Binary Heterogroup-Templated Scaffolds of Polyoxopalladates as Precatalysts for Plasma-Assisted Ammonia Synthesis

In addition to improving the synthetic efficiency, the template method can do a lot more in the chemistry of polyoxopalladates (POPs), such as the establishment of novel metal-oxo scaffolds. In this endeavor, a binary system comprising heterogroups of nonmetallic {As/ SiO4} and metallic {VO4/5} successfully fulfills the templated growth of two POPs with unprecedented seesaw- and spindle-like prototypes. Of these, self-aggregation of heterogroups beacons an effective route to break the highly symmetrical Pd-II- oxo matrix and to force the arrangement of addenda in a nonconventional manner. Aside from the interest in their structural features, the as-made POPs are available for immobilization on the mesoporous SBA-15 as precatalysts for ammonia synthesis. The outer cover of heterogroups in the POP precursors contributes to the ultrafine size and uniform distribution of derived Pd-0 nanoparticles (PdNPs). With the help of plasma activation on H-2 and N-2, such PdNPs-SBA15 catalysts significantly improve the production performance of NH3, showcasing the maximum synthesis rate of 64.42 mu mol/(min center dot g(cat)) with the corresponding energy yield as high as 4.38 g-NH3/kWh.

Automated summary

Template method not only improves the synthetic efficiency of polyoxopalladates (POPs), but also plays many other roles in polyoxopalladate chemistry, such as establishing novel metal-oxo scaffolds. A binary system composed of nonmetallic {As/SiO4} and metallic {VO4/5} heterogroups successfully creates two POPs with unprecedented seesaw- and spindle-like prototypes. The self-aggregation of heterogroups helps break the highly symmetrical Pd-II-oxo matrix and force the unconventional arrangement of addenda. Additionally, the as-made POPs can be immobilized on mesoporous SBA-15 as precatalysts for ammonia synthesis. The outer cover of heterogroups in the POP precursors contributes to the ultrafine size and uniform distribution of derived Pd-0 nanoparticles (PdNPs).