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Hydrogenation properties were investigated on the effect of Ti-based catalysis TiF4, TiO2 and TiH2 on MgH2. All these additives significantly improved the dehydrogenation performances of MgH2 but among them TiF4 shows best catalytic effect followed by TiO2 and TiH2 sequentially. Activation energy of dehydrogenation was calculated by using Kissinger’s equation. By adding Ti based additives activation energy is reduced to various degrees. Best result obtained for the MgH2+ 10 wt% TiF4. Thermogravimetric analysis (TGA) and XPS studies showed the formation of different active species due to the catalytic effects on hydrogenation/dehydrogenation kinetics.