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 PdII-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 Pd0 nanoparticles (PdNPs). With the help of plasma activation on H2 and N2, such PdNPs-SBA15 catalysts significantly improve the production performance of NH3, showcasing the maximum synthesis rate of 64.42 μmol/(min·gcat) with the corresponding energy yield as high as 4.38 g-NH3/kWh.
Keywords: X-ray diffraction; ammonia synthesis; polyoxometalates; polyoxopalladates; template effect.