LAUSR

Desulfurization is a significant approach to producing clean fuel. The design of novel host–guest catalysts with multiple active sites at atomic‐ and nano‐scales, opens a new door to gain an ultrahigh synergistic performance for targeted applications. Herein, an in situ solvent‐free approach is conducted for synchronously implanting Pd single sites (PdSS) and nanoparticles (PdNP) into a novel Zr‐based metal–organic framework (Zr‐MOF). The optimal catalyst exhibits ultrahigh oxidative desulfurization (ODS) performance that can oxidize 1 000 ppm sulfur with diluted oxidant at 40 °C within 5 min. The turnover frequency of the catalyst at 40 °C reaches 774.7 h−1 which is 47.4 times higher than host Zr‐MOF and surpasses the most reported ODS catalysts. A substantial synergistic effect between PdSS and PdNP is responsible for the upgradation of ODS performance. Experimental and theoretical results indicate that PdSS in Zr‐MOF can readily absorb H2O2, and synergistically decompose H2O2 with the assistance of PdNP for accelerated generation of •OH radicals that dominates the ODS performance. This work provides a new solvent‐free way for in situ implanting synergistic catalytic sites into MOFs to upgrade their catalytic performance in targeted reactions.