Core@Shell Heterostructured NiMoP_x@Ni₅P₄ Nanorod Arrays Promoting Direct Electro‐Oxidation of Methanol and Hydrogen Evolution under Industry Conditions

Abstract Methanol‐electrooxidation‐reaction (MOR) to value‐added formate is a promising alternative to water oxidation for cost‐efficient hydrogen production. It is generally proposed that the MOR kinetics on Ni‐based catalysts are highly limited by the transition rate of Ni(OH)₂/NiOOH. Yet, how to define the catalyst following the direct pathway without Ni²⁺/Ni³⁺ transition remains challenging. Herein, a core@shell heterostructured NiMoP_x@Ni₅P₄ catalyst is developed to selectively promote the MOR at a large current density (> 500 mA cm⁻²). A series of operando spectroscopic studies reveal negligible formation of NiOOH with 1.0 m methanol in a wide potential range, where MOR is predominant. Theoretical calculations demonstrate that the Ni‐P site of NiMoP_x@Ni₅P₄ favors the adsorption of ^*CH₃OH over ^*OH while the heterostructure contributes to the significantly reduced energy barrier of ^*OCH₃ →^*OCH₂, hence promoting the MOR along a direct pathway without the formation of NiOOH. Moreover, further study suggests that the catalyst also performs well toward cathodic hydrogen evolution reaction (HER). As a result, an electrode pair of NiMoP_x@Ni₅P₄//NiMoP_x@Ni₅P₄ is employed to enable concurrent MOR/HER electrolysis at 1.81 V to yield formate/H₂ with FEs of ca. 90/100% and long‐term (100‐h) sustainability at 500 mA cm⁻² under the industrial conditions (6.0 m KOH, 65 °C).