Electrocatalyst Performances in Direct Alcohol Fuel Cells: Defect Engineering Protocols, Electrocatalytic Pathways, Key Parameters for Improvement, and Breakthroughs on the Horizon

In direct alcohol fuel cells (DAFCs), energy conversion co‐occurs at the anode (alcohol oxidation reaction [AOR]) and cathode (oxygen reduction reaction [ORR]). The sluggishness of AOR and ORR needs highly electrocatalytically active and stable electrocatalysts that boost electrokinetics, which is central in electrocatalysts’ architectural design and modulation. This design entails enhanced engineering synthesis protocols, heteroatomic doping, metallic doping/alloying, and deliberate introduction of defective motifs within the electrocatalyst matrix. The electrocatalyst activity and behavior depend on the electrocatalysts’ nature, type, composition, and reaction media, acidic or alkaline. Alkaline media permits cheap nonplatinum group metals. This review elucidates the roles and electrocatalytic pathways on different AOR and ORR electrocatalysts and outlines the aspects distinguishing ORR in alkaline and acidic media. It gives up‐to‐date and ultramodern strategies, protocols, and underlying mechanisms pointing to the efficacy and efficiency of electrocatalysts. The focus centers on heteroatomic, metallic dopants, defects effects correlated to electrocatalytic properties and experimental and theoretical findings. For the advancement in the field, the present study discusses critical parameters for improving the performances of electrocatalysts for DAFCs and breakthroughs on the horizon. Conclusively, knowledge gaps and prospects of these materials for industrial viability and reigning futuristic research directions are presented. Electrochemical performance in direct alcohol fuel cells (DAFCs) is influenced by several factors, including deliberately inducing defects (heteroatomic and metallic dopants, defects, dislocations) on electrocatalysts using different engineering methods, and governs electrocatalytic pathways for the oxygen reduction and alcohol oxidation, and the ultimate improvement of DAFCs reactions is fundamental to the industrialization of fuel cell technology.