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 CoN4 (+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 CoN4 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═CoN4 ) to form, the O═CoN4 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 CoN4 . 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.

Bifunctional hydrous RuO2 nanocluster electrocatalyst embedded in carbon matrix for efficient and durable operation of rechargeable zinc-air batteries.

Ruthenium oxide (RuO2) is the best oxygen evolution reaction (OER) electrocatalyst. Herein, we demonstrated that RuO2 can be also efficiently used as an oxygen reduction reaction (ORR) electrocatalyst, thereby serving as a bifunctional material for rechargeable Zn-air batteries. We found two forms of RuO2 (i.e. hydrous and anhydrous, respectively h-RuO2 and ah-RuO2) to show different ORR and OER electrocatalytic characteristics. Thus, h-RuO2 required large ORR overpotentials, although it completed the ORR via a 4e process. In contrast, h-RuO2 triggered the OER at lower overpotentials at the expense of showing very unstable electrocatalytic activity. To capitalize on the advantages of h-RuO2 while improving its drawbacks, we designed a unique structure (RuO2@C) where h-RuO2 nanoparticles were embedded in a carbon matrix. A double hydrophilic block copolymer-templated ruthenium precursor was transformed into RuO2 nanoparticles upon formation of the carbon matrix via annealing. The carbon matrix allowed overcoming the limitations of h-RuO2 by improving its poor conductivity and protecting the catalyst from dissolution during OER. The bifunctional RuO2@C catalyst demonstrated a very low potential gap (ΔE OER-ORR = ca. 1.0 V) at 20 mA cm-2. The Zn||RuO2@C cell showed an excellent stability (i.e. no overpotential was observed after more than 40 h).