Nanostructured Pd[sbnd]Pt nanoparticles: evidences of structure/performance relations in catalytic H2 production reactions

Abstract

A widespread approach to modulate the performances of heterogeneous catalysts is the use of bimetallic nanoparticles (NPs) as the active phase. However, studying the relationship between the NPs structure and catalytic properties requires well-defined systems, having uniform composition, size and nanostructure, which cannot be achieved by traditional methods (e.g. impregnation). Here, we developed wet-chemistry synthetic routes to prepare PdPt NPs or Pt-core@Pd-shell NPs of small size and well-controlled composition and structure, protected by mercaptoundecanoic acid (MUA) moieties. The pristine NPs were tested for H2 production by NH3BH3 hydrolysis, in order to systematically investigate the effect of composition and of synthetic route on the activity of the systems. Depending on the preparation method, two distinct trends of activity were observed, rationalized in terms of the extent of surface functionalization by MUA. The MUA protective layer was found to effectively stabilize the NPs dispersion while maintaining high activity in certain cases (Pt-rich NPs), and was demonstrated to be essential for catalyst recycling. In order to further study structure-activity relationships of PdPt NPs after ligand removal, nanostructured PdPt@CeO2-based catalysts were prepared by self-assembly route. Regardless of the starting NPs structure (alloy or core-shell), similar water gas shift reaction performances were observed, due to the structural rearrangements occurring upon oxidation and reduction thermal treatments, which led to the formation of Pt-rich core@PdPt-shell under reducing conditions.