Flexible Active-Site Engineering of Monometallic Co-Layered Double Hydroxides for Achieving High-Performance Bifunctional Electrocatalyst toward Oxygen Evolution and H2O2 Reduction

It is highly desirable but challenging to develop a facile and scalable strategy to synthesize efficient bifunctional electrocatalysts for oxygen evolution and H₂O₂ reduction by engineering the active site of monometallic-layered double hydroxides (LDHs). Herein, we developed a convenient, efficient, and scalable method for the construction of monometallic Co-LDHs with tunable Coⁿ⁺ (n = 2, 3) concentration by a one-pot solvothermal reaction in a short time (e.g., 2 and 4 h) using only cobalt nitrate and hexamine as raw materials. The catalytic performance of Co-LDHs was mainly determined by the Coⁿ⁺ (n = 2, 3) concentration, which could be simply regulated by tuning the solvothermal time. Combining the joint merits of three-dimensional flowerlike architecture (abundant accessible active sites and a fast electron/mass transport), Co-LDHs-4 with abundant Co³⁺ species exhibited an excellent electrocatalytic activity for oxygen evolution reaction in terms of a low overpotential at 10 mA cm^-2 (η₁₀ = 241 mV) and long-term durability for 70 h at 100 mA cm^-2, better than the state-of-the-art IrO₂ and most of the reported analogues. Besides, Co-LDHs-2 enriched in Co²⁺ displayed a superior electrochemical activity for H₂O₂ detection with a broad linear range (0.002-20 mM), a low detection limit (0.002 mM), and a high response sensitivity (272.02 μA mM^-1 cm^-2). Therefore, this work opens a new horizon for the rational development of a highly active electrocatalyst with tunable concentrations of active components.