Synergistic Interface Engineering in Co ₃ N/Co Heterostructure Enhances Catalytic Dehydrogenation of Formic Acid

ABSTRACT Formic acid (HCOOH, FA), as one of the effective liquid organic hydrogen carriers (LOHCs), demonstrates promising potential in high‐efficiency hydrogen (H 2 ) storage and release systems. It is essential yet challengeable to assemble the non‐noble metal catalysts applied in the FA dehydrogenation with satisfied performance to employ FA as a valid H 2 carrier. In this work, the zeolitic imidazolate framework‐67 (ZIF‐67) was selected as a precursor, through a simple ligand exchange of 2‐Methylimidazole with 1H‐1,2,3‐Triazole, following by the pyrolysis treatment, different cobalt (Co)‐based catalysts, Co/Co 3 N heterostructure supported on the carbon‐nitrogen material (CN), CN‐Co/Co 3 N‐x (where x represents different ligand exchange times; x = 1, 2, 3 correspond to ligand exchange times of 10, 20, and 50 min, respectively) with a heterointerface were constructed and applied in the H 2 generation by FA dehydrogenation successfully. Experimental results reveal that the optimized catalyst CN‐Co/Co 3 N‐1 could achieve a H 2 evolution rate of 5159 mL·g −1 ·h −1 under ambient pressure at 393.15 K, surpassing other reference catalysts and most of the reported non‐noble metal catalytic systems. The commendable FA dehydrogenation performance by CN‐Co/Co 3 N‐1 could be ascribed to the effective heterointerface formation between the metallic Co nanoparticles (NPs) and Co 3 N moiety, thereby exhibiting a unidirectional electron transfer from Co NPs to Co 3 N. The synergistically interfacial electronic redistribution of the Co NPs and Co 3 N could impressively modulate the adsorption of formate ions (HCOO − ) and protons (H + ) in the catalytic process of FA dehydrogenation, thereby lowering the reaction energy barrier for the improved catalytic performance. This work offers a new strategy for constructing non‐noble metal‐based heterogeneous catalysts for H 2 generation by FA dehydrogenation.