Active site-exposed Bi₂WO₆@BiOCl heterostructures for photocatalytic hydrogenation of nitroaromatic compounds

Constructing heterostructured photocatalysts with highly exposed active sites proves to be an efficient strategy to improve the photocatalytic performance of bismuth-based photocatalysts. In this work, active site-exposed Bi₂WO₆@BiOCl (BWO@BOC) heterostructure composites based on two bismuth-based materials were fabricated by an in situ growth method for improving the photocatalytic hydrogenation of 4-aniline (4-NA) to p-phenylenediamine (PPD). BWO@BOC exhibited enhanced photoactivity for 4-NA hydrogenation compared to pure BWO and BOC. The optimal BWO@BOC composites displayed the highest conversion rate of 4-NA to PPD up to 99.3% within 12 min, with an apparent reaction rate constant of 0.414 min^-1, which is 3.3 times that of pure BOC. The photoactivity enhancement is mainly ascribed to the construction of a tight Z-scheme heterostructure with improved light harvesting properties and charge carrier transport efficiency, which were revealed by optical and photoelectrochemical characterization, respectively. Furthermore, the products of the hydrogenation process were monitored by in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) to gain a better insight into the 4-NA hydrogenation mechanism.