Toward Electrocatalytic Methanol Oxidation Reaction: Longstanding Debates and Emerging Catalysts

Abstract The study of direct methanol fuel cells (DMFCs) has lasted around 70 years, since the first investigation in the early 1950s. Though enormous effort has been devoted in this field, it is still far from commercialization. The methanol oxidation reaction (MOR), as a semi‐reaction of DMFCs, is the bottleneck reaction that restricts the overall performance of DMFCs. To date, there has been intense debate on the complex six‐electron reaction, but barely any reviews have systematically discussed this topic. To this end, the controversies and progress regarding the electrocatalytic mechanisms, performance evaluations as well as the design science toward MOR electrocatalysts are summarized. This review also provides a comprehensive introduction on the recent development of emerging MOR electrocatalysts with a focus on the innovation of the alloy, core–shell structure, heterostructure, and single‐atom catalysts. Finally, perspectives on the future outlook toward study of the mechanisms and design of electrocatalysts are provided.