Enthalpy-Driven Design Rules for Multi-Shell Multimetallic Nanoparticles
- 1Center for High Entropy Alloy Catalysis, Department of Chemistry, University of Copenhagen, Universitetsparken 5, København Ø, Denmark, 2100
- 2Center for Sustainable Energy Materials, Department of Chemistry, Aarhus University, Langelandsgade 140, Aarhus C, Denmark, 8000
Abstract
Multimetallic nanoparticles (NPs) offer access to a vast compositional and architectural design space, yet controlled formation of core-shell and multi-shell architectures rapidly becomes unpredictable as compositional complexity increases. As a result, architectural outcomes are often regarded as system-specific and governed primarily by kinetic effects. Here, we identify a unifying thermodynamic principle that governs shell formation in multimetallic NPs based on binary mixing enthalpies and phase behaviour. By systematically establishing enthalpy-driven rules in binary NPs and extending them to higher-order compositions, we show that elemental segregation and the composition and sequence of multiple shells in NPs containing up to five elements are predictable despite their combinatorial complexity, even when synthesised in a simple one-pot wet-chemical reaction. These results demonstrate that thermodynamic interactions maintain predictive power as compositional complexity increases and provide a general framework for rationalising architectural design in multimetallic NPs.
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BibTeX
@misc{mathiesen2026enthalpydriven,
title = {{Enthalpy-Driven Design Rules for Multi-Shell Multimetallic Nanoparticles}},
author = {Jette Katja Mathiesen and Tobias Mølgaard Nielsen and Rasmus Rohde and Rebekka Klemmt and Christian Møgelberg Clausen and Ulrik Friis-Larsen and Rebecca Katharina Pittkowski and Jan Rossmeisl and Kirsten Marie Ørnsbjerg Jensen and Espen Drath Bøjesen},
howpublished = {ChemRxiv},
year = {2026},
month = oct,
doi = {10.26434/chemrxiv.15010887/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010887/v1},
note = {CC BY-NC-ND},
}
RIS
TY - UNPB
TI - Enthalpy-Driven Design Rules for Multi-Shell Multimetallic Nanoparticles
AU - Jette Katja Mathiesen
AU - Tobias Mølgaard Nielsen
AU - Rasmus Rohde
AU - Rebekka Klemmt
AU - Christian Møgelberg Clausen
AU - Ulrik Friis-Larsen
AU - Rebecca Katharina Pittkowski
AU - Jan Rossmeisl
AU - Kirsten Marie Ørnsbjerg Jensen
AU - Espen Drath Bøjesen
PY - 2026
DA - 2026/10/22
PB - ChemRxiv
DO - 10.26434/chemrxiv.15010887/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010887/v1
AB - Multimetallic nanoparticles (NPs) offer access to a vast compositional and architectural design space, yet controlled formation of core-shell and multi-shell architectures rapidly becomes unpredictable as compositional complexity increases. As a result, architectural outcomes are often regarded as system-specific and governed primarily by kinetic effects. Here, we identify a unifying thermodynamic principle that governs shell formation in multimetallic NPs based on binary mixing enthalpies and phase behaviour. By systematically establishing enthalpy-driven rules in binary NPs and extending them to higher-order compositions, we show that elemental segregation and the composition and sequence of multiple shells in NPs containing up to five elements are predictable despite their combinatorial complexity, even when synthesised in a simple one-pot wet-chemical reaction. These results demonstrate that thermodynamic interactions maintain predictive power as compositional complexity increases and provide a general framework for rationalising architectural design in multimetallic NPs.
ER -