Metalloporphyrin organic polymers as effective and stable electrocatalysts for the oxygen and hydrogen evolution reactions

• One-pot synthesis of free-base, Fe, and Co porphyrin-based polymer with enhanced catalytic properties. • Fe and Co porphyrin polymers are active in both OER and HER across basic and acidic conditions. • Perfluorinated linkers improve overpotential, catalytic activity, and stability in OER. Metalloporphyrin polymers have attracted much attention due to their efficient electron transfer, their ability to form metal-oxo adducts, and due to their improved mass transport and efficiency. Here, we report cobalt and iron porphyrin-based organic polymers as heterogeneous electrocatalysts for the oxygen and hydrogen evolution reaction (OER and HER) in basic and acidic solutions. The porphyrin organic polymers (Por)OP and F(Por)P were synthesized from a one-step condensation reaction without further cross-coupling followed by direct metalation to form the metalloporphyrin polymers: Co(Por)OP, CoF(Por)P, Fe(Por)OP, and FeF(Por)P. Both metalated porphyrin polymers are active for the oxygen and hydrogen evolution reaction with moderate overpotentials and Tafel slope in the range of 72.8 to 91.7 mV dec ‑1 for OER and 131 to 167 mV dec ‑1 for HER. At the same time, the metal-free (Por)OP and F(Por)OP show poor catalytic activity. These metalloporphyrin organic polymers show a remarkable stability of up to 14 h, whereas the cobalt polymers exhibit a Faradaic efficiency of 99 % for OER.