Engineering atomic Pt-N3 sites on CdS nanorods for overcoming the rate-determining organic dehydrogenation in photocatalytic coproduction of H2 and value-added?…
Abstract
Employing water and biomass fuels, such as benzyl alcohol, as feedstocks for co-producing hydrogen (H2) and value-added organic chemicals under solar irradiation presents a promising strategy towards accomplishing net-zero emission objectives. However, simultaneously building the optimal hydrogen-evolution and organic-dehydrogenation centers on photocatalyst surface has long been the pursuit. Herein, a facile vacancy-based strategy was utilized to engineer atomically dispersed Pt species coordinated with three foreign ligand nitrogen atoms (Pt-N3) instead of intrinsic S atoms on CdS nanorods. The experimental observation demonstrates a distinctive electron-rich characteristics of Pt-N3 structure, markedly augmenting the photogenerated charge separation efficiency via one interfacial charge effects. The density functional theory (DFT) simulation further indicates that the foreign ligand N atoms not only maintain the low hydrogen-evolution energy barrier of Pt center, but also greatly reduce the energy barrier of rate-determining benzyl alcohol dehydrogenation by forming the strong chemical interaction between ligand N atom and intermediate. Consequently, PtN3-CdS exhibited a high photocatalytic activity for coproduction of H2 (5.4?mmol?g-1h?1) and benzaldehyde (5.2 mmol?g-1h?1) with a selectivity of 95.9?% for value-added benzaldehyde, with the anticipation of bolstering its commercial accessibility and expediting its integration into industrial applications.