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• Ultrafine RuNPs are stabilised by amino-modified polymer immobilized ionic liquid. • High activity for hydrolytic evolution of hydrogen from NaBH 4. • Kinetic studies confirm the hydrolysis is first order in catalyst and hydride. • Kinetic isotope studies with H 2 O/D 2 O and NaBH 4 /NaBD 4 support the proposed mechanism. • High activity retained over five reuses with only a minor reduction in conversion. Ruthenium nanoparticles stabilised by polymer immobilized ionic liquids catalyse the hydrolytic release of hydrogen from sodium borohydride. The composition of the polymer influences performance and ruthenium nanoparticles stabilised by an amine-decorated imidazolium-based polymer immobilised ionic liquid (RuNP@NH 2 -PIILS) was the most efficient with a maximum initial turnover frequency (TOF) of 177 mole H2.mol Ru −1.min−1, obtained at 30°C with a catalyst loading of 0.08 mol%; markedly higher than that of 69 mol H2.mol Ru −1.min−1 obtained with 5 wt% Ru/C and one of the highest to be reported for a RuNP catalyst. The apparent activation energy (Ea) of 38.9 kJ mol−1 for the hydrolysis of NaBH 4 catalysed by RuNP@NH 2 -PIILS is lower than that for the other polymer immobilized ionic liquid stabilised RuNPs, which is consistent with its efficacy. Comparison of the initial rates of hydrolysis in H 2 O and D 2 O catalysed by RuNP@NH 2 -PIILS gave a primary kinetic isotope effect (k H / k D) of 2.3 which supports a mechanism involving rate limiting oxidative addition of one of the O-H bonds in a strongly hydrogen-bonded surface-coordinated [BH 3 H−]—-H 2 O ensemble. The involvement of a surface-coordinated borohydride is further supported by an inverse kinetic isotope effect of 0.65 obtained from a comparison of the initial rates for the hydrolysis of NaBH 4 and NaBD 4 under the conditions of catalysis i.e., at a high hydride/catalyst mole ratio. Interestingly though, when the comparison of the initial rates of hydrolysis of NaBH 4 and NaBD 4 was conducted in dilute solution with a hydride/catalyst mole ratio of 1 a kinetic isotope effect (k H / k D) of 2.72 was obtained; this would be more consistent with concerted activation of both an O-H and B-H bond in the rate limiting step, possibly via a concerted oxidative addition-hydride transfer in the surface-coordinated hydrogen-bonded ensemble. Catalyst stability and reuse studies showed that RuNP@NH 2 -PIILS retained 71% of its activity over five runs; the gradual drop in the initial TOF with run number appears to be due to passivation of the catalyst by the sodium borate by-product as well as an increase in viscosity of the reaction mixture rather than leaching of the catalyst. [Display omitted] [ABSTRACT FROM AUTHOR]