and BPDH = 2,5-bis(4-pyridyl)-3,4-diaza-2,4-hexadiene), for the synthesis of the KNbO3@TMU-5 hybrid material. KNbO3@TMU-5 achieved a NH3 production rate of 39.9 μmol·L-1·h-1·g-1 upon UV light irradiation, as compared to 20.5 μmol·L-1·h-1·g-1 recorded for KNbO3 under similar experimental conditions. Using different characterization techniques especially gas adsorption, cyclic voltammetry, X-ray photoelectron spectroscopy, photocurrent measurements, and Fourier transform infrared spectroscopy, it has been found that the higher photoactivity of KNbO3@TMU-5 in ammonia production is due to its higher surface area, higher electron-hole separation efficiency, and higher density of negative charges on Nb sites. This work shows that hybridization of conventional semiconductors (SCs) with photoactive MOFs can improve the photoactivity of the SC@MOF hybrid material in different reactions, especially kinetically complex reactions like photoconversion of nitrogen to ammonia.