Discrete Au1(0) Stabilized by 15-Crown-5 for High-Efficiency Catalytic Reduction of Nitrophenol and Nitroaniline

Abstract

Single-atom catalysts (SACs) have been synthesized using a variety of methods in recent years, and they have shown excellent catalytic activities. However, metal atoms show a high tendency to agglomerate in liquid media, making the single atom synthesis more difficult in liquid media. The synthesis of such metal single-atom catalysts that do not have strong ligand coordination is rarely reported in the literature. Herein, we report the facile synthesis of monodispersed Au atoms (Au1) through the reduction in HAuCl4 in 15-crown-5. The complete reduction in HAuCl4 was confirmed through UV-Vis spectroscopy. In addition, the Au was found in a zero valence state after reduction, which was confirmed through XPS and XANES results. Moreover, the dispersion of Au was confirmed as a single atom (Au1) through transmission electron microscopy and spherical aberration electron microscopy. The possible structure of this catalyst was proposed by matching the EXAFS results with the structure of Au1@15-crown-5 as -(OC2H4O)-AuCl2H2. The Au1@15-crown-5 showed high activity (TOF as high as 22,075) in the reduction in nitrophenol and nitroaniline to aminophenol and phenylenediamine by sodium borohydride. Because of the monodispersion of Au atoms, its performance is much better than noble nanoparticles and non-precious metal catalysts.