Low-Voltage Hydrogen Production via Hydrogen Peroxide Oxidation Facilitated by Oxo Ligand Axially Coordinated to Cobalt in Phthalocyanine Moiety.

A cobalt phthalocyanine having an electron-poor CoN 4 (+δ) in its phthalocyanine moiety was presented as an electrocatalyst for hydrogen peroxide oxidation reaction (HPOR). We suggested that hydrogen peroxide as an electrolysis medium for hydrogen production and therefore as a hydrogen carrier, demonstrating that the electrocatalyst guaranteed high hydrogen production rate by hydrogen peroxide splitting. The electron deficiency of cobalt allows CoN 4 to have the highly HPOR-active monovalent oxidation state and facilitates HPOR at small overpotentials range around the onset potential. The strong interaction between the electron-deficient cobalt and oxygen of peroxide adsorbates in Co─OOH - encourages an axially coordinated cobalt oxo complex (O═CoN 4 ) to form, the O═CoN 4 facilitating the HPOR efficiently at high overpotentials. Low-voltage oxygen evolution reaction guaranteeing low-voltage hydrogen production is successfully demonstrated in the presence of the metal-oxo complex having electron-deficient CoN 4 . Hydrogen production by 391 mA cm -2 at 1 V and 870 mA cm -2 at 1.5 V is obtained. Also, the techno-economic benefit of hydrogen peroxide as a hydrogen carrier is evaluated by comparing hydrogen peroxide with other hydrogen carriers such as ammonia and liquid organic hydrogen carriers.