Regulating Reversible Oxygen Electrocatalysis by Built‐in Electric Field of Heterojunction Electrocatalyst with Modified d‐Band

Developing bifunctional catalysts for oxygen electrochemical reactions is essential for high-performance electrochemical energy devices. Here, a Mott-Schottky heterojunction composed of porous cobalt-nitrogen-carbon (Co-N-C) polyhedra containing abundant metal-phosphides for reversible oxygen electrocatalysis is reported. As a demonstration, this catalyst shows excellent activity in the oxygen electrocatalysis and thus delivers outstanding performance in rechargeable zinc-air batteries (ZABs). The built-in electric field in the Mott-Schottky heterojunction can promote electron transfer in oxygen electrocatalysis. More importantly, an appropriate d-band center of the heterojunction catalyst also endows oxygen intermediates with a balanced adsorption/desorption capability, thus enhancing oxygen electrocatalysis and consequently improving the performance of ZABs. The work demonstrates an important design principle for preparing efficient multifunctional catalysts in energy conversion technologies.