The development of a highly efficient and secure system for hydrogen storage and delivery is currently imperative, yet has great challenges. Herein, a series of highly dispersed and small cobalt nanoparticles supported by MOF-derived hierarchically porous carbon were synthesized by employing a selective atom evaporated-isolation strategy with bimetal Co/Zn-MOF-74 used as sacrificial template. The formation of ultrasmall Co nanoparticles in the hierarchically porous carbon was largely due to the assistance of doped Zn atoms in Co/Zn-MOF-74 precursors, which restricted their agglomeration during pyrolysis. Detailed catalytic results indicated that both the mole ratio of Co/Zn and the pyrolysis temperature were crucial to modulate their dehydrogenation performance for ammonia–borane, of which the as-synthesized 30% Co/HPC catalyst pyrolyzed under 900 °C exhibited the highest catalytic activity. Furthermore, these Co/HPC catalysts also showed good structure stability and magnetically reusability, which, together with the superior activity, enabled them to hold great promise for practical applications.

Transition‐metal phosphides (TMP), particularly cobalt phosphide (CoP) has drawn considerable attention in heterogeneous catalysis during the past few years due to their robust stability, corrosion resistance and low cost. In this work, a series of hierarchically porous carbon supported non‐precious CoP NPs by using Co–MOF‐74 as self‐sacrificed templates have been synthesized through a stepwise calcinations and phosphorization method. The catalytic performance of the resulted CoP@HPC−T composites toward the hydrolytic dehydrogenation of ammonia‐borane (AB) has been systematically investigated, of which, the resultant CoP@HPC−T calcinated at 500 °C showed the best catalytic performance with a TOF value of 27.7 min−1, and relatively low activation energy (42.55 kJ/mol) even comparable to those reported noble metal catalysts. Furthermore the robust structure of CoP@HPC−T compared to the Co@HPC−T counterpart in the recycle tests, demonstrating their great potential for practical application.

In situ synthesis of core–shell carbon enclosed CoNi alloys achieves efficient heterogeneous catalysis.