Defect engineering and Ni promoter synergistically accelerating electron transfer to Ru0 sites in UiO-66(Ce) for dicyclopentadiene hydrogenation under mild condition
Rushuo Li, Tao Ban, Danfeng Zhao, Jing Lin, Zhiyuan Liu, Linmeng Wang, Xiubing Huang, Zhiping Tao, Ge Wang
Abstract
Olefin hydrogenation under mild condition is crucial and challenging for industrial applications. Herein, defective UiO-66(Ce) was constructed by using cyanuric acid as the molecular etching “scissors” and further to synthesize heterogeneous catalyst with highly dispersed RuNi nanoparticles (Ru 1 Ni 1.5 @UiO-66(Ce)-12 h). The construction of Ce-O-Ru/Ni heterogeneous interfaces and Ni–Ru bonds provide electron transfer channels from Ce-oxo clusters and Ni species to Ru species. Furthermore, the microenvironment and electronic structure of Ru 0 active sites were synergistically regulated by adjusting the content of metal-organic frameworks (MOFs) defects and Ni promoter, thereby enhancing the adsorption and activation ability of H–H and C=C bonds. Therefore, Ru 1 Ni 1.5 @UiO-66(Ce)-12 h achieved dicyclopentadiene saturated hydrogenation (100% conversion) to tetrahydrodicyclopentadiene (∼ 100% selectivity) under mild condition (35 °C, 1 MPa) with only 25 min. Meanwhile, the sample exhibited excellent structural stability after 6 cycles test. This study provides a promising strategy for the rational design of remarkable noble metal-based catalysts for practical applications.