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

Mathiesen, Jette K.; Bøjesen, Espen D.; Pedersen, Jack K.; Kjær, Emil T. S.; Juelsholt, Mikkel; Cooper, Susan; Quinson, Jonathan; Anker, Andy S.; Cutts, Geoff; Keeble, Dean S.; Thomsen, Maria S.; Rossmeisl, Jan; Jensen, Kirsten M. Ø.

doi:10.1002/smtd.202200420

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

Journal Article · 22 April 2022 · Small Methods

DOI: https://doi.org/10.1002/smtd.202200420 · OSTI ID:1872483

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Department of Chemistry and Nano‐Science Center University of Copenhagen Universitetsparken 5 Copenhagen 2100 Denmark
Interdisciplinary Nanoscience Center &, Aarhus University Centre for Integrated Materials Research Aarhus University Gustav Wieds Vej 14 Aarhus C 8000 Denmark
Department of Materials University of Oxford Parks Road Oxford OX1 3PH UK
Diamond Light Source Harwell Campus Oxford OX11 0DE UK

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.

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Sponsoring Organization:: USDOE

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1872483

Journal Information:: Small Methods, Journal Name: Small Methods Journal Issue: 6 Vol. 6; ISSN 2366-9608

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: United States

Language:: English

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