Regulating coordination number in atomically dispersed Pt species on defect-rich graphene for n-butane dehydrogenation reaction

Xiaowen Chen,Zhimin Jia,Xiangbin Cai,Mi Peng,Yunlei Chen,Yuchen Deng,Ding Ma,Hongyang Liu,Dequan Xiao,Bingbao Mei,Zheng Jiang,Ning Wang,Xiaodong Wen

doi:10.1038/s41467-021-22948-w

Abstract

Metal nanoparticle (NP), cluster and isolated metal atom (or single atom, SA) exhibit different catalytic performance in heterogeneous catalysis originating from their distinct nanostructures. To maximize atom efficiency and boost activity for catalysis, the construction of structure–performance relationship provides an effective way at the atomic level. Here, we successfully fabricate fully exposed Pt3 clusters on the defective nanodiamond@graphene (ND@G) by the assistance of atomically dispersed Sn promoters, and correlated the n-butane direct dehydrogenation (DDH) activity with the average coordination number (CN) of Pt-Pt bond in Pt NP, Pt3 cluster and Pt SA for fundamentally understanding structure (especially the sub-nano structure) effects on n-butane DDH reaction at the atomic level. The as-prepared fully exposed Pt3 cluster catalyst shows higher conversion (35.4%) and remarkable alkene selectivity (99.0%) for n-butane direct DDH reaction at 450 °C, compared to typical Pt NP and Pt SA catalysts supported on ND@G. Density functional theory calculation (DFT) reveal that the fully exposed Pt3 clusters possess favorable dehydrogenation activation barrier of n-butane and reasonable desorption barrier of butene in the DDH reaction.

Highlights

Metal nanoparticle (NP), cluster and isolated metal atom exhibit different catalytic performance in heterogeneous catalysis originating from their distinct nanostructures
It has been found that well-dispersed nanoparticles (NPs), clusters, and isolated metal atoms exhibited surprisingly different catalytic performances from bulk materials with the development of the advanced characterization tools and wellcontrolled synthesis technology, leading to the establishment of the structure–performance relationship at the atomic level[3,4,5,6,7,8,9,10,11]
The highly dispersed subnanometer-sized metal clusters (

Summary

Introduction

Metal nanoparticle (NP), cluster and isolated metal atom (or single atom, SA) exhibit different catalytic performance in heterogeneous catalysis originating from their distinct nanostructures. We successfully fabricate fully exposed Pt3 clusters on the defective nanodiamond@graphene (ND@G) by the assistance of atomically dispersed Sn promoters, and correlated the n-butane direct dehydrogenation (DDH) activity with the average coordination number (CN) of Pt-Pt bond in Pt NP, Pt3 cluster and Pt SA for fundamentally understanding structure (especially the sub-nano structure) effects on n-butane DDH reaction at the atomic level. The highly dispersed subnanometer-sized metal clusters (

Methods

Results

Conclusion