The anodic methanol oxidation reaction (MOR) plays a crucial role in coupling with the cathodic hydrogen evolution reaction (HER) and enables the sustainable production of the high‐valued formate. Nickel‐based hydroxide (Ni(OH)2) as MOR electrocatalyst has attracted enormous attention. However, the key factor determining the intrinsic catalytic activity remains unknown, which significantly hinders the further development of Ni(OH)2 electrocatalyst. Here, we found that the dx2‐y2 electronic state within antibonding bands plays a decisive role in the whole MOR process. The onset potential depends on the deprotonation ability (Ni2+ to Ni3+), which was closely related to the band center of dx2‐y2 orbital. The closer of dx2‐y2 orbital to the Fermi level showed the stronger the deprotonation ability. Meanwhile, in the high potential region, the broadening of dx2‐y2 orbital would facilitate the electron transfer from methanol to catalysts (Ni3+ to Ni2+), further enhancing the catalytic properties. Our work for the first time clarifies the intrinsic relationship between dx2‐y2 electronic state and the MOR activities, which adds a new layer of understanding to the methanol electrooxidation research scene.

中文翻译：

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揭示 dx2-y2 电子态在甲醇氧化镍基氢氧化物电催化剂中的关键作用

阳极甲醇氧化反应（MOR）在与阴极析氢反应（HER）的耦合中发挥着至关重要的作用，使得高价值甲酸盐的可持续生产成为可能。镍基氢氧化物（Ni(OH)2）作为MOR电催化剂引起了极大的关注。然而，决定其内在催化活性的关键因素仍然未知，这极大地阻碍了Ni(OH)2电催化剂的进一步发展。在这里，我们发现反键带内的 dx2-y2 电子态在整个 MOR 过程中起着决定性作用。起始电位取决于去质子化能力（Ni2+到Ni3+），这与dx2-y2轨道的能带中心密切相关。 dx2-y2轨道越接近费米能级，表明去质子化能力越强。同时，在高电势区，dx2-y2轨道的展宽将有利于电子从甲醇转移到催化剂（Ni3+到Ni2+），进一步增强催化性能。我们的工作首次阐明了 dx2-y2 电子态与 MOR 活性之间的内在关系，这为甲醇电氧化研究领域增添了新的理解。