Dual-atom Pt heterogeneous catalyst with excellent catalytic performances for the selective hydrogenation and epoxidation

Youqi Zhu,Bingxue Wang,Qinghua Zhang,Xiaoming Sun,Shubo Tian,Huijun Zhao,Qiang Fu,Wanbing Gong,Zizhan He,Jiarui Yang,Yuxiang Bu,Qi Xu,Dingsheng Wang,Lin Gu,Yadong Li,Chun Chen,Wenxing Chen

doi:10.1038/s41467-021-23517-x

Abstract

Atomically monodispersed heterogeneous catalysts with uniform active sites and high atom utilization efficiency are ideal heterogeneous catalytic materials. Designing such type of catalysts, however, remains a formidable challenge. Herein, using a wet-chemical method, we successfully achieved a mesoporous graphitic carbon nitride (mpg-C3N4) supported dual-atom Pt2 catalyst, which exhibited excellent catalytic performance for the highly selective hydrogenation of nitrobenzene to aniline. The conversion of ˃99% is significantly superior to the corresponding values of mpg-C3N4-supported single Pt atoms and ultra-small Pt nanoparticles (~2 nm). First-principles calculations revealed that the excellent and unique catalytic performance of the Pt2 species originates from the facile H2 dissociation induced by the diatomic characteristics of Pt and the easy desorption of the aniline product. The produced Pt2/mpg-C3N4 samples are versatile and can be applied in catalyzing other important reactions, such as the selective hydrogenation of benzaldehyde and the epoxidation of styrene.

Highlights

Monodispersed heterogeneous catalysts with uniform active sites and high atom utilization efficiency are ideal heterogeneous catalytic materials
The application of the superior Pt2/ mpg-C3N4 catalyst has been extended to the selective hydrogenation of benzaldehyde to benzyl alcohol and the epoxidation of styrene to styrene oxide, demonstrating the versatility of the dual-atom Pt species in heterogeneous catalysis
Upon the loading of the dual-atom Pt precursor, neither Pt nanoparticles nor nanoclusters were observed in the TEM (Supplementary Fig. 3) and high-angle annular dark field scanning transmission electron microscopy (HAADF-STEM) images (Fig. 1a)

Summary

Introduction

Monodispersed heterogeneous catalysts with uniform active sites and high atom utilization efficiency are ideal heterogeneous catalytic materials. Compared with the single-atom catalysts, dualatom catalysts possess the same advantages of uniformity in the active sites and high atom utilization efficiency[26,27,28,29], the involved two metal atoms can cooperate and play a synergistic role in optimizing interactions between the active sites and the reactants or intermediates[30,31,32,33,34,35] This may help to break the intrinsic linear scaling relationships between adsorption energies of reaction intermediates and further improve the catalytic performances. The dual-atom Pt species exhibited excellent catalytic performance toward the selective hydrogenation of nitrobenzene to aniline, and behaved much better than the corresponding Pt single-atom catalysts and Pt nanoparticles (~2 nm).

Methods

Results

Conclusion