Browse by author
Lookup NU author(s): Dr Simon DohertyORCiD, Dr Julian Knight, Dr Hussam Alharbi, Reece Paterson, Dr Corinne Wills, Dr Casey Dixon, Professor Lidija Siller
This work is licensed under a Creative Commons Attribution 4.0 International License (CC BY 4.0).
Platinum nanoparticles stabilized by imidazolium-based phosphine-decorated Polymer Immobilized Ionic Liquids (PPh2-PIIL) catalyze the hydrolytic evolution of hydrogen from sodium borohydride with remarkable efficiency, under mild conditions. The composition of the polymer influences efficiency with the catalyst based on a polyethylene glycol modified imidazolium monomer (PtNP@PPh2-PEGPIILS) more active than its N-alkylated counterpart (PtNP@PPh2-N-decylPIILS). The maximum initial TOF of 169 moleH2.molcat-1.min-1 obtained at 30 °C with a catalyst loading of 0.08 mol% is among the highest to be reported for the aqueous phase hydrolysis of sodium borohydride catalyzed by a PtNP-based system. Kinetic studies revealed that the activation energy (Ea) of 23.9 kJ mol-1 for the hydrolysis of NaBH4 catalyzed by PtNP@PPh2-PEGPIILS is significantly lower than that of 35.6 kJ mol-1 for PtNP@PPh2-N-decylPIILS. Primary kinetic isotope effects kH/kD of 1.8 and 2.1 obtained with PtNP@PPh2-PEGPIILS and PtNP@PPh2-N-decylPIILS, respectively, for the hydrolysis with D2O support a mechanism involving rate determining oxidative addition or s-bond metathesis of the O-H bond. Catalyst stability and reuse studies showed that PtNP@PPh2-PEGPIILS retained 70% of its activity across five runs; the gradual drop in conversion appears to be due to poisoning of the catalyst by the accumulated metaborate product as well as the increased viscosity of the reaction mixture.
Author(s): Doherty S, Knight JG, Alharbi HY, Paterson R, Wills C, Dixon C, Siller L, Chamberlain TW, Griffiths A, Collins SM, Wu KJ, Simmonds SD, Bourne RA, Lovelock KRJ, Seymour J
Publication type: Article
Publication status: Published
Journal: ChemCatChem
Year: 2022
Volume: 14
Issue: 4
Print publication date: 18/02/2022
Online publication date: 20/12/2021
Acceptance date: 17/12/2021
Date deposited: 28/01/2022
ISSN (print): 1867-3880
ISSN (electronic): 1867-3899
Publisher: Wiley-VCH
URL: https://doi.org/10.1002/cctc.202101752
DOI: 10.1002/cctc.202101752R1
Altmetrics provided by Altmetric