Disentangling Competitive and Synergistic Chemical Reactivities During the Seeded Growth of High-Entropy Alloys on High-Entropy Metal Sulfide Nanoparticles.

The seeded growth of one type of nanoparticle on the surface of another is foundational to synthesizing many multifunctional nanostructures. High-entropy nanoparticles that randomly incorporate five or more elements offer enhanced properties due to synergistic interactions. Incorporating high-entropy nanoparticles into seeded growth platforms is essential for merging their unique properties with the functional enhancements that arise from particle-particle interactions. However, the complex compositions of high-entropy materials complicate the seeded growth process due to competing particle growth and chemical reactivity pathways. Here, we design and synthesize a 36-member nanoparticle library to identify and disentangle these competitive interactions, ultimately defining chemical characteristics that underpin the seeded growth of high-entropy alloys on high-entropy metal sulfide nanoparticles. As a model system, we focus on (Cu,Zn,Co,In,Ga)S-SnPdPtRhIr, which combines a high-entropy metal sulfide semiconductor with a high-entropy alloy catalyst. We study the seeded growth of all possible pairwise combinations of Sn, Pd, Pt, Rh, Ir, and SnPdPtRhIr on the metal sulfides CuS, ZnS, CoS, CuInS, CuGaS, and (Cu,Zn,Co,In,Ga)S, which have comparable morphologies and sizes. Through these studies, we uncover unexpected chemical reactivities, including cation exchange, redox reactions, and diffusion. Reaction temperature, threshold reduction potentials, metal/sulfide chemical reactivity, and the relative strengths of the various bonds that could be formed during particle growth emerge as the primary factors that underpin seeded growth. Finally, we disentangle these competitive and synergistic chemical reactivities to generate a reactivity map that provides practical guidelines for achieving seeded growth in compositionally complex systems.