Breaking with the principles of coreduction to form stoichiometric intermetallic PdCu nanoparticles

DOI: 10.1002/smtd.202200420

Authors: Jette K. Mathiesen (University of Copenhagen) , Espen D. Bøjesen (Aarhus University) , Jack K. Pedersen (University of Copenhagen) , Emil T. S. Kjær (University of Copenhagen) , Mikkel Juelsholt (University of Oxford) , Susan Cooper (University of Copenhagen) , Jonathan Quinson (University of Copenhagen) , Andy S. Anker (University of Copenhagen) , Geoff Cutts (Diamond Light Source) , Dean S. Keeble (Diamond Light Source) , Maria S. Thomsen (University of Copenhagen) , Jan Rossmeisl (University of Copenhagen) , Kirsten M. Ø. Jensen (University of Copenhagen)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Small Methods , VOL 68

State: Published (Approved)
Published: April 2022
Diamond Proposal Number(s): 20187

Abstract: 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.

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

Subject Areas: Chemistry, Materials


Instruments: I15-1-X-ray Pair Distribution Function (XPDF)

Other Facilities: 11-ID-B at APS

Added On: 25/04/2022 09:14

Documents:
Small Methods - 2022 - Mathiesen - Breaking with the Principles of Coreduction to Form Stoichiometric Intermetallic PdCu.pdf

Discipline Tags:

Physical Chemistry Catalysis Chemistry Materials Science Nanoscience/Nanotechnology

Technical Tags:

Scattering Pair Distribution Function (PDF)