Passivating Oxygen Evolution Activity of NiFe‐LDH through Heterostructure Engineering to Realize High‐Efficiency Electrocatalytic Formate and Hydrogen Co‐Production

An electrocatalytic methanol oxidation reaction (MOR) is proposed to replace oxygen evolution reaction (OER) in water electrolysis owing to the favorable thermodynamics of MOR than OER. However, there is still a competition between the MOR and the OER when the applied potential is in the conventional OER zone. How to inhibit OER while maintaining efficient MOR is an open and challenging question, and there are few reports focusing on this thus far. Herein, by taking NiFe layered double hydroxide (LDH) as a model catalyst due to its intrinsically high catalytic activity for the OER, the perspective of inhibiting OER is shown and thus promoting MOR through a heterogenous engineering of NiFe-LDH. The engineered heterostructure comprising NiFe-LDH and in situ formed NiFe-hexylaminobenzene (NiFe-HAB) coordination polymer exhibits outstanding electrocatalytic capability for methanol oxidation to formic acid (e.g., the Faradaic efficiencies (FEs) of formate product are close to 100% at various current densities, all of which are much larger than those (53-65%) on unmodified NiFe-LDH). Mechanism studies unlock the modification of NiFe-HAB passivates the OER activity of NiFe-LDH through tailoring the free energies for element reaction steps of the OER and increasing the free energy of the rate-determining step, consequently leading to efficient MOR.