A systematic investigation is performed on the dehydrogenation performance of TiB2-doped NaAlH4. A dramatic enhancement in the dehydrogenation kinetics of NaAlH4 is achieved by adding as-prepared TiB2 catalyst based on a low temperature solid phase reaction, whereas pure NaAlH4 exhibits a poor desorption kinetics. Thermodynamic analyses show that the onset dehydrogenation temperature of as-prepared TiB2-doped NaAlH4 is lowered to about 75 degrees C. In addition, the experimental results show that as-prepared TiB2-doped NaAlH4 after milling releases 3.60 wt.% H-2 for 1 h and 5.21 wt % H-2 for 4 h at 190 degrees C with a excellent dehydriding rate and capacity. (c) 2012 Elsevier B.V. All rights reserved.