Ni(II)-Incorporated Ethylene Glycol-Linked Tetraphenyl Porphyrin-Based Covalent Organic Polymer as a Catalyst for Methanol Electrooxidation.

Methanol oxidation reaction (MOR) is a perfect alternative to the conventional oxygen evolution reaction (OER), generally utilized as the anode reaction for hydrogen generation via the electrochemical water splitting method. Moreover, MOR is also relevant to direct methanol fuel cells (DMFCs). These facts motivate the researchers to develop economical and efficient electrocatalysts for MOR. Herein, we have introduced an ethylene glycol-linked tetraphenyl porphyrin-based (EG-POR) covalent organic polymer (COP). The Ni(II)-incorporated EG-POR material Ni-EG-POR displayed excellent OER and MOR activities in an alkaline medium. The materials were thoroughly characterized using 13C solid-state NMR, Fourier transform infrared spectroscopy (FT-IR), Brunauer-Emmett-Teller (BET) surface area analyzer, X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), thermogravimetric analyzer (TGA), and powder X-ray diffraction (PXRD) techniques. These organic-inorganic hybrid materials showed high chemical and thermal stability. Ni-EG-POR requires an overpotential of 400 mV (vs RHE) in OER and 190 mV (vs RHE) in MOR to achieve a current density of 10 mA cm-2. In addition, the catalyst also showed excellent chronoamperometric and chronopotentiometric stability, indicating that the catalyst can provide stable current over a longer period and its potential as a non-noble metal MOR catalyst.