Silica Amino - Functionalized H2NOSiO2 nanoparticles are shown to boost by >700% the TONs of H-2 production by the [Ru/P(CH2CH2PPh2)(3)] homogeneous catalyst, using Formic Acid (FA) as substrate. Thermodynamic analysis reveals that a significant decrease of the activation energy from Ea = 41 +/- 9 kJ/mol to Ea = 28 +/- 5 kJ/mol occurs when the H2N@SiO2 solid material is used as cocatlasyt vs. the corresponding propylamine in homogeneous phase. The molecular basis of this thermodynamic mechanism was traced using EPR and variable-Temperature UV Vis spectroscopy. It is shown that H2N@SiO2 particles play a dual role: [i] they act as cocatalyst, and [ii] they serve as a template which assembles the [Ru/P(CH2CH2PPh2)(3)] catalyst on its surface, thus promoting rapid formate decomposition via [Run-hydride] species. Moreover we exemplify, for the first time, that the use of heterogenised H2N@SiO2 cocatalyst alleviates the so far required-need of excess of amines as additives i.e. a ratio [amine (H2N@SiO2): Ru complex] = [1:1] is adequate to promote high TONs, instead of [50:1] typically needed for liquid amines. (C) 2018 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.