Deciphering the Space Charge Effect of the CoNiLDH/FeOOH n–n Heterojunction for Efficient Electrocatalytic Oxygen Evolution

Abstract Space charge transfer is an effective strategy to regulate the electron density of narrow bandgap semiconductors for enhancing electrocatalytic activity. Herein, the CoNiLDH/FeOOH n–n heterojunction hollow nanocages structure is constructed. The hollow structure provides abundant catalytic active sites and enhances mass transfer. The space charge region in the n–n heterojunction significantly promotes the adsorption of OH − and electron transfer; and the built‐in electric field accelerates the electron transport, optimizes the electronic structure during the catalytic reaction process, and ensures the stability of surface charged active center sites in the heterojunction. Thus, CoNiLDH/FeOOH delivers an excellent oxygen evolution reaction (OER) overpotential of 250 mV to achieve a current density of 10 mA cm −2 with a small Tafel slope of 60 mV dec −1 , and superior electrocatalytic durability for 210 h at a high current density. Density functional theory calculations further verify that the space charge effect and built‐in electric field in the n–n heterojunction of CoNiLDH/FeOOH can improve the electron transfer and lower the adsorption energy of OH − and the reaction energy barrier of the rate‐determining step. This work provides a new fundamental understanding of the space charge effect of semiconductor heterojunction during the electrocatalytic process for developing more efficient OER electrocatalysts.