Unraveling the Synergistic Catalytic Effects of TiO₂ and Pr₆O₁₁ on Superior Dehydrogenation Performances of α-AlH₃

The pivotal steps for the practical application of dehydrogenation of aluminum hydride (AlH3) have been to decrease the temperature and increase the content of AlH3. Herein, the initial dehydrogenation temperature of AlH3 decreased to 43 °C with the amount of released hydrogen of 8.3 wt % via introducing TiO2 and Pr6O11 with synergistic catalysis effects, and its apparent activation energy of the dehydrogenation reaction decreased to 56.1 kJ mol–1, which is 52% lower than that of pure AlH3. These differences in performances of the samples are further evaluated by determining the electron density of Al–H bonds during dehydrogenation. The multiple valence state conversions of TiO2 and Pr6O11 promoted the electron transfer of H in AlH3, and a novel dehydrogenation pathway of PrH2.37 formed simultaneously, which could accelerate the breakage of Al–H bonds. The density functional theory calculations further exhibit that there are fewer electrons around H in AlH3 and the Al–H bond energy is weaker at the atomic levels, which is more conducive to the release of hydrogen. A higher hydrogen storage capacity and a lower dehydrogenation temperature make AlH3 one of the most promising hydrogen source media for mobile applications.