Developing catalysts for dicyclopentadiene (DCPD) hydrogenation to tetrahydrodicyclopentadiene (THDCPD) at low temperature is crucial and challenging for the green and energy-saving production of high energy density aviation fuel. Herein, hierarchically porous UiO-66(Ce) encapsulate Ru nanoclusters (NCs) was successfully customized by soft template method and in-situ reduction. The mesoporous UiO-66(Ce) promoted the high dispersion of Ru NCs, and the transfer of substrate molecules. By controlling the synthesis conditions, the electronic state, abundance, and microenvironment of Ru NCs were precisely regulated. Theory calculation and experimental results revealed that metallic Ru as the main active sites greatly promoted the adsorption and activation of substrate molecules. Therefore, mesoporous UiO-66(Ce) encapsulated Ru NCs showed remarkable catalytic DCPD hydrogenation performance with DCPD conversion of 100% and THDCPD selectivity of ~100% (60 °C, only 35 min). This study has brought new inspiration and guidance to the rational design of function materials for various catalytic applications.
Li Rushuo,Ban Tao,Zhao Danfeng,Lin Jing,Liu Zhiyuan,Wang Linmeng,Huang Xiubing,Tao Zhiping,Wang Ge
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.
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