Microcrystallization and lattice contraction of NiFe LDHs for enhancing water electrocatalytic oxidation

Abstract The lattice‐oxygen‐mediated mechanism is considered as a reasonable mechanism for the electrochemical catalytic oxygen evolution reaction (OER) of NiFe layered double hydroxides (LDHs). A NiFe LDH with distinct lattice contraction and microcrystallization was synthesized via a simple one‐step method using sodium gluconate. The lattice contraction is attributed to the interaction of carbon in sodium gluconate and iron in NiFe LDH. The NiFe LDH with optimized microcrystallization and lattice contraction shows a low overpotential of 217 mV at a current density of 10 mA cm⁻² and excellent durability of 20 h at a high current density of 100 mA cm⁻². The results revealed that a contractive metal–oxygen bond could boost the intrinsic activity of active sites and the microcrystallization promotes an increase in the number of active sites in terms of unit area. The chemical environment of oxygen elemental characterization and resistance at different chronopotentiometry times confirm that the lattice oxygen element is indeed involved in the process of OER, supporting the lattice‐oxygen‐mediated mechanism of NiFe LDH. Density functional theory calculations reveal that contractive metal–oxygen bonds induced a reduction of the adsorption energy barrier of intermediate products, thus improving the intrinsic catalytic activity. The special characteristics of microcrystallization and lattice contraction of NiFe LDH provide a strategy to improve both the number and the intrinsic activity of active sites in a versatile manner.