In this study for the first time p(4-VP) (poly(4-vinyl pyridine)) colloidal ionic liquid particles derived from 4-VP (4-vinyl pyridine) are reported, used in the preparation of a catalyst system by loading metal salts such as CoCI2 and NiCl2 from ethyl alcohol solutions into the modified p(4-VP) particles, and used for hydrogen generation from NaOH-free hydrolysis of NaBH4. Colloidal ionic liquids containing 0.054 mmol Co and Ni were used in NaOH-free hydrolysis of 0.30 g NaBH4 in 50 mL water at 40 degrees C and 1000 rpm mixing rate. The reaction rates relating to hydrolysis of NaBH4 were 3148 (mL H-2) (min)(-1) (g of Co)(-1) for Co, and 1803 (mL H2) (min)(-1) (g of Ni)(-1) for Ni. The effect of metal loading time, NaBH4 concentration, temperature, and kinetic parameters were also investigated. The activation energy, enthalpy, and activation entropy for the reaction of NaBH4 in the presence of the colloidal dicationic catalyst system were calculated as 43.98 kJ/mol, 40.38 kJ/mol, and -178.22 J/mol.K, respectively. (C) 2013 Elsevier Ltd. All rights reserved.