Aromatic Base Confined Ultrafine Cobalt Nickel Nanoparticles for Selective Dehydrogenation of Ammonia Borane

The rational design of highly active non‐precious metal catalysts remains a significant challenge in the field of heterogeneous catalysis. In this study, we developed a novel alkaline engineering two‐dimensional titanium carbide nitride (Ti 3 CN) support via aromatic base phenylenediamine (PDA) modification and subsequently immobilized ultrafine Co 0.9 Ni 0.1 nanoparticles (NPs) using a wet chemical reduction method. By virtue of alkaline coordinating configuration, PDA‐Ti 3 CN‐supported Co 0.9 Ni 0.1 nanocatalytic systems not only exhibited a high specific surface area and excellent metal dispersion, but also possessed an unique electron‐rich microenvironment due to abundant amine groups as Lewis base sites. Such a novel coordinating configuration significantly enhanced the adsorption and polarization of water molecules and optimized the adsorption–desorption processes of H 2 O and ammonia borane (AB). The optimized Co 0.9 Ni 0.1 /PDA‐Ti 3 CN catalyst demonstrated exceptional catalytic performance for AB hydrolysis, achieving a remarkable turnover frequency (TOF) of 2298 h −1 with 100% hydrogen selectivity. This study presents a versatile strategy for the rational design and development of efficient catalysts for hydrogen production.