This review explores the viability of selectively upgrading methanol to formate as a potential route for hydrogen production, with a particular emphasis on replacing the anodic oxygen evolution reaction in electrolyzers. Transition metal-based electrocatalysts demonstrate significant potential for selectively upgrading methanol to formate. The review elucidates the challenges associated with noble metal-based electrocatalysts, including catalyst deactivation resulting from carbon monoxide (CO) intermediate adsorption and restricted methanol-to-formate selectivity. Mechanistic insights are delved into, with a focus on electrochemical methanol oxidation pathways such as O–H and C–H activation. The impact of methanol concentration on selectivity is examined, alongside the interaction between methanol oxidation and oxygen evolution. Catalyst composition is scrutinized, highlighting nickel-based and Ni-free materials, while exploring strategies to reduce cell voltage, advanced characterization techniques (e.g., in-situ Raman, X-ray absorption fine structure spectroscopy), nanotechnology advancements, and cost-effective hydrogen production through methanol-assisted water splitting. Additionally, the review underscores the potential of methanol upgrading for hydrogen production, acknowledges existing challenges, and proposes innovative avenues for future research.

中文翻译：

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选择性电化学甲醇提质与节能制氢研究进展：机理、进展与展望

本综述探讨了选择性将甲醇升级为甲酸盐作为制氢潜在途径的可行性，特别强调取代电解槽中的阳极析氧反应。过渡金属基电催化剂表现出将甲醇选择性升级为甲酸盐的巨大潜力。该综述阐明了与贵金属基电催化剂相关的挑战，包括一氧化碳 (CO) 中间体吸附导致的催化剂失活和有限的甲醇转化为甲酸盐的选择性。深入研究机理，重点关注电化学甲醇氧化途径，例如 O-H 和 C-H 活化。研究了甲醇浓度对选择性的影响，以及甲醇氧化和氧气释放之间的相互作用。仔细审查催化剂成分，重点关注镍基和无镍材料，同时探索降低电池电压的策略、先进的表征技术（例如原位拉曼、X射线吸收精细结构光谱）、纳米技术进步和成本效益通过甲醇辅助水分解生产氢气。此外，该审查强调了甲醇升级用于制氢的潜力，承认现有的挑战，并提出了未来研究的创新途径。