Metal‐Phthalocyanine‐Based Two‐Dimensional Conjugated Metal‐Organic Frameworks for Electrochemical Glycerol Oxidation Reaction

Abstract Electrochemical glycerol oxidation reaction (GOR) is a promising candidate to couple with cathodic reaction, like hydrogen evolution reaction, to produce high‐value product with less energy consumption. Two dimensional conjugated metal–organic frameworks (2D c ‐MOFs), comprising square‐planar metal‐coordination motifs (e.g., MO 4 , M(NH) 4 , MS 4 ), are notable for their programable active sites, intrinsic charge transport, and excellent stability, making them promising catalyst candidates for GOR. In this study, we introduce a novel class of 2D c ‐MOFs electrocatalysts, M 2 [NiPcS 8 ] (M=Co/Ni/Cu), which are synthesized via coordination of octathiolphthalocyaninato nickel (NiPc(SH) 8 ) with various metal centers. Due to a fast kinetic and high activity of CoS 4 sites for GOR, the electrocatalytic tests demonstrate that Co 2 [NiPcS 8 ] supported on carbon paper displays a low GOR potential of 1.35 V vs. RHE at 10 mA cm −2 , significantly reducing the overall water‐electrolysis‐voltage reduction by 0.27 V from oxygen evolution reaction to GOR, thereby outperforming Ni 2 [NiPcS 8 ] and Cu 2 [NiPcS 8 ]. Additionally, we have determined that the GOR activity of CoX 4 linkage sites varies with different heteroatoms, following an experimentally and theoretically confirmed activity order of CoS 4 >CoO 4 >Co(NH) 4 . The GOR performance of Co 2 [NiPcS 8 ] not only demonstrate superior performance among non‐noble metal complex, but also provides critical insights on designing high‐performance MOF electrocatalysts upon optimizing the electronic environment of active sites.