Metalloporphyrin/Phthalocyanine Catalysts for Electrocatalytic Nitrogen Fixation

Metalloporphyrin/phthalocyanine complexes serve as excellent electrocatalytic models due to their well-defined MN₄, structural tunability, and chemical stability. They have been applied in many catalytic fields and have shown excellent catalytic activity, such as oxygen reduction reaction (ORR) and carbon dioxide reduction reaction (CO₂RR), etc. The application of these complexes in electrocatalytic nitrogen fixation, such as nitrogen reduction reactions (NRR), nitrate reduction reactions (NO₃RR), nitrite reduction reactions (NO₂RR), and nitrate/nitrite/nitrogen-carbon dioxide co-reduction (N₂/NO_x-CO₂RR) for urea production, has been emphasized in recent years. The main obstacles for these complexes to function effectively as electrocatalysts involve the necessity for a well-thought-out design of porphyrin/phthalocyanine structures and a more comprehensive understanding of their structure-activity relationships. This review summarizes the modifying porphyrin/phthalocyanine complex methods, constructing derivative strategies, and exploring the relevant electrocatalytic reaction mechanisms and their applications for electrocatalytic nitrogen fixation. Optimization strategies based on reaction mechanisms and catalytic performance are proposed. Finally, this comprehensive overview aims to provide professional insights that will guide future experimental and theoretical advancements in porphyrin/phthalocyanine complexes and highlight their challenges and prospects for electrocatalytic systems.