Electronic state, abundance and microenvironment modulation of Ru nanoclusters within hierarchically porous UiO-66(Ce) for efficient hydrogenation of dicyclopentadiene

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.