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Lookup NU author(s): Dr Simon DohertyORCiD, Dr Julian Knight, Dr Reece Paterson, Dr Corinne Wills, Dr Elisabetta Arca, Professor Richard Bourne
This work is licensed under a Creative Commons Attribution 4.0 International License (CC BY 4.0).
Palladium nanoparticles stabilised by confinement in crosslinked amine-decorated polymer immobilised ionic liquids catalyse the hydrolytic evolution of hydrogen from NaBH4 under mild conditions. A series of three PIIL supports NH2-ImxPIIL (1a-c, x = 1 (1a), x = 2 (1b), x = 3 (1c), where x corresponds to the number of imidazolium cations in the repeat unit) were prepared with an increasing number of imidazolium cations such that bis(styryl)-based crosslinkers 1a and 1b contain one and two imidazolium cations, respectively, while 1c is a more extensive tris(styryl)-based crosslinker with three imidazolium cations. The composition of the support influences the performance of the PdNPs as catalysts for the hydrolysis of NaBH4 and a comparison with the corresponding unmodified polymer (PdNP@H-Im2PIIL) confirmed that incorporation of the surface coordinated amine improved catalyst performance. Palladium nanoparticles stabilised by NH2-Im2PIIL was the most efficient catalyst and the maximum initial turnover frequency of 81 molH2.molPd-1.min-1 is higher than the 59 molH2.molPd-1.min-1 and 32 molH2.molPd-1.min-1 obtained with PdNPs supported by NH2-Im1PIIL and NH2-Im3PIIL, respectively, as well as the 19 molH2.molPd-1.min-1 obtained with commercial 10 wt% Pd/C. The results of kinetic studies, apparent activation energies and deuterium isotope effects have been compared with those in the literature and support a mechanism involving rate limiting activation of an O-H bond in water. Catalyst reuses studies showed that PdNP@NH2-Im2PIIL recycled with remarkable efficiency as high conversion were maintained across five runs with the catalyst retaining over 92% of its initial activity, an improvement on the 70% retention of activity with palladium nanoparticles supported by linear amine-modified imidazolium-based polymer and supports the beneficial effect of introducing the crosslinking on catalyst longevity.
Author(s): Doherty S, Knight JG, Burgen T, Paterson Reece, Wills Corinne, Arca Elisabetta, Bourne Richard, Yan H, Chamberlain Tom
Publication type: Article
Publication status: Published
Journal: Canadian Journal of Chemistry
Year: 2025
Pages: epub ahead of print
Online publication date: 21/04/2025
Acceptance date: 03/03/2025
Date deposited: 04/03/2025
ISSN (print): 0008-4042
ISSN (electronic): 1480-3291
Publisher: Canadian Science Publishing
URL: https://doi.org/10.1139/cjc-2024-0257
DOI: 10.1139/cjc-2024-0257
ePrints DOI: 10.57711/1zcq-wk28
Data Access Statement: Data generated or analyzed during this study are provided in full within the published article and its supplementary materials. Synthesis and characterisation of crosslinkers (1a-c), amine decorated cross-linked polymer immobilised ionic liquids (2a-c), tetrachloropalladate loaded precatalysts (3a-c) and PdNP catalysts (4a-c)
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