Conjugated Nickel Phthalocyanine Derivatives for Heterogeneous Electrocatalytic H2O2 Synthesis

Abstract Electrocatalytic hydrogen peroxide (H 2 O 2 ) production has emerged as a promising alternative to the chemical method currently used in industry, due to its environmentally friendly conditions and potential for higher activity and selectivity. Heterogeneous molecular catalysts are promising in this regard, as their active site configurations can be judiciously designed, modified, and tailored with diverse functional groups, thereby tuning the activity and selectivity of the active sites. In this work, nickel phthalocyanine derivatives with various conjugation degrees are synthesized and identified as effective pH‐universal electrocatalysts for H 2 O 2 production after heterogenized on nitrogen‐decorated carbon, with increased conjugation degrees leading to boosted selectivity. This is explained by the regulated d‐band center, which optimized the binding energy of the reaction intermediate, reducing the energy barrier for oxygen reduction and leading to optimized H 2 O 2 selectivity. The best catalyst, NiPyCN/CN, exhibits a high H 2 O 2 electrosynthesis activity with ≈95% of H 2 O 2 faradic efficiency in an alkaline medium, demonstrating its potential for H 2 O 2 production.