Rh nanoparticles supported on porous hexagonal boron nitride nanorods with hierarchical structure for highly efficient hydroformylation of olefins

Abstract

Hydroformylation would be a promising alternative for partial technological process in petrochemical industry because it is a 100% atom-economical route for large-scale production of aldehydes and alcohols from olefins and synthesis gas (H2 and CO). However, there are still a few problems such as cost-intensive recycling and harsh operating conditions etc. encountering in the ligand-modified cobalt and rhodium as homogeneous catalysts in practical applications. Responding to the challenges, to exploit heterogeneous catalysts especially supported catalysts is desired and needs to make more efforts. Here, porous boron nitride (p-BN) with hierarchical structure is designed through a facile thermal polymerization procedure for catalyst support. The p-BN possesses nanorod morphology assembled by numerous highly crystallized hexagonal boron nitride (h-BN) nanoparticles with the diameter of about 20 nm as building blocks, thereby forming abundant interparticle pores. The Rh nanoparticles are then supported on p-BN by an impregnation-borohydride reduction method using RhCl3 as metal precursor, and the obtained catalyst of Rh nanoparticle supported on p-BN (Rh/p-BN) is applied in hydroformylation of styrene. The high porosity and accessible boron acid sites arising from hierarchical structure of p-BN nanorods make Rh nanoparticles homogeneously disperse on the surface of p-BN nanorods and also keep the diameter about 5 nm without further aggregations. Just for this reason, Rh/p-BN exhibits excellent activity of styrene hydroformylation with the highest turnover frequency of styrene as high as 12000 h−1, in comparison with other supported catalysts using different catalyst supports. Besides the detailed investigation of the catalytic properties of Rh/p-BN under different reaction conditions, the recycle of Rh/p-BN is also conducted for five times during which there is no significant decrease in catalytic activity. The present findings indicates that the combination of catalyst support of p-BN and metal nanoparticle catalysts could be an attractive strategy for designing heterogeneous hydroformylation catalysts.