In Situ Growth of 3D NiFe LDH‐POM Micro‐Flowers on Nickel Foam for Overall Water Splitting

Abstract Rational design and preparation of efficient and durable bifunctional electrocatalyst is an eternal yet challenging goal for sustainable energy conversion processes, such as water splitting. Herein, 3D NiFe layered double hydroxide‐polyoxometalate (LDH‐POM; polyoxometalate, i.e., K 8 [SiW 11 O 39 ]·13H 2 O) with micro‐flower morphology is in situ grown on Ni foam via a facile one‐step hydrothermal method, which can be used as a high‐efficient bifunctional catalyst for overall water splitting. The as‐prepared catalyst achieves overall water splitting current density of 10 mA cm −2 at low overpotentials (oxygen evolution reaction (OER): ≈ 200 mV; hydrogen evolution reaction (HER): ≈ 156 mV) in 0.1 m KOH over a period of 20 h operation. Experimental investigation and density functional theory calculation indicate that, compared to pristine NiFe LDH, W 6+ in NiFe LDH‐POM can effectively minimize the adsorption energy barriers of *OH and therefore improve the kinetics of OER. This result may provide a promising strategy to synthesize 3D LDH micro‐flowers by employing POM as a structure–direction agent for catalysis and energy applications.