LiBH4@xZZCO composites are successfully synthesized by confining LiBH4 in hierarchical porous ZnO/ZnCo2O4 (ZZCO) nanoparticles via a chemical impregnation method, and the effect of ZZCO on the dehydrogenation performance is systematically investigated. It is found that dehydrogenation properties of LiBH4 are significantly improved, especially for the LiBH4@2ZZCO composite. The onset desorption temperature of LiBH4@2ZZCO is decreased to 169 degrees C, and the majority of hydrogen release occurs at 275 degrees C, much lower than raw LiBH4. In addition, 8.7 wt% H-2 could be released below 500 degrees C. Moreover, the apparent activation energy (Ea) has been reduced from 146 kJ/mol (pure LiBH4) to 120.22 kJ/mol. The improved dehydrogenation properties are attributed to the synergistic effect of nanoconfinement and destabilization of ZZCO nanoparticles. (C) 2017 Elsevier B.V. All rights reserved.