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In Situ Small-Angle X-ray Scattering Studies on the Growth Mechanism of Anisotropic Platinum Nanoparticles.

ABSTRACT: Shape-controlled platinum nanoparticles exhibit extremely high oxygen reduction activity. Platinum nanoparticles were synthesized by the reduction of a platinum complex in the presence of a soft template formed by organic surfactants in oleylamine. The formation of platinum nanoparticles was investigated using in situ small-angle X-ray scattering experiments. Time-resolved measurements revealed that different particle shapes appeared during the reaction. After the nuclei were generated, they grew into anisotropic rod-shaped nanoparticles. The shape, size, number density, reaction yield, and specific surface area of the nanoparticles were successfully determined using small-angle X-ray scattering profiles. Anisotropic platinum nanoparticles appeared at a low reaction temperature (∼100 °C) after a short reaction time (∼30 min). The aspect ratio of these platinum nanoparticles was correlated with the local packing motifs of the surfactant molecules and their stability. Our findings suggest that the interfacial structure between the surfactant and platinum nuclei can be important as a controlling factor for tailoring the aspect ratio of platinum nanoparticles and further optimizing the fuel cell performance.

SUBMITTER: Yoshimune W

PROVIDER: S-EPMC8153930 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:Polymerization-induced self-assembly (PISA) is a powerful platform technology for the rational and efficient synthesis of a wide range of block copolymer nano-objects (e.g., spheres, worms or vesicles) in various media. In situ small-angle X-ray scattering (SAXS) studies of reversible addition-fragmentation chain transfer (RAFT) dispersion polymerization have previously provided detailed structural information during self-assembly (see M. J. Derry et al., Chem. Sci. 2016 , 7 , 5078 - 5090 ). However, conducting the analogous in situ SAXS studies during RAFT aqueous emulsion polymerizations poses a formidable technical challenge because the inherently heterogeneous nature of such PISA formulations requires efficient stirring to generate sufficiently small monomer droplets. In the present study, the RAFT aqueous emulsion polymerization of 2-methoxyethyl methacrylate (MOEMA) has been explored for the first time. Chain extension of a relatively short non-ionic poly(glycerol monomethacrylate) (PGMA) precursor block leads to the formation of sterically-stabilized PGMA-PMOEMA spheres, worms or vesicles, depending on the precise reaction conditions. Construction of a suitable phase diagram enables each of these three morphologies to be reproducibly targeted at copolymer concentrations ranging from 10 to 30% w/w solids. High MOEMA conversions are achieved within 2 h at 70 °C, which makes this new PISA formulation well-suited for in situ SAXS studies using a new reaction cell. This bespoke cell enables efficient stirring and hence allows in situ monitoring during RAFT emulsion polymerization for the first time. For example, the onset of micellization and subsequent evolution in particle size can be studied when preparing PGMA29-PMOEMA30 spheres at 10% w/w solids. When targeting PGMA29-PMOEMA70 vesicles under the same conditions, both the micellar nucleation event and the subsequent evolution in the diblock copolymer morphology from spheres to worms to vesicles are observed. These new insights significantly enhance our understanding of the PISA mechanism during RAFT aqueous emulsion polymerization.

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In Situ Small-Angle X-ray Scattering Studies on the Growth Mechanism of Anisotropic Platinum Nanoparticles.

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