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Despite its potential, the development of efficient MTF systems faces significant challenges, including insufficient mechanistic understanding and suboptimal catalyst design. This review highlights recent advances in MTF electrocatalysis, focusing on three key aspects: 1) reaction mechanisms at molecular level, 2) rational catalyst design strategies, and 3) practical applications in energy systems. Critical factors governing catalytic performance, including active site engineering, intermediate stabilization, and reaction pathway modulation are systematically analyzed. The integration of MTF with hydrogen production and carbon utilization technologies is also discussed as a potential approach for sustainable energy cycles. Finally, current limitations are identified in product selectivity and system efficiency, while proposing future research directions to advance this field. 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