Rational Design of Ruthenium and Cobalt-Based Composites with Rich Metal–Insulator Interfaces for Efficient and Stable Overall Water Splitting in Acidic Electrolyte

The great promise of hydrogen energy and hydrogen production from water through proton exchange membrane (PEM) or membrane-free electrolysis drives the pursuit of highly active and acid-stable electrocatalysts with dual functionality and reduced cost for overall water splitting in acidic media. Here, we report a new Ru-modified cobalt-based electrocatalyst embedded in a nitrogen-doped carbon (NC) matrix with rationally designed Mott–Schottky heterostructure to realize high activity and stability toward overall water splitting in a strongly acidic environment. Such a composite was facilely prepared by carbonization of cobalt-based MOF, followed by galvanic exchange between cobalt and Ru, and then controlled partial oxidation. The partial oxidation of RuCo implanted inside the NC matrix led to the formation of a class of RuO2/Co3O4–RuCo@NC composites with rich metal–semiconductor interfaces to facilitate the charge-transfer process. As a result, the composite displayed remarkable electrocatalytic activity toward both oxygen/hydrogen evolutions in acidic media. Significantly, they also afforded low overpotentials of 247 and 141 mV for OER and HER, respectively, and a cell voltage of 1.66 V for overall water splitting at 10 mA cm–2. In addition, excellent operation stability in 0.5 M H2SO4 solutions, comparable to those of them working in alkaline conditions, is demonstrated due to the protection of a coated carbon thin film. The presented work opens a new opportunity toward designing bifunctional electrocatalysts for acidic water electrolysis.