Naphthalene Monoanhydride and Perylene Composites for Efficient Photocatalytic Hydrogen Evolution and Metal-Free Heterogeneous Oxidative Amidation.

Abstract

This study explores the synthesis of two visible light active organic chromophore-based composites using naphthalene monoanhydride (Np) and 1,7-dibromoperylene monoanhydride diester (PMDE). These chromophores feature favorable optical and electronic properties and polyaromatic skeletons with anhydride functionalities that facilitate π-π interactions between the chromophore and polymeric carbon nitride (CN) or covalent connections of chromophores with NH2 groups of CN. Accordingly, heterogeneous chromophore-CN composite photocatalysts namely, Np/CN(c) and PMDE/CN(c) were prepared by adopting in situ calcination (c) and composites Np/CN(a) and PMDE/CN(a) were prepared by ex situ physical adsorption (a) methods. In situ prepared Np/CN(c) and PMDE/CN(c) composites exhibited H2 evolution rates (HER) of 1069 and 705 μmol h-1 g-1, respectively, which are significantly higher than ex situ Np/CN(a) and PMDE/CN(a) composites with HER of 465 and 252 μmol h-1 g-1, respectively. These rates are 10, 7, 4.8, and 2.5 times higher than the bulk-CN, indicating the potential of these composites for efficient photocatalytic H2 evolution. Surface area normalized HER enhancements were 3.8, 5.3, 6.6, and 4.2 times higher for Np/CN(c), PMDE/CN(c), Np/CN(a), and PMDE/CN(a) respectively compared to bulk-CN. These composite photocatalysts exhibited excellent stabilities under prolonged photoirradiation, with H2 evolution consistently increasing with the light exposure time. Additionally, these metal-free heterogeneous composites demonstrated efficient photocatalytic activities towards oxidative amidation of aromatic aldehydes, with up to 80% product yields, establishing the prospects of combining homogeneous and heterogeneous entities in a metal-free active material in solar energy harvesting.