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April 1, 2026ACS Applied Materials & Interfaces0 citationsOpen Access

A Straightforward Access to Sustainable and Reusable Melanin-Supported Palladium Catalysts: Characterization and Application in Sonogashira Cross-Coupling Reactions

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SPSimone PotentiPLPasquale LionielloEMElisabetta Mazzotta

Key Points

  • The aim is to develop sustainable palladium catalysts using melanin for catalytic applications in cross-coupling reactions.
  • Designed and synthesized Pd@melanin hybrids from eumelanin and allomelanin.
  • Conducted XPS, HR-TEM, and XRD analyses for characterization of the catalysts.
  • Tested catalytic activity in Sonogashira cross-coupling reactions with varying substrate conditions.
  • Performed stability tests over multiple reaction cycles to evaluate leaching and performance.
  • Pd@DHImel showed the highest product yields and lowest palladium loading among tested catalysts.
  • Catalysts remained stable and gave high yields for up to eight reaction cycles without leaching.
  • Palladium was successfully reduced from Pd(II) to Pd(0) via interactions with melanin catechol groups.

Abstract

In the last decades, the impact of the emergent concept of sustainable development has driven the impressive evolution of catalytic methodologies, also stimulated by the breakthrough of new materials and nanotechnologies. Based on this evidence, we report herein the design of sustainable catalysts by addressing the unexploited potential of melanin, a class of pigments widely diffused in nature. By pursuing a straightforward and sustainable approach, we prepared a series of Pd@melanin hybrids inspired from mammalian eumelanin and fungal allomelanin. XPS analyses revealed that DHImel (DHI: 5,6-dihydroxyindole) can support palladium by promoting the reduction of Pd(II) to Pd(0) thanks to the catechol groups that can be converted into quinones. HR-TEM and XRD analyses revealed that palladium atoms are uniformly distributed, forming nanoaggregates in the face-centered cubic crystal structure with an average dimension of 8 nm. The catalytic activity of the hybrids was tested in the Sonogashira cross-coupling reaction. Overall, the collected data suggested that Pd@DHImel, with the highest product yields and lowest Pd loading, is the most efficient catalyst, even when working with deactivated aromatic iodides. Finally, stability tests indicated that the hybrid did not suffer leaching phenomena, leading to high yields for up to eight cycles.

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Cite This Study

Potenti et al. (2026) studied this question.

synapsesocial.com/papers/69cd7b575652765b073a957fhttps://doi.org/10.1021/acsami.5c23680
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