Synthesis of Platinum Single-Twinned Right Bipyramid and {111}-Bipyramid through Targeted Control over Both Nucleation and Growth Using Specific Peptides

Abstract

Shape-controlled synthesis requires rigorous kinetic control over both nucleation and growth. For platinum (Pt), to date it is still challenging to generate twinned seeds in nucleation in a controllable fashion. Here, we report that a specific Pt binding peptide BP7A is able to mediate and stabilize single-twinned seeds formation at the nucleation stage under mild conditions. Importantly, it targets the control over nucleation directly. Combining with control over growth, we further demonstrate the rational design and synthesis of single-twinned structures, right bipyramid and {111}-bipyramid, by incorporating targeted facet stabilization over {100} facet and {111} facet, respectively. To the best of our knowledge, this is the first report on the successful synthesis of single-twinned bipyramids for Pt nanocrystals (NCs) with high yields. The work here demonstrates the power of biomolecules in recognizing and mediating inorganic nanomaterials synthesis, guiding the formation of material structures that are otherwise unconventional, and hence presenting one step further toward predictable and programmable biomimetic synthesis.

Small Adsorbate‐Assisted Shape Control of Pd and Pt Nanocrystals

“…The structure of the octapods was also verified by a set of tilted TEM measurements. When octapod crystals were oriented along the [110] zone axis, some of their (411) faces were driven parallel to the TEM beam. Indeed, some (2n-1, 1, 1) steps [e.g., (311), (511)] made of subfacets of (111) and (100) planes were clearly observed (Figure 6i).…”

“…In addition to halide, CO, and monodendate amines that have been studied, carboxylic acids, alkenes, alkynes and multidendate ligands including biomolecules should be considered and may represent a future avenue of research. [110,111] …”

Facile synthesis of high-purity single-twinned Au nanocrystals through manipulation of reaction kinetics

“…Great efforts have been explored and singletwinned structures were obtained for Au, 3 Ag, 4 Pd, 5 and Pt. 6 For Au NCs, to our knowledge, although single-twinned bipyramids with different shapes (e.g., hexagonal, pentagonal, and {110}-covered triangular bipyramids) 3a-c as well as singly twinned squashed dodecahedron 3d and shield-like NCs with high-index facets 3e have been reported, no effective strategy was identified to control the formation of single-twinned Au seeds and obtain high-yield Au RBPs. Single-crystal and multi-twinned NCs are usually coexisted as side products along with the generation of singly twinned structures in one batch of synthesis.…”

Biomimetic Synthesis of an Ultrathin Platinum Nanowire Network with a High Twin Density for Enhanced Electrocatalytic Activity and Durability

“…[34][35][36][37][38] Particularly, peptide BP7A has been demonstrated to lead to exclusive formation of twinned Pt nanoparticles, which is uncommon in conventional syntheses. [38] Here, we further exploit its potential for the synthesis of 1D Pt nanowire with dense twin defects. Although nanowires with twin defects have been observed before, the occurrence of twinning appeared relatively random and rare.…”

“…[39,40] The occurrence of abundant twinning may be the result of the attachment growth mode of the nanowire mediated by the peptide, which will be discussed in the following; and also comes from the specific stabilization of the peptide to twinning defects as previously reported. [38] More mechanistic studies regarding the stabilization of the peptide to twinning defects are under way. Despite its ultrathin and twin-rich nature, the crystallinity of Pt MTNN was confirmed by powder X-ray diffraction (Figure 1 H).…”