As a model reaction for the electrooxidation of many small organic molecules, formic acid electrooxidation (FAEO) has aroused wide concern. The promises of direct formic acid fuel cells (DFAFC) in application further strengthen people’s attention to the related research. However, despite decades of study, the FAEO mechanism is still under debate due to the multi-electron and multi-pathway nature of the catalytic process. In this review, the progresses towards understanding the FAEO mechanism along with the developed methodology (electrochemistry, in-situ spectroscopy, and theoretical calculation and simulation) are summarized. We especially focused on the construction of anti-poisoning catalysts system based on understanding of the catalytic mechanism, with anti-poisoning catalyst design being systemically summarized. Finally, we provide a brief summarization for current challenges and future prospects towards FAEO study.

作为许多有机小分子电氧化的模型反应，甲酸电氧化（FAEO）引起了广泛关注。直接甲酸燃料电池（DFAFC）的应用前景进一步加强了人们对相关研究的关注。然而，尽管经过数十年的研究，由于催化过程的多电子和多路径性质，FAEO 机制仍存在争议。在这篇综述中，在理解 FAEO 机制以及开发的方法（电化学、原位光谱和理论计算和模拟）进行了总结。在了解催化机理的基础上，我们特别关注抗中毒催化剂体系的构建，系统总结了抗中毒催化剂的设计。最后，我们简要总结了 FAEO 研究的当前挑战和未来前景。