Directional design of the pyridine ligand functional block fine-tuned hydrophobicity to improve the electrocatalytic nitrogen fixation performance of the Co/Ni based MOFs-derived materials

A series of isostructural Co/Ni-MOFs with different linearly bridged bipyridines as organic linkers has been designed and synthesized. Experimental studies reveal that linker engineering by tuning the functional block of the pyridine-bridging units renders these MOFs derived materials with significantly improved electrocatalytic nitrogen reduction reactions (eNRR) to NH3. Among them, at −0.4 V vs reversible hydrogen electrode the one containing a 1,3,4-thiadiazole unit exhibits the best eNRR performance in 0.1 M Na2SO4 with the highest NH3 yield (39.7 μg h−1 mg−1) and Faraday efficiency (33.3 %). This excellent nitrogen fixation performance comes from the synergistic effect of the heterojunction formed by the Co2N component that is conducive to nitrogen fixation and the Co9S8 component that inhibits hydrogen evolution in the derived material. Significantly, the systematic tuning of the bridging ligands in MOFs provides a new pathway to develop eNRR electrocatalysts.