skip to main content

Explore Research Products in the PAR
It may take a few hours for recently added research products to appear in PAR search results.


Title: A combined TEM and SAXS study of the growth and self-assembly of ultrathin Pt nanowires
Abstract Ultrathin Pt nanowires possess high activity for various electrocatalytic applications. However, little work has focused on understanding their growth mechanisms. Herein, we utilize a combination of time-dependent, ex situ transmission electron microscopy (TEM) and small angle x-ray scattering (SAXS) techniques to observe the growth process in addition to associated surfactant-based interactions. TEM images indicate that initially nanoparticles are formed within 30 s; these small ‘seed’ particles quickly elongate to form ultrathin nanowires after 2 min. These motifs remain relatively unchanged in size and shape up to 480 min of reaction. Complementary SAXS data suggests that the initial nanoparticles, which are coated by a surfactant bilayer, arrange into a bcc superlattice. With increasing reaction time, the bcc lattice disappears as the nanoparticles grow into nanowires, which then self-assemble into a columnar hexagonal structure in which the individual nanowires are covered by a CTAB monolayer. The hexagonal structure eventually degrades, thereby leading to the formation of lamellar stacking phases comprised of surfactant bilayers. To the best of our knowledge, this is the first time that SAXS has been used to monitor the growth and self-assembly of Pt nanowires. These insights can be used to better understand and rationally control the formation of anisotropic motifs of other metallic nanostructures.  more » « less
Award ID(s):
1807640
PAR ID:
10382132
Author(s) / Creator(s):
; ;
Date Published:
Journal Name:
Nanotechnology
Volume:
33
Issue:
47
ISSN:
0957-4484
Page Range / eLocation ID:
475602
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. ; ; ; ; ; ; ; ; ; ( , ChemNanoMat)
    Abstract

    We have successfully synthesized ultrathin nanowires of pure Pt, Pt99Ni1, Pt9Ni1, and Pt7Ni3using a modified room‐temperature soft‐template method. Analysis of both methanol oxidation reaction (MOR) and ethanol oxidation reaction (EOR) results found that the Pt7Ni3samples yielded the best performance with specific activities of 0.36 and 0.34 mA/cm2respectively. Additionally, formic acid oxidation reaction (FAOR) tests noted that both Pt and PtNi nanowires oxidize small organic molecules (SOMs) via an indirect pathway. CO oxidation data suggests little measurable performance without any pre‐reduction treatment; however, after annealing in H2, we detected significantly improved CO2formation for both Pt9Ni1and Pt7Ni3motifs. These observations highlight the importance of pre‐treating these nanowires under a reducing atmosphere to enhance their performance for CO oxidation. To explain these findings, we collected extended x‐ray adsorption fine structure (EXAFS) spectroscopy data, consistent with the presence of partial alloying with a tendency for Pt and Ni to segregate, thereby implying the formation of a Pt‐rich shell coupled with a Ni‐rich core. We also observed that the degree of alloying within the nanowires increased after annealing in a reducing atmosphere, a finding deduced through analysis of the coordination numbers and calculations of Cowley's short range order parameters.

     
    more » « less
  2. ; ; ; ; ; ( , Chemical Science)
    null (Ed.)
    A number of complementary, synergistic advances are reported herein. First, we describe the ‘first-time’ synthesis of ultrathin Ru 2 Co 1 nanowires (NWs) possessing average diameters of 2.3 ± 0.5 nm using a modified surfactant-mediated protocol. Second, we utilize a combination of quantitative EDS, EDS mapping (along with accompanying line-scan profiles), and EXAFS spectroscopy results to probe the local atomic structure of not only novel Ru 2 Co 1 NWs but also ‘control’ samples of analogous ultrathin Ru 1 Pt 1 , Au 1 Ag 1 , Pd 1 Pt 1 , and Pd 1 Pt 9 NWs. We demonstrate that ultrathin NWs possess an atomic-level geometry that is fundamentally dependent upon their intrinsic chemical composition. In the case of the PdPt NW series, EDS mapping data are consistent with the formation of a homogeneous alloy, a finding further corroborated by EXAFS analysis. By contrast, EXAFS analysis results for both Ru 1 Pt 1 and Ru 2 Co 1 imply the generation of homophilic structures in which there is a strong tendency for the clustering of ‘like’ atoms; associated EDS results for Ru 1 Pt 1 convey the same conclusion, namely the production of a heterogeneous structure. Conversely, EDS mapping data for Ru 2 Co 1 suggests a uniform distribution of both elements. In the singular case of Au 1 Ag 1 , EDS mapping results are suggestive of a homogeneous alloy, whereas EXAFS analysis pointed to Ag segregation at the surface and an Au-rich core, within the context of a core–shell structure. These cumulative outcomes indicate that only a combined consideration of both EDS and EXAFS results can provide for an accurate representation of the local atomic structure of ultrathin NW motifs. 
    more » « less
  3. ; ; ; ; ; ; ; ; ; ; et al ( , Advanced Materials)
    Abstract

    Facile fabrication of advanced catalysts toward oxygen reduction reaction with improving activity and stability is significant for proton‐exchange membrane fuel cells. Based on a generic solid‐state reaction, this study reports a modified hydrogen‐assisted, gas‐phase synthesis for facile, scalable production of surfactant‐free, thin, platinum‐based nanowire‐network electrocatalysts. The free‐standing platinum and platinum–nickel alloy nanowires show improvements of up to 5.1 times and 10.9 times for mass activity with a minimum 2.6% loss after an accelerated durability test for 10k cycles; 8.5 times and 13.8 times for specific activity, respectively, compared to commercial Pt/C catalyst. In addition, combined with a wet impregnation method, different substrate‐materials‐supported platinum‐based nanowires are obtained, which paves the way to practical application as a next‐generation supported catalyst to replace Pt/C. The growth stages and formation mechanism are investigated by an in situ transmission electron microscopy study. It reveals that the free‐standing platinum nanowires form in the solid state via metal‐surface‐diffusion‐assisted oriented attachment of individual nanoparticles, and the interaction with gas molecules plays a critical role, which may represent a gas‐molecular‐adsorbate‐modified growth in catalyst preparation.

     
    more » « less
  4. ; ; ; ( , Molecules)
    null (Ed.)
    We synthesized and subsequently rationalized the formation of a series of 3D hierarchical metal oxide spherical motifs. Specifically, we varied the chemical composition within a family of ATiO3 (wherein “A” = Ca, Sr, and Ba) perovskites, using a two-step, surfactant-free synthesis procedure to generate structures with average diameters of ~3 microns. In terms of demonstrating the practicality of these perovskite materials, we have explored their use as supports for the methanol oxidation reaction (MOR) as a function of their size, morphology, and chemical composition. The MOR activity of our target systems was found to increase with decreasing ionic radius of the “A” site cation, in order of Pt/CaTiO3 (CTO) > Pt/SrTiO3 (STO) > Pt/BaTiO3 (BTO). With respect to morphology, we observed an MOR enhancement of our 3D spherical motifs, as compared with either ultra-small or cubic control samples. Moreover, the Pt/CTO sample yielded not only improved mass and specific activity values but also a greater stability and durability, as compared with both commercial TiO2 nanoparticle standards and precursor TiO2 templates. 
    more » « less
  5. ; ; ; ; ( , Advanced Functional Materials)
    Abstract

    The nucleation and growth of nanoparticles are critical processes determining the size, shape, and properties of resulting nanoparticles. However, understanding the complex mechanisms guiding the formation and growth of colloidal multielement alloy nanoparticles remains incomplete due to the involvement of multiple elements with different properties. This study investigates in situ colloidal synthesis of multielement alloys using transmission electron microscopy (TEM) in a liquid cell. Two different pathways for nanoparticle formation in a solution containing Au, Pt, Ir, Cu, and Ni elements, resulting in two distinct sets of particles are observed. One set exhibits high Au and Cu content, ranging from 10 to 30 nm, while the other set is multi‐elemental, with Pt, Cu, Ir, and Ni, all less than 4 nm. The findings suggest that, besides element miscibility, metal ion characteristics, particularly reduction rates, and valence numbers, significantly impact particle composition during early formation stages. Density functional theory (DFT) simulations confirm differences in nanoparticle composition and surface properties collectively influence the unique growth behaviors in each nanoparticle set. This study illuminates mechanisms underlying the formation and growth of multielement nanoparticles by emphasizing factors responsible for chemical separation and effects of interplay between composition, surface energies, and element miscibility on final nanoparticles size and structure.

     
    more » « less
  • Citation Formats
  • MLA
  • APA
  • Chicago
  • BibTeX
  • Save / Share this Record
  • Send to Email