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

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 Ni 2+ /Ni 3+ transition remains challenging. Herein, a core@shell heterostructured NiMoP x @Ni 5 P 4 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 @Ni 5 P 4 favors the adsorption of * CH 3 OH over * OH while the heterostructure contributes to the significantly reduced energy barrier of * OCH 3 → * OCH 2 , 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 @Ni 5 P 4 //NiMoP x @Ni 5 P 4 is employed to enable concurrent MOR/HER electrolysis at 1.81 V to yield formate/H 2 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).