Formic acid (FA) represents a convenient H-2-source/storage material. Herein, we introduce two highly efficient heterogeneous catalysts for H-2-generation from FA, Fe-II/RPPh2@SiO2 and Fe-II/polyRPhphos@SiO2, prepared by covalently immobilizing Fell-phosphine-complexes on SiO2 particles. EPR shows that in both the homogeneous and the heterogenized system the Fe atom has similar ligand-field parameters, which indicate a moderately-tight coordination of the Fe atom (D=0.455 cm(-1)) that allows rapid substrate accessibility. Heterogenization of the-commonly used -Fe-II/P(CH2CH2PPh2)(3) system, increased its TOF by 170% vs. the homogeneous catalyst. Remarkably, Fe-II/RPPh2@SiO2 is able to generate up to 14lt of H-2 within 6h while homogeneous Fe-II/RPPh2 was totally inactive. Both heterogeneous catalysts are able to produce H-2 from FA at near-ambient temperatures (55-90 degrees C) with no co-catalyst added, with high selectivity and activity, and show excellent stability and reusability. (C) 2015 Elsevier B.V. All rights reserved.