ePrints

Efficient Hydrogen Evolution from Sodium Borohydride Catalyzed by Palladium Nanoparticles Stabilized by Amine-Decorated Cross-Linked Polymer Immobilized Ionic Liquids

Lookup NU author(s): Dr Simon DohertyORCiD, Dr Julian Knight, Dr Reece PatersonORCiD, Dr Corinne Wills, Dr Elisabetta Arca, Professor Richard Bourne

Downloads

• Accepted version [.pdf]

Licence

This work is licensed under a Creative Commons Attribution 4.0 International License (CC BY 4.0).

Abstract

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-Im_xPIIL (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.

Publication metadata

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

Volume: 103

Issue: 12

Pages: 796-809

Print publication date: 01/12/2025

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)

Altmetrics

Share