TiO ₂ ‐Engineered MOFs Activate Electron‐Rich Ni Sites for Efficient and Durable Hydrogen Production

Controlling the electronic structure of non‐noble metal active sites is the central challenge to unlocking fast and durable hydrogen release from hydrous hydrazine (N 2 H 4 ·H 2 O, 8.0 wt%), a promising liquid hydrogen‐storage material. Herein, for the first time, we demonstrate that TiO 2 ‐engineered NH 2 ‐MIL‐101(Cr) enables strong electronic metal–support interaction (EMSI) to generate confined electron‐rich Ni active sites with an ultrafine size of 3.2 nm, thereby markedly accelerating the rate‐determining N–H bond activation. As a result, the Ni/TiO 2 ‐NH 2 ‐MIL‐101 delivers a turnover frequency (TOF) of 422 h −1 at 343 K for N 2 H 4 ·H 2 O dehydrogenation, 28, 10, and 4 times higher than unsupported Ni NPs (15 h −1 ), Ni/MIL‐101 (42 h −1 ), and Ni/NH 2 ‐MIL‐101 (98 h −1 ), respectively, while maintaining 100% H 2 selectivity and exceptional stability over 20 cycles, outperforming the state‐of‐the‐art nonprecious metal catalysts reported for this reaction. It also exhibits superior catalytic activity and robust durability toward hydrazine borane (N 2 H 4 BH 3 , 15.4 wt%) dehydrogenation, achieving a TOF up to 881 h −1 at 343 K. These findings demonstrate that TiO 2 ‐driven electronic activation of Ni sites in MOFs offers a generalizable support‐engineering strategy for efficient and durable hydrogen production from liquid hydrogen‐storage materials.