Sharp, Gregory, Lewis, Richard J., Magri, G., Liu, J., Morgan, David J.  ORCID: https://orcid.org/0000-0002-6571-5731, Davies, Thomas E., Lopez-Martín, Ángeles, Murphy, Damien M. ORCID: https://orcid.org/0000-0002-5941-4879, Folli, Andrea ORCID: https://orcid.org/0000-0001-8913-6606, Chen, Liwei, Liu, Xi and Hutchings, Graham J. ORCID: https://orcid.org/0000-0001-8885-1560
2025.
Highly efficient benzyl alcohol valorisation via the in situ synthesis of H2O2 and associated reactive oxygen species.
Green Chemistry
27
(19)
, pp. 5567-5580.
10.1039/D5GC00680E
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Abstract
The selective oxidation of chemical feedstocks via in situ production of reactive oxygen species (H2O2, ˙OOH, ˙OH, ˙O2−), represents an attractive, environmentally friendly alternative to the use of stoichiometric oxidants. Within this contribution, we demonstrate the efficacy of the in situ approach to the selective oxidation of benzyl alcohol to the commodity chemical benzaldehyde, with the alloying of Au with Pd shown to be key in significantly promoting catalytic performance. The immobilisation of AuPd nanoalloys, particularly on to a γ-Al2O3 carrier, is demonstrated to result in high selective utilisation of H2 (ca. 80%), overcoming a major hurdle that has often precluded the adoption of the in situ approach to chemical synthesis on a commercial scale, while also achieving yields of benzaldehyde in excess of 60%, over successive experiments, representing a significant step towards competitiveness with traditional oxidative processes reliant on stoichiometric oxidants. Evaluation of catalyst performance towards individual reaction pathways (i.e. H2O2 direct synthesis and benzyl alcohol oxidation in the presence of preformed H2O2), analysis by EPR spectroscopy and radical quenching experiments, indicates that reactive oxygen-based species (ROS), rather than H2O2, are primarily responsible for the observed catalysis. While the origin of these oxygen-based radicals is not fully understood, we consider that they are generated primarily as reaction intermediates formed during H2O2 synthesis over active metal surfaces.
| Item Type: | Article |
|---|---|
| Date Type: | Publication |
| Status: | Published |
| Schools: | Schools > Chemistry Research Institutes & Centres > Cardiff Catalysis Institute (CCI) |
| Publisher: | Royal Society of Chemistry |
| ISSN: | 1463-9262 |
| Funders: | Cardiff University and the Max Planck Centre for Fundamental Heterogeneous Catalysis (FUNCAT) |
| Date of First Compliant Deposit: | 9 May 2025 |
| Date of Acceptance: | 20 April 2025 |
| Last Modified: | 28 May 2025 10:45 |
| URI: | https://orca.cardiff.ac.uk/id/eprint/178174 |
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