Synergistic Palladium Single Sites and Nanoparticles Implanted Into a Novel Zr-Based Metal-Organic Framework via Solvent-Free Processing for Upgrading Oxidative Desulfurization Performance

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 degrees C within 5 min. The turnover frequency of the catalyst at 40 degrees 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 center dot 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. 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. The optimal catalyst exhibits ultrahigh oxidative desulfurization (ODS) performance that can oxidize 1 000 ppm sulfur at 40 degrees C within 5 min. A substantial synergistic effect between PdSS and PdNP is responsible for the upgradation of ODS performance. image