Efficient hydrolytic hydrogen evolution from sodium borohydride catalyzed by polymer immobilized ionic liquid‐stabilized platinum nanoparticles

Doherty, S. ORCID: https://orcid.org/0000-0003-1103-8090, Knight, J. G., Alharbi, H. Y., Paterson, R., Wills, C., Dixon, C., Šiller, L., Chamberlain, T. W., Griffiths, A., Collins, S. M., Wu, K., Simmons, M. D., Bourne, R. A., Lovelock, K. R. J. ORCID: https://orcid.org/0000-0003-1431-269X and Seymour, J. (2022) Efficient hydrolytic hydrogen evolution from sodium borohydride catalyzed by polymer immobilized ionic liquid‐stabilized platinum nanoparticles. ChemCatChem, 14 (4). e202101752. ISSN 1867-3899 doi: 10.1002/cctc.202101752

Abstract/Summary

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 apparent 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 σ‐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.

Item Type	Article
URI	https://reading-clone.eprints-hosting.org/id/eprint/102316
Identification Number/DOI	10.1002/cctc.202101752
Refereed	Yes
Divisions	Life Sciences > School of Chemistry, Food and Pharmacy > Department of Chemistry
Uncontrolled Keywords	Research Article, Research Articles, catalytic hydrogen generation, deuterium labelling studies, metal nanoparticles, kinetics, recycle and catalyst poisoning, sodium borohydride
Publisher	Wiley
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