Enhancing hydrogen storage performance of MgH2 with hollow Bi2Ti2O7 catalyst: Synergistic effects of Bi2Mg3 alloy phase and Ti polyvalency

• The hollow Bi 2 Ti 2 O 7 catalysts were synthesized by a simple thermal method. • The Bi 2 Ti 2 O 7 can effectively catalyze the hydrogen ab/desorption of MgH 2 . • The synergistic effect of multivalent Ti and Bi 2 Mg 3 promoted performance. The role of catalysts in enhancing the hydrogen storage kinetics of the Mg/MgH 2 system is pivotal. However, the exploration of efficient catalysts and the underlying principles of their design remain both a prominent focus and a significant challenge in current research. In this study, we present a bimetallic oxide of Bi 2 Ti 2 O 7 hollow sphere as a highly effective catalyst for MgH 2 . As a result, the Bi 2 Ti 2 O 7 -catalyzed Mg/MgH 2 system lowers the hydrogen desorption initiation temperature to 194.3 °C, reduces the peak desorption temperature to 245.6 °C, decreases the dehydrogenation activation energy to 82.14 kJ·mol −1 , and can absorb 5.4 wt. % of hydrogen within 60 s at 200 °C, demonstrating outstanding hydrogen ab/desorption kinetics, compared to pure MgH 2 . Additionally, it can maintain a high hydrogen capacity of 5.2 wt. %, even after 50 dehydrogenation cycles, showing good cycle stability. The characterization results show that the high-valent Bi and Ti in Bi 2 Ti 2 O 7 are reduced to their low-valent or even zero-valent metallic states during the dehydrogenation and hydrogenation process, thus establishing an in-situ multivalent and multi-element catalytic environment. Density functional theory calculations further reveal that the synergistic effects between Bi and Ti in the Bi-Ti mixed oxide facilitate the cleavage of Mg-H bonds and lower the kinetic barrier for the dissociation of hydrogen molecules, thereby substantially enhancing the kinetics of the Mg/MgH 2 system. This study presents a strategic method for developing efficient catalysts for hydrogen storage materials by harnessing the synergistic effects of metal elements. The MgH 2 –10 wt. % Bi 2 Ti 2 O 7 composite material was prepared using a combination of hydrothermal and ball milling methods, providing an effective approach to enhance hydrogen storage performance. The initial hydrogen desorption temperature of the MgH 2 –10 wt. % Bi 2 Ti 2 O 7 composite was 194.3 °C, with an initial hydrogen capacity of 6.59 wt. %. After 50 desorption cycles, the high capacity retention rate exceeded 80 %. Mechanistic analysis indicates that the synergistic effect of the in situ-formed Bi 2 Mg 3 alloy phase and the multivalent Ti can simultaneously enhance the adsorption/desorption kinetics of Mg/MgH 2 .