Exploring bulk and colloidal Mg/Al hydrotalcite–Au nanoparticles hybrid materials in aerobic olefin epoxidation

Sónia R. Leandro, Ana C. Mourato, Urszula Łapińska, Olinda C. Monteiro, Cristina I. Fernandes, Pedro D. Vaz, Carla D. Nunes

Research output: Contribution to journalArticlepeer-review

24 Citations (Scopus)

Abstract

Au nanoparticles (AuNPs) were immobilized on S-containing amino acids (cysteine and methionine) Mg/Al hydrotalcite clay in both bulk and exfoliated (colloidal) forms. The Au nanoparticles were prepared by a biomimetic method using an anti-oxidant tea extract to reduce the Au salt solution. The performance of bulk and exfoliated clays with Au nanoparticles in aerobic olefin epoxidation was assessed with very interesting results. Both catalysts were very active towards the epoxide products; selectivity was found to be dependent on the catalyst form. The exfoliated catalysts yielded higher product stereoselectivity in the case of limonene epoxidation. These results can be explained by the existence of a confined environment around the AuNPs structures provided by the clay nanosheets wrapping the nanoparticles, modulating how substrates interact with the catalytic active centres. Based on experimental data mechanistic proposals were also rationalized for these catalysts showing how they assist the catalytic process.

Original languageEnglish
Pages (from-to)187-198
Number of pages12
JournalJournal of Catalysis
Volume358
DOIs
Publication statusPublished - Feb 2018
Externally publishedYes

Bibliographical note

Publisher Copyright:
© 2017 Elsevier Inc.

Funding

The authors are grateful to FCT for financial support (project UID/MULTI/00612/2013). CIF (SFRH/BD/81029/2011) and AM (SFRH/BPD/35036/2007) also acknowledge FCT for financial support. G09 calculations were made possible due to the computing resources provided by STFC Scientific Computing Department's SCARF cluster. We are also highly indebted to the expert reviewers who have pointed out critical issues deserving discussion.

FundersFunder number
Fundação para a Ciência e a TecnologiaSFRH/BD/81029/2011, UID/MULTI/00612/2013, SFRH/BPD/35036/2007

    Keywords

    • Aerobic oxidation catalysis
    • Amino acids
    • Clays
    • Gold
    • Heterogeneous catalysis
    • Nanoparticles
    • Radical mechanism

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