4.8 Article

Breaking with the Principles of Coreduction to Form Stoichiometric Intermetallic PdCu Nanoparticles

Journal

SMALL METHODS
Volume 6, Issue 6, Pages -

Publisher

WILEY-V C H VERLAG GMBH
DOI: 10.1002/smtd.202200420

Keywords

formation mechanism; in situ X-ray total scattering; intermetallic nanoparticles; synthesis by design

Funding

  1. Villum Foundation [VKR00015416, 14922]
  2. Danish Ministry of Higher Education and Science (Structure of Materials in Real Time (SMART) grant)
  3. Danish National Research Foundation Center for High Entropy Alloy Catalysis (DNRF) [DNRF 149]
  4. Carlsberg Foundation [CF18-0705]
  5. Danish Research Council [EE20187]
  6. U.S. DOE [DE-AC02-06CH11357]

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By carefully selecting additives in nanoparticle synthesis, the morphology and structure of intermetallic PdCu NPs can be controlled. This study reveals that the formation of stoichiometric intermetallic NPs is not solely determined by standard reduction potential matching and coreduction mechanisms, but also driven by changes in the local chemistry. These findings open up new opportunities to expand the library of intermetallic NPs through synthesis by design.
Intermetallic nanoparticles (NPs) have shown enhanced catalytic properties as compared to their disordered alloy counterparts. To advance their use in green energy, it is crucial to understand what controls the formation of intermetallic NPs over alloy structures. By carefully selecting the additives used in NP synthesis, it is here shown that monodisperse, intermetallic PdCu NPs can be synthesized in a controllable manner. Introducing the additives iron(III) chloride and ascorbic acid, both morphological and structural control can be achieved. Combined, these additives provide a synergetic effect resulting in precursor reduction and defect-free growth; ultimately leading to monodisperse, single-crystalline, intermetallic PdCu NPs. Using in situ X-ray total scattering, a hitherto unknown transformation pathway is reported that diverges from the commonly reported coreduction disorder-order transformation. A Cu-rich structure initially forms, which upon the incorporation of Pd(0) and atomic ordering forms intermetallic PdCu NPs. These findings underpin that formation of stoichiometric intermetallic NPs is not limited by standard reduction potential matching and coreduction mechanisms, but is instead driven by changes in the local chemistry. Ultimately, using the local chemistry as a handle to tune the NP structure might open new opportunities to expand the library of intermetallic NPs by exploiting synthesis by design.

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